JP5297805B2 - Flame retardant treatment for polyester and flame retardant treatment method using the same - Google Patents

Abstract

Disclosed is a flameproofing composition for polyesters, which provides flame retardancy by firmly fixing a flame retardant onto the surface of an undyed or dyed polyester. This flameproofing composition for polyesters is composed of an aqueous solution containing a phosphorus flame retardant, an emulsifying agent and a fixing agent. This novel flameproofing agent containing a phosphorus flame retardant enables flameproofing of polyester products such as fibers, fabrics, nonwoven fabrics and films of polyester.

Description

  The present invention relates to a flame retardant capable of flame-retarding undyed and dyed products such as polyester fibers, woven fabrics, knitted fabrics, nonwoven fabrics and films, and a flame retardant treatment method using the same. .

  Since halogen-containing flame retardants generate dioxins upon combustion, phosphorus-containing flame retardants and other non-halogen flame retardants have been developed for flame retardants of polymer materials such as resins, films and fibers. .

In order to make a polymer flame retardant, for example, a non-halogen flame retardant, a flame retardant component such as a flame retardant polymer is contained in a resin, and this is molded to form a fiber, a woven fabric, a film, a molded product, or the like. In the woven fabric, flame retardant fibers are blended and the like.
There is a technique of applying a flame retardant to the surface of non-flame retardant fibers and fabrics that do not contain a flame retardant component. For example, as a technique for applying a non-halogen flame retardant to polyester fibers, woven fabrics, etc. and imparting flame retardancy, for example, Patent Document 1 discloses a polyester fiber fabric mixed with a phosphinic acid derivative and a phosphorus flame retardant. Among them, a flame retarding method has been proposed in which padding is performed at a drawing ratio of 60%, followed by drying at 100 ° C. and heat treatment at 170 ° C.

  In addition, for example, in Patent Document 2, after a polyester fiber is immersed in a dispersion in which a phosphorus-based flame retardant is dispersed in water and squeezed to a predetermined adhesion amount, the temperature is in a range of 110 to 130 ° C. A method of drying and further a dry heat treatment has been proposed.

However, in the padding method, if the amount of flame retardant attached is small, sufficient flame retardancy cannot be obtained.On the other hand, if the amount of flame retardant attached is large, sufficient flame retardancy is exhibited, but oil-based flame retardant There have been problems such as stickiness on the surface of fibers and fabrics.
Furthermore, in Patent Document 3, a batch treatment is performed at 50 to 140 ° C. in a treatment bath containing a flame retardant containing a phosphine derivative and an inorganic acid salt without reducing the texture of the polyester fiber, followed by a heat drying treatment. Although this method is also a padding treatment in principle, it is a method of attaching a flame retardant to the surface of the polyester fiber, so the amount of flame retardant attached There was a problem with the controls.

  In addition, in the flame retardant processing method using pre-dyed yarn, when the flame retardant is exhausted in the treatment bath, it is necessary to raise the treatment temperature to the temperature at the time of dyeing. ), And the padding method has problems such as discoloration due to adhesion of the flame retardant. As a method for solving this, Patent Document 4 proposes a method of flame-retardant processing at the same time as dyeing. However, since the processing conditions are simultaneous exhaustion of dye, the processing temperature is 120 to 120. There was a problem that it must be carried out in a narrow temperature range of 130 ° C. and under pressure.

  In addition, flame retardancy of polyester film is mostly done by molding a resin raw material containing a flame retardant into a flame retardant film. However, flame retardancy is imparted by coating the surface of the polyester film with a flame retardant. For example, Patent Document 5 proposes a technique for forming a flame retardant layer by coating and drying a tetraethoxysilane hydrolyzed solution.

