JPH0231151B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for flameproofing a fabric, and more particularly to a process for imparting a good feel and flameproofing properties to a polyester synthetic fiber fabric. Traditionally, many suede-like fabrics have been produced by forming napped on the surface of polyester synthetic fiber fabrics and adding urethane resin, etc. Recently, they have been used not only for clothing but also for interior decoration such as curtains. Various suede fabrics are also used. However, when used for interior purposes, it is necessary to have flame retardant properties, but it is difficult to impart flame retardant properties to fabrics that have raised naps and are coated with resin. At present, nothing that has durability against dry cleaning has been obtained. Organic compounds containing phosphorus and halogens are generally used as flame retardants for polyester synthetic fibers, but in order to impart sufficient flame retardancy to raised fabrics, it is necessary to apply a large amount of flame retardant. However, it has the disadvantage of impairing its texture. Furthermore, if a urethane resin or the like is added to improve the texture, there is a risk that the flame retardancy will decrease. The present invention was made in view of the current situation, and is a polyester synthetic fiber that has durable flame retardant properties and good texture by using a special flame retardant and a special urethane resin. The object of the present invention is to provide a method for manufacturing a raised fabric. That is, in the present invention, a fabric made of polyester synthetic fibers is immersed in an aqueous emulsified dispersion of the following compounds (A), (B), and (C) at a temperature of 100°C or higher, and after drying, the surface of the fabric is raised by raising. A method for flameproofing a fabric made of polyester-based synthetic fibers, which comprises forming a nape, then applying the following compound (D), heat-treating, and then washing the fabric bridge. It is. (A) 7- to 12-membered brominated cyclic hydrocarbon. (B) Equation (However, R ₁ and R ₂ are one of -H, -CH ₃ and -CH ₂ Br, and n is an integer of 1 to 6) Bisphenyl sulfone. (C) A phosphoric ester of dibroneopentyl glycol and phosphoric anhydride, or a reaction product of the phosphoric ester and an alkylene oxide. (D) A polyurethane that is a reaction product of an organic isocyanate and a polyol or polyester, and is a copolymer of a phosphorus- and halogen-containing polyol. The present invention will be explained in detail below. The polyester synthetic fiber in the present invention is a fiber obtained by spinning polyethylene terephthalate, polypropylene terephthalate, polyethylene propylene terephthalate, etc., and the fabric refers to woven fabric, knitted fabric, nonwoven fabric, etc. In the present invention, first, a fabric made of polyester fibers is immersed in an aqueous emulsified dispersion of the compounds (A), (B), and (C) and treated at a temperature of 100° C. or higher for a certain period of time. Through this process, flame retardant properties are imparted to the polyester synthetic fiber itself. Compound (A) mainly adheres to the fiber surface and provides good flame retardant properties against surface combustion, and compound (C) ) is mainly exhausted inside the fiber,
Demonstrates high flame resistance against internal combustion. Compound (B)
has the role of binding compounds (A) and (C), and further improves durability against washing and dry cleaning. 7- to 12-membered brominated cyclic hydrocarbon [compound
(A)] is a compound in which bromine is added to heptane, octane, nonane, decane, undecane or dodecane, and preferably the number of added bromine is in the range of 4 to 12. When the number of bromines is less than 4, it is difficult to obtain good flame resistance, and when it exceeds 12, the light fastness becomes extremely poor. Brominated cyclic hydrocarbons are generally obtained by adding bromine to a cyclic hydrocarbon having an unsaturated bond, or by substituting hydrogen and bromine in a cyclic hydrocarbon, and the compounds of the present invention can also be obtained by this method. You can get it. Then the general formula (However, R ₁ and R ₂ are one of -H, -CH ₃ and -CH ₂ Br, and n is an integer of 1 to 6.) The bisphenyl sulfone [compound (B)] represented by It is obtained by adding bromine to sulfone and then reacting it with alkylene oxide in the presence of an alkali catalyst. Specific compounds include the following. In addition, specific examples of phosphoric acid esters of dibromneopentyl glycol and phosphoric anhydride include: (However, m is an integer from 1 to 3.) etc., and can be obtained by reacting dibrome neopentyl glycol and phosphoric anhydride at high temperature. Although these phosphoric acid esters are usually obtained as a mixture, they may be used as a mixture in the present invention. Furthermore, a reaction product of the above-mentioned phosphoric acid ester and alkylene oxide can also be used. Alkylene oxides include ethylene oxide, propylene oxide, epichlorohydrin, etc. Specific examples of reactants include etc. These reactants are also mainly used as a mixture, and may also be used in combination with the above-mentioned phosphoric esters. In the method of the present invention, a polyester synthetic fiber fabric is first immersed in an aqueous emulsified dispersion of these three types of compounds and treated at a temperature of 100°C or higher, preferably 120°C or higher. If the temperature is less than 100°C, the adhesion of the compound to the polyester fibers will be insufficient, making it impossible to obtain good flame resistance. To obtain a mixed emulsified dispersion aqueous liquid of three types of compounds, first disperse or emulsify each compound at an appropriate concentration using a surfactant or an organic solvent, and then mix each dispersion aqueous liquid and emulsified aqueous liquid. Bye. Regarding the amount of the three types of compounds applied to the fabric, it is desirable that the total amount of the three types of compounds is 2% by weight or more based on the weight of the fabric to be treated, and if it is 2% by weight or less, good flame retardant properties can be obtained. is difficult. Further, the mixing ratio of each compound varies depending on the type, form, etc. of the fabric to be treated, but it is sufficient that the weight ratio of the bromine component and the phosphorus component after mixing is in the range of 50:1 to 1:10. The method for treating fabric in the emulsified dispersion aqueous liquid is as follows:
Dyeing may be carried out in the same manner as ordinary immersion dyeing, and it is also possible to carry out dyeing at the same time by adding dyes, dyeing aids, etc. to the treatment bath at the same time. After treating a polyester synthetic fiber fabric in an aqueous mixed emulsion dispersion of three types of compounds, the fabric is dried and then raised to form napped on the surface of the fabric. Raising can be done by using a cloth-type raising machine equipped with a cloth roll, or by bringing the fabric into contact with sandpaper or sand cloth, etc. In the present invention, any method may be used to achieve the desired raising. The napping may be done under appropriate conditions depending on the nap length and nap density of the fabric. After raising the fluff, the fluff is trimmed by shearing or brushing if necessary, and then resin processing is performed. The resin processing of the present invention is made of a special urethane resin that does not impede flame retardancy and gives a good texture, that is, a reaction product of organic isocyanate and polyol or polyester, and is copolymerized with phosphorus and halogen-containing polyol. The obtained polyurethane [compound (D)] is used. Organic isocyanate has the general formula OCN-R-NCO (where R is an organic compound)
A compound having two or more isocyanate groups represented by: tolylene diisocyanate (TDI), naphthylene diisocyanate (NDI),
Examples include diphenylmethane diisocyanate (MDI), and those commonly used in the production of polyurethane may be used. In addition, polyols and polyesters that are normally used in the production of polyurethane can be used, and the general formula for polyols is (However, a, b, c, d are positive integers). Polyester contains adipic acid or phthalic anhydride as an acid component, ethylene glycol as an alcohol component,
Polymerized materials of known substances such as butylene glycol, glycerin, and trimethylolpropane can be used. The degree of polymerization of polyol or polyester may be selected as appropriate depending on the need, but usually,
It is desirable that the molecular weight is 400 to 2000. The polyurethane used in the present invention is obtained by copolymerizing a reaction product of the organic isocyanate and polyol or polyester with a polyol containing phosphorus and a halogen. Specific examples of polyols containing phosphorus and halogen include the following. (However, a, b, c, d, and e are positive integers.) In addition, the above-mentioned phosphoric acid ester of dibrome neopentyl glycol and phosphoric anhydride, and the reaction product of the phosphoric acid ester and alkylene oxide also contain phosphorus and halogen. It may also be copolymerized with urethane as a polyol. The content of phosphorus and halogen in urethane resin varies depending on the type of organic isocyanate, polyol, polyester, and halogen, but the total content of phosphorus and halogen components is 5% relative to urethane resin.
% or more, and it is more effective to contain the halogen component at least 10 times the phosphorus component in order to obtain a polyurethane resin that does not inhibit flame retardancy. The method for applying the polyurethane resin to a raised fabric made of polyester synthetic fibers includes immersing the raised fabric in an aqueous polyurethane liquid and then squeezing it uniformly with a mangle, or commonly used methods such as spraying and coating. Use methods. The amount of polyurethane resin to be applied may be selected optimally depending on the type of raised fabric and the desired texture. After applying the polyurethane resin, the standing fabric is dried and further heat treated at a high temperature to fix the resin. The heat treatment temperature varies depending on the type of polyurethane resin and the amount applied, but it is usually carried out at 150°C or higher. After the heat treatment, the raised fabric is washed to remove the dispersant and emulsifier contained in the flame retardant and the urethane resin solution. If the dispersant or emulsifier remains on the fabric, sufficient flame resistance cannot be imparted.
Cleaning includes surfactants and alkalis if necessary
It may be carried out in warm water of 60 to 100°C. After washing, it is dried, and if necessary, brushing or the like may be performed. In this way, a raised fabric with better appearance and feel can be obtained. The present invention has the above configuration, and according to the present invention, it is possible to obtain a raised fabric that has an excellent feel and appearance and also has flame retardant properties that can withstand washing and dry cleaning. The raised fabric obtained by the method of the present invention can be used for high-end interiors such as drape curtains and wall coverings. Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto. Example 1 Polyethylene terephthalate fiber 75d/warp
A 5-ply satin fabric using 36f false twisted yarn and polyethylene terephthalate fiber 75d/72f for the weft was prepared, and after relaxing and scouring, it was dyed using a jet dyeing machine in a bath with the following formulation 1 at 130℃ for 30 minutes. The process was carried out for 1 minute. Formulation 1 (a) Aqueous dispersion containing 50% cyclobromooctane
...15%owf (b) Chemical formula Dispersed aqueous liquid containing 50% of the compound......5% owf (c) A compound obtained by reacting 3 moles of dibrome neopentyl glycol with 1 mole of phosphoric anhydride.