However, there is no technique for imparting flame retardancy by fixing a phosphorus flame retardant on the surface of the polyester film.
Furthermore, there is no technology to make polyester films flame retardant at the same time.
In this way, there is no excellent technique for imparting flame retardancy to products such as polyester fibers, woven fabrics, non-woven fabrics, films, etc., regardless of the presence or absence of dyeing, by directly attaching a flame retardant to their surface. Therefore, the development of a technology for easily making flame-retardant polyester products has been strongly desired.
JP 2002-294554 A JP 2004-332187 A JP 2003-293268 A JP 2003-27368 A JP 2003-33986 A

  Under the circumstances as described above, the inventors of this application developed a novel flame retardant treatment and a flame retardant treatment method for directly fixing the flame retardant on the polyester surface from an academic and technical viewpoint. We studied diligently. As a result, the following findings were obtained.

  The inventor of the present application selects a phosphorus-based flame retardant as the non-halogen flame retardant, and develops a flame retardant technology for the polyester surface in an aqueous system (in an aqueous solution) that has the best adaptability. The flame retardant is fixed on the polyester surface in an aqueous solution of the flame retardant, or the flame retardant is adhered to the polyester surface by dipping (padding), and then fixed by heating and drying. Then, an excess flame retardant adhering to the polyester surface is removed. Development of flame retardant polyester products that do not feel sticky is important in solving problems, as this is a simple and energy-saving technology that involves washing and removing by soaping.

  In order to solve this problem, it was considered that the development of a novel fixing agent capable of fixing the flame retardant to the polyester surface more strongly is an important key. If a flame retardant fixing method that does not exist in the prior art can be developed, it is possible to develop a mild condition of 80 ° C. to 100 ° C. under normal pressure as well as a temperature range of more than 100 ° C. to 140 ° C. under pressure. It is expected that the polyester can be made flame-retardant even under conditions or by heat drying after padding at room temperature.

  From such a background, the present invention aims to provide a technology for making a polyester product flame-retardant by post-processing using a phosphorus-based flame retardant, regardless of whether it is dyed or undyed in a flame retardant treatment solution. .

  The invention of this application is to solve the above-mentioned problems. First, the flame retarding of the polyester for fixing the flame retardant to the surface of the undyed or dyed surface of the polyester to exhibit flame retardancy There is provided a flame retardant composition, which is an aqueous solution containing a phosphorus-based flame retardant, an emulsifier and a fixing agent.

  Second, a polyester flame retardant composition for fixing a flame retardant on the surface thereof simultaneously with dyeing of an undyed polyester product to develop flame retardancy, comprising a phosphorus-based flame retardant, an emulsifier and an adhesion Provided is a flame retardant composition which is an aqueous solution containing a dye together with an agent.

  In any one of the above flame retardant compositions, thirdly, the fixing agent includes a flame retardant containing polyphenols, and fourth, the polyphenols are tannic acid. The flame retardant characterized by the above is provided. Fifth, the polyester is a fiber, woven fabric, knitted fabric, non-woven fabric, or film.

  Sixth, there is provided a method for flame retardant treatment of a polyester for fixing a flame retardant on the surface to exhibit flame retardancy, wherein the polyester is not yet dissolved in an aqueous solution containing a phosphorus flame retardant, an emulsifier and a sticking agent. Provided is a flame retardant treatment method characterized by immersing a dyed product and a dyed product in a temperature range of 80 ° C. or higher and 140 ° C. or lower.

  Seventh, in an aqueous solution containing a phosphorus-based flame retardant and an emulsifier, an undyed or dyed polyester is immersed in a temperature range of 80 ° C. or higher and 140 ° C. or lower, and then in an aqueous solution containing a fixing agent. And the flame-retarding method characterized by immersing in the said temperature range is provided.

  Eighth, an undyed polyester product is immersed in an aqueous solution containing a dye together with a phosphorus-based flame retardant, an emulsifier and a fixing agent at a temperature range of 80 ° C. to 140 ° C. Provided is a flame retardant treatment method characterized by carrying out the conversion.

Ninth, in an aqueous solution containing a dye together with a phosphorus-based flame retardant and an emulsifier, an undyed polyester is immersed in a temperature range of 80 ° C. or higher and 140 ° C. or lower, and then in an aqueous solution containing a fixing agent. Provided is a flame retardant treatment method characterized in that it is immersed in the same temperature range and flame retardant is performed simultaneously with dyeing.
Tenth is a method for flame retardant treatment of polyester, wherein the polyester is dipped (padded) in an aqueous solution containing a phosphorus-based flame retardant, an emulsifier and a fixing agent at room temperature, and then the excess aqueous solution is dehydrated. Then, there is provided a flame retardant treatment method characterized by heat-drying treatment.

  And about the above 6th to 10th flame-retardant processing methods, 11th, the fixing agent contains polyphenol, 12th, polyphenols are tannic acid, 13th, The polyester is characterized by being a fiber, woven fabric, knitted fabric, non-woven fabric, or film.

  The fourteenth is characterized in that after the above flame retardant fixing treatment, the excessively attached flame retardant is washed away by a soaping treatment.

  According to the present invention as described above, there is provided a flame retardant treatment comprising at least a phosphorus-based flame retardant, an emulsifier and a fixing agent for achieving flame retardancy of products such as polyester fibers, woven fabrics, nonwoven fabrics, and films. Further, it is difficult to fix the flame retardant to the polyester surface in a wide temperature range of 80 ° C. or higher and 140 ° C. or lower when the textile is immersed in an aqueous solution of the flame retardant treatment. In addition to providing a flame retardant treatment method, it is possible to provide a flame retardant treatment method in which a flame retardant is fixed to the polyester surface by performing a padding treatment at room temperature and then a heat drying treatment. According to the flame retardant treatment and the flame retardant treatment method of the present invention containing, for example, polyphenols in the flame retardant fixing agent, the flame retardant can be easily made flame retardant at a temperature of 100 ° C. or lower under normal pressure. In addition, it is possible to make it flame-retardant by heat-drying after padding at room temperature, which contributes to energy saving. In addition, materials such as polyester fibers, woven fabrics, nonwoven fabrics, and films may be undyed or dyed. Therefore, according to the technology of the present invention, various types of polyester products can be made flame retardant without limiting the types of flame retardant treatment devices, and the polyester surface properties after treatment are excellent. Can be provided. Further, according to the present invention, it is possible to make the polyester flame-retardant simultaneously with the dyeing. The excellent effect of flame retardancy of such polyester products according to the present invention is completely unexpected from the prior art.

  The invention of this application has the features as described above, and the embodiments thereof will be described in detail below.

  In the invention of this application, the polyester is not particularly limited as long as it has an ester bond in the polymer main chain, but polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polybutylene. Suitable are semi-aromatic polyesters such as naphthalate, aliphatic polyesters such as polyhydroxybutyric acid, polylactic acid, polycaprolactone, and polybutylene succinate, copolymers and blends thereof, and polymer alloys using these as a matrix. Illustrated as a subject.

  Examples of such polyesters include undyed products and dyed products, and the form is not particularly limited, but products such as fibers, woven fabrics, non-woven fabrics, and films are suitable examples. Polyester fabrics include monofilament fabrics such as polyester organdy, cationic dyeable polyester fabrics, and polyester tropical fabrics, screens for precision printing substrates, monofilaments for papermaking processes, projection screens, speaker cones, automotive seat belts and airbags. Examples of suitable objects include an aero shelter for large temporary tents, a curing sheet for civil engineering construction, a safety net, and a tent. Examples of suitable multifilaments include sewing threads and ropes. Laser printer brushes are also exemplified as suitable objects. As the polyester film, regardless of whether it is amorphous or crystalline, the form is exemplified by a non-oriented film, a uniaxially stretched film and a biaxially stretched film as suitable objects. A film, an electromagnetic wave shielding material, and an adhesive tape are mentioned.