Emulsified aqueous liquid containing 50%...10% owf (d) Forom Yellow SE-CTL (disperse dye manufactured by Sandoz Co., Ltd.)...2% owf (e) Nitsuka Sunsalt RZ-8F (manufactured by NICCA Chemical Co., Ltd.) Dispersant)...0.5g/ (f) Glacial acetic acid...0.2cc/ After treatment, the sample was washed with hot water at 80°C for 20 minutes, and then dried. Hydraulic cloth raising machine after drying (number of cloth rolls: 24)
The napping was carried out 10 times at a processing speed of 20 m/min. Next, after brushing the surface of the fabric, it was immersed in the liquid of the following formulation 2, and squeezed uniformly at a squeezing rate of 80%.
After drying, heat treatment was performed at 170°C for 1 minute. Formulation 2 (a) TDI-80 (Isocyanate manufactured by Nippon Soda Co., Ltd.)
60 copies, Hiflex D-2000 (Daiichi Kogyo Seiyaku)
Polyol Co., Ltd.) 20 parts and formula Polyurethane copolymerized with 80 parts of the polyol shown by ...50 parts (b) Sodium hydrogen carbonate ...5 parts (c) Water ...945 parts Finally, 0.5 parts of Sunmoor FL (manufactured by Nicca Chemical Co., Ltd.)
The sample was washed at 80° C. for 20 minutes in a bath containing g/g/ml and dried. The resulting napped fabric has a good texture,
The flame retardant properties were also excellent as shown in Table 1. The flame retardancy was measured in accordance with the method specified in Ministry of Home Affairs Ordinance No. 13, and washing and dry cleaning were carried out in accordance with the method specified in Ministry of Home Affairs Ordinance Fire and Disaster Management Agency Notification No. 11.

[Table] Example 2 A knitted fabric with a Motsuku Milano rib structure using polyethylene terephthalate fibers 75d/36f was prepared, and after scouring, it was dyed in a bath of the following formulation 3 using a jet dyeing machine at 130%
℃ for 30 minutes. Formulation 3 (a) Aqueous dispersion containing 30% cyclobromedecane and 20% tetrabromooctane...10% owf (b) Chemical formula Dispersed aqueous liquid containing 50% of the compound......5% owf (c) After reacting 3 moles of dibroneopentyl glycol with 2 moles of phosphoric anhydride, the resulting compound was reacted with 4 moles of epichlorohydrin. Emulsified aqueous liquid containing 15% owf (d) Foron Blue SE-CTL (Sandoz Co., Ltd. disperse dye) 2% owf (e) Nitsuka Sunsalt RZ-8F 0.5g/ (f) Ice Acetic acid 0.2cc/After treatment, wash with hot water at 80℃ for 20 minutes, and after drying.
The cloth was brought into contact with five rolls wrapped with sandpaper having a grain size of No. 120 and rotated at a speed of 1200 rpm to form naps on the surface of the cloth. Next, it was immersed in a liquid of the following formulation 4, squeezed uniformly at a squeezing rate of 100%, and then heat-treated at 170° C. for 1 minute after drying. Prescription 4 (a) TDI-80 50 parts, Hyflex D-2000 10
part and chemical formula Polyurethane copolymerized with 90 parts of polyol (b)...50 parts (b) Water...950 parts Finally, it was washed in hot water at 80°C for 20 minutes using a jet dyeing machine, and then dried. The obtained knitted fabric had a good surface texture and excellent flame retardancy as shown in Table 2. The flame retardant properties were measured in exactly the same manner as in Example 1.

【table】

Claims (1)

[Claims] 1. A fabric made of polyester synthetic fibers is placed in an emulsified dispersion of the following compounds (A), (B) and (C) at 100°C.
The fabric is dipped at a temperature above, dried and raised to form a nap on the surface of the fabric, and then the following compound is added to the fabric.
1. A method for flameproofing a fabric made of polyester synthetic fibers, which comprises applying (D), heat-treating the fabric, and then washing the fabric. (A) 7- to 12-membered brominated cyclic hydrocarbon. (B) Equation (However, R ₁ and R ₂ are one of -H, -CH ₃ and -CH ₂ Br, and n is an integer of 1 to 6) Bisphenyl sulfone. (C) A phosphoric ester of dibroneopentyl glycol and phosphoric anhydride, or a reaction product of the phosphoric ester and an alkylene oxide. (D) A polyurethane that is a reaction product of an organic isocyanate and a polyol or polyester, and is a copolymer of a phosphorus- and halogen-containing polyol.