  In addition, the phosphorus flame retardant is not particularly limited as long as it is a phosphate ester compound that does not contain a halogen atom and has an aromatic group or an aliphatic group. However, tricresyl phosphate (also known as tricresyl phosphate, phosphoric acid) Tritolyl), triphenyl phosphate (also known as triphenyl phosphate), cresyl diphenyl phosphate, resorcinol bisdiphenyl phosphate, xylylene diphenyl phosphate, tributyl phosphate, triethyl phosphate, tris 2-ethylhexyl phosphate (also known as trioctyl phosphate), octyl Diphenyl phosphate, trisisopropylphenyl phosphate, trisbutoxyethyl phosphate, phosphaphenanthrene oxide derivatives, methyl group, t-butyl group, hydroxy acid Mixtures of bets biphenyl phosphate substitutions (cyclic phosphate compound) and its derivatives and the phosphoric acid esters of, can be mentioned as a preferable target the like.

  Next, examples of the emulsifier for emulsifying the phosphorus-based flame retardant into an aqueous system include surfactants having a phosphate ester group, among which polyoxyethylene alkyl ether phosphates, polyoxyethylene phenyl ether phosphates And mixtures thereof are exemplified as suitable subjects. Furthermore, anionic surfactants such as sulfonates and sulfates are exemplified, among which alkylbenzenesulfonates, alkylnaphthalenesulfonates, formalin polycondensates of naphthalenesulfonate, formalin polycondensates of melaminesulfonate, Dialkyl sulfosuccinic acid ester salts, alkyl sulfoacetic acid salts, α-olefin sulfonic acid salts, N-acyl-N-methyl taurine salts, dimethyl terephthalate sulfonic acid salts and the like, and higher alcohol sulfuric acid ester salts, secondary higher alcohol sulfuric acid Ester salts, polyoxyethylene alkyl sulfates, secondary higher alcohol ethoxy sulfates, sulfates such as polyoxyethylene alkyl phenyl ether sulfates, and Emissions salt, mixture of sulfuric acid ester salts can be mentioned as a preferable target.

  And as a sticking agent, the polyphenols which have a phenolic hydroxyl group and an aromatic group, especially natural tannic acid and synthetic tannic acid are illustrated as a suitable object. These tannic acids may be used alone or as a mixture. Furthermore, an aqueous solution extracted from a natural product such as a plant containing tannic acid may be used as the fixing agent.

  Furthermore, as other components, in the aqueous solution of the fixing agent, salts such as ammonium phosphate and ammonium acetate, aluminum salts such as potassium aluminum sulfate (alum), silicates such as sodium metasilicate, and alkaline earth such as calcium chloride. It is more preferable that at least one selected from the group consisting of metal salts, urea, formic acid, acetic acid, organic acids such as sodium p-toluenesulfonate, melamine resins, and epoxy resins.

  Furthermore, as the soaping agent, a conventional soaping agent used in a dyeing process or a flame-retardant processing process of polyester fiber is exemplified as a suitable target.

  Next, the method for flame-retarding polyester using at least the flame retardant comprising the phosphorus-based flame retardant, the emulsifier and the fixing agent will be described in detail.

  The flame retardant is preferably used as a mixed aqueous solution of the above components.

  The concentration of the phosphorus flame retardant in the flame retardant aqueous solution is exemplified to be in the range of 0.5 to 20% by weight, more preferably in the range of 1 to 15% by weight with respect to water. .

  Further, the concentration of the emulsifier in the flame retardant aqueous solution is exemplified to be in the range of 0.1 to 10% by weight, more preferably in the range of 0.5 to 7% by weight with respect to water. The

  The concentration of the polyphenols in the flame retardant aqueous solution is, for example, 0.3 to 10% by weight, more preferably 0.5 to 5% by weight with respect to water.

  Further, the concentration of the soaping agent is exemplified to be in the range of 0.2 to 5% by weight with respect to water, as in the method usually used after dyeing polyester fiber or flame-retardant processing.

  In the flame retardant aqueous solution containing each component in the above-mentioned concentration range, in a state in which products such as polyester fiber, woven fabric, nonwoven fabric, film, etc. are immersed, a temperature range of 80 ° C. or higher and 140 ° C. or lower, more preferably Treatment at a temperature range of 85 ° C. to 130 ° C. for a reaction time in the range of 10 minutes to 90 minutes, more preferably 30 minutes to 60 minutes, and then drying by drying the aqueous solution of the flame retardant. Subsequently, the flame retardant and the like that are excessively adhered (non-adhered) to the polyester surface can be removed by washing in the soaping solution in the temperature range of 70 ° C. to 90 ° C. for 10 minutes to 30 minutes. The preferred embodiment of the flame retardant treatment method for polyester fiber, woven fabric, non-woven fabric, film and the like.

  That is, the flame retardant treatment can be performed in a temperature range of more than 100 ° C. and 140 ° C. or less under pressure, but can be performed in a temperature range of 80 ° C. or more and 100 ° C. or less under normal pressure. It is a technology with a wide range of application that can achieve safety and energy saving.

  In addition, in the case of performing dyeing and flame-retarding of undyed polyester fiber, woven fabric, nonwoven fabric, film, etc. at the same time using a flame retardant aqueous solution containing a dye, in the flame retardant aqueous solution containing a dye The undyed polyester is treated at the same time as dyeing in a temperature range of 80 ° C. to 140 ° C., more preferably in a temperature range of 85 ° C. to 130 ° C. for 20 minutes to 60 minutes, and then flame retardant. The dehydrating agent aqueous solution was only dehydrated and not dried by heating. Subsequently, the solution was excessively adhered to the polyester surface by treatment in the soaping solution at a temperature range of 70 ° C. to 90 ° C. for 10 minutes to 30 minutes ( Washing and removing the unfixed dye and the flame retardant is a preferred embodiment of a treatment method for simultaneously dyeing and flame-retarding polyester fibers, woven fabrics, nonwoven fabrics, films and the like.

  That is, the temperature range in which the dyeing and the flame retardant treatment are performed simultaneously is not only a temperature range exceeding 100 ° C. and 140 ° C. or less under pressure, but also a temperature range from 80 ° C. to 100 ° C. under normal pressure. In any temperature range, undyed polyester products can be made flame retardant at the same time as dyeing, so there is no need to perform a flame retardant treatment separately, and this is a technology that can greatly improve productivity and energy saving.

  Furthermore, after the polyester product is immersed (padding) in an aqueous solution containing a phosphorus-based flame retardant, an emulsifier and a fixing agent at room temperature, the excess aqueous solution is dehydrated, and the temperature is in the range of 80 ° C. to 190 ° C. This is a technology that can further diversify the processing equipment, reduce productivity, and save energy because the flame retardant is fixed on the surface of the polyester product by heating and drying for 1 minute to 1 minute to make it flame retardant.

  Examples will be shown below and described in more detail. Of course, the invention is not limited by the following examples, and it goes without saying that there are various modes for details.

(1) Undyed fabric and film In the examples and comparative examples, 150 denier warp yarn (density 76 / inch) and 150 as a raw sample (undyed fabric) for flame-retardant treatment were used for a polyester fabric sample. A polyester tropical fabric (hereinafter abbreviated as “tropical fabric”) having a basis weight of 120 g / m ^{2 made} of denier weft (density 68 / inch) and polyester organdy 2040 (a monofilament fabric used for lace curtain fabric, etc.) In the following, abbreviated as POG cloth) and, as a polyester film, Lumirror Polyfilm 25T70A (hereinafter abbreviated as film sample) manufactured by Toray Industries, Inc. was used.
(2) Dyed fabrics The dyed polyester fabrics used for the flame retardant treatment are the following two types. The dyed cloth 1 is a mixture of quinoline and azo disperse dyes manufactured by Dystar Japan Co., Ltd., Dianix Yellow AC-E New (hereinafter abbreviated as D yellow), anthraquinone series, and a stainless steel pot usually used for dyeing tests. 150 mL of a dyeing bath and a tropical cloth containing 0.1% by weight of each of the disperse dye Dianix Red AC-E 01 (hereinafter abbreviated as D red) and the anthraquinone-based disperse dye Dianix Blue AC-E (hereinafter abbreviated as D blue) 10 g was added and dyed at 130 ° C. for 40 minutes, and then washed with a post-treatment aqueous solution containing 0.2 mL of acetic acid and 10 mL of surfactant RM-340E (hereinafter abbreviated as 340E) manufactured by Nikka Chemical Co., Ltd., washed with water, It is a tropical dyed cloth obtained by drying.

The dyed cloth 2 is a POG dyed cloth dyed under the same conditions as the dyed cloth 1 except that a POG cloth is used and the concentration of each dye is 0.3% by weight.
(3) Flame Retardant Composition Component As a flame retardant, a phosphoric flame retardant aqueous solution Nikkafinon HF-77 (hereinafter abbreviated as HF-77) manufactured by Nikka Chemical Co., Ltd. and phosphoric acid manufactured by Wako Pure Chemical Industries, Ltd. Tritolyl (hereinafter abbreviated as TTP) was used.

  As an emulsifier, Nikka Chemical Co., Ltd. anionic surfactant aqueous solution Nikkasan Salt 7000 (hereinafter abbreviated as N7000), Asahi Denka Co., Ltd. polyoxyethylene alkylphenyl ether sulfate 60N (hereinafter abbreviated as 60N) and A dispersant (emulsifier) 340E (hereinafter abbreviated as 340E) manufactured by Nikka Chemical Co., Ltd. was used.

  As a sticking agent, Wako Pure Chemical Industries, Ltd. tannic acid (CAS number 1401-55-4, hereinafter abbreviated as tannic acid) and Fuji Chemical Industry Co., Ltd. fix agent FK-707 (hereinafter abbreviated as FK-707). ) Was used.

Other components added to the flame retardant aqueous solution include acetic acid, ammonium acetate, ammonium sulfate, sodium p-toluenesulfonate (hereinafter abbreviated as TS), and Sumitomo Chemical Co., Ltd. SMITEX Accelerator ACX (hereinafter referred to as ACX). (Abbreviation) was used.
(4) Treatment method The stainless steel pot is filled with 150 mL of a flame retardant aqueous solution comprising a predetermined concentration of a flame retardant, an emulsifier (surfactant), a fixing agent and other components and a polyester original sample or 10 g of the dyed sample. The flame retardant treatment was performed at a predetermined temperature for a predetermined time.

  The simultaneous dyeing and flame retardant treatment of the undyed polyester sample was performed in the same manner as the flame retardant treatment except that the dye having a predetermined concentration was added.

  In the flame retardant treatment by padding, the polyester sample was immersed in the same flame retardant aqueous solution as described above at room temperature, and then the sample was taken out, dehydrated, and then heat dried to perform the flame retardant treatment.

As a soaping agent for cleaning and removing unfixed flame retardant after flame retardant treatment, Rakkor ISF-2 (hereinafter referred to as ISF), which is a surfactant mixed solution (including butyl cellosolve, methanol, etc.) manufactured by Meisei Chemical Industry Co., Ltd. -2) and sodium tripolyphosphate mixed solution. As a soaping agent after the flame retardant treatment by padding, a flameproofing post-treatment agent FZ manufactured by Nikka Chemical Co., Ltd. was used.
(5) Evaluation method Moreover, the flame retardance evaluation of the flame-retardant-treated sample was performed by the following method.

For flame retardancy evaluation of polyester fabrics, textile products flammability test method JIS L1091 D method according (coil method), using a Suga combustion tester FL-45M (45 ⁰ flammability tester), flame retardant treatment The number of flame contact of the sample was measured three times. In addition, the case where the frequency | count of flame contact was 3 or more was evaluated as flame retardance.

  Furthermore, the fire-treated sample was subjected to water washing treatment 5 times in accordance with the Fire and Disaster Management Agency Notification No. 1 of February 21, 1986, and then the combustion test (L-5) was repeated 3 times. went. Also in this case, the flame contact number of 3 or more was evaluated as flame retardant.

Next, according to A-1 method (45 ^o micro burner method) of flammability test method JIS L1091, the carbonized area of the flame retardant treated sample after water washing treatment was measured five times, and the carbonized area No. 30 cm ² or less (Category 3) was evaluated as flame retardant.

About change of dyeing property with flame retardant treatment of dyed cloth and simultaneous dyeing, flame retardant treatment, using SICOMUC20 spectrophotometer (computer color matching system for textiles and dyeing) manufactured by Sumika Chemical Analysis Co., Ltd. Measure the dye concentration ratio (% display) before and after flame retardant dyed fabric, or the dye concentration ratio (% display) when dyeing alone and simultaneous dyeing and flame retardant treatment, The case where the concentration ratio was within 100 ± 5% was evaluated as having no influence of the flame retardant treatment on the dyeability. Further, as a control, visual comparative evaluation was also performed.
(6) Examples of flame retardant treatment As Examples 1 to 13, the flame retardant treatment conditions of various polyester samples and the flame retardant test results of the treated samples are shown below.
<Examples 1-4>
Commercially available HF-77 as a flame retardant, N7000 as an emulsifier, tannic acid or FK-707 as a sticking agent, and unstained tropical cloth (original sample) as a flame retardant described in Examples 1 to 4 in Table 1 With the bath composition, a flame retardant treatment was performed according to the above operation, and then soaping was performed to obtain a flame retardant sample. All the samples after the flame retardant treatment had a flame contact number of 4 or more, and all the L-5 flame contact times were 3 or more. Furthermore, the classification by the carbonized area method of the samples after the L-5 treatment was all 3, and from these results, it was found that all the flame retardant treated tropical fabrics were excellent in flame retardancy.

It was found that the flame retardant treatment of Example 1 was performed at 130 ° C. and high flame retardancy was obtained. On the other hand, the flame retardant treatment of Examples 2 to 4 was performed at 95 ° C. under normal pressure. Conventionally, tannin was also obtained under the treatment conditions (95 ° C. under normal pressure) where it was difficult to flame retardant polyester fabrics. The fact that excellent flame retardancy can be imparted by using an acid as a fixing agent for the flame retardant indicates that the technique of the present invention is excellent.
<Examples 5-7>
Using TTP as the flame retardant, 60N as the emulsifier, tannic acid as the sticking agent, and undyed POG cloth (original sample) with the flame retardant bath composition described in Examples 5 to 7 in Table 1, according to the above operation Flame retardant treatment was performed, and then soaping was performed to obtain a flame retardant sample. All the samples after the flame retardant treatment had a flame contact number of 3 or more, and all the flame contact times of L-5 were 3 or more. Furthermore, the classification by the carbonized area method of the samples after the L-5 treatment was all 3. From these results, it was found that all the flame-retardant treated POG cloths have high flame retardancy.

From Example 7, even if the phosphorus flame retardant was replaced with TTP and the undyed cloth was replaced with POG cloth, the tannin was treated under the treatment conditions (95 ° C. under normal pressure) that were conventionally difficult to make the polyester fabric flame retardant. The fact that high flame retardancy can be imparted by using acid as a flame retardant fixing agent proves that tannic acid has made a very important contribution to flame retardant fixation. This shows that the technique of the present invention is excellent.
<Example 8>
Except that the undyed cloth was changed to POG cloth, flame retardancy treatment was performed under the same conditions as in Example 4, and then soaping was performed to obtain a flame retarded sample. The flame contact number of the sample after the flame retardant treatment was 3 or more, and the flame contact number of L-5 was all 3 or more. Furthermore, the classification by the carbonized area method of the sample after the L-5 treatment is 3, and from these results, it was found that the flame-retardant treated POG cloth has high flame retardancy.

From the results of Example 7 and Example 8, the technique of the present invention is at least a phosphorus-based flame retardant under mild processing conditions (95 ° C. under normal pressure) even for POG cloth, which was difficult with the prior art. The effectiveness of a flame retardant comprising an aqueous solution of a mixture containing an emulsifier and tannic acid (sticking agent) was proved.
<Example 9>
In order to investigate the fixing agent performance of tannic acid, a phosphoric flame retardant (HF-77), an emulsifier (340E) and other components (acetic acid) are included, but in a flame retardant bath containing no fixing agent at 130 ° C. After treating the undyed cloth (POG cloth) for 40 minutes, the POG cloth is taken out of the treatment bath and treated in an aqueous solution containing only the fixing agent (tannic acid) at 95 ° C. for 40 minutes. The number of times was 3 or more, and the number of times of flame contact of L-5 was 3 or more. Furthermore, the classification by the carbonized area method of the sample after the L-5 treatment was 3.

From the results of Examples 1-8 and Example 9, tannic acid may be included in the treatment bath together with the flame retardant, and after treatment in the flame retardant treatment bath, then tannic acid It can also be said that the flame retardant can be fixed to the fiber. In addition, when the soaping process was performed without performing the second stage fixing agent process, the flame retardancy of the obtained sample was not sufficient.
<Example 10>
It is preferable from a practical aspect that the flame retardant treatment of the polyester fabric can also make the dyed fabric flame retardant. A flame retardant treatment was performed under the same conditions as in Example 4 except that the sample was a tropical dyed cloth 1. As a result, it was found that the number of flame contact after the flame retardant treatment and after the L-5 treatment was 3 or more, indicating sufficient flame retardancy. The classification by the carbonized area method was 3. That is, the technology of the present invention makes it possible to impart sufficient flame retardancy to the tropical dyed fabric 1 even when the flame retardant treatment temperature is 95 ° C., and the wide applicability of this technology is recognized. It was.

Furthermore, the dye concentration of the dyed fabric before the flame retardant treatment relative to the dyed fabric after the flame retardant treatment measured using a SICOMUC20 spectrophotometer is 99.2%, and the color tone of both cannot be visually observed. It was. This result means that even when the dyed fabric is flame-retardant treated, the dye discharge phenomenon (crying) hardly occurred, indicating that this technique is excellent.
<Example 11>
In order to investigate the further applicability of the flame retardant treatment of the polyester fabric with the flame retardant of the present invention, POG dyeing in a flame retardant bath composed of TTP, N7000, tannic acid and ACX for 60 minutes at 95 ° C. Fabric 2 was treated. The number of times of flame contact was 3 or more after the flame retardant treatment and after the L-5 treatment, and the classification by the carbonization area method was 3, and it became clear that the technique of the present invention has wide applicability. .

Furthermore, the dye concentration of the dyed fabric before the flame retardant treatment relative to the dyed fabric after the flame retardant treatment measured using a SICOMUC20 spectrophotometer is 98.1%. It was. This result means that even when the flame retardant treatment was performed under conditions different from those of Example 10, the dye discharge phenomenon (colored crying) hardly occurred. It has been proved that it has broad utility.
<Example 12>
With conventional technology, it is difficult to achieve sufficient flame retardancy unless the product after flame retardant treatment is oil-stained, yellowed, etc., and the flame retardant treatment conditions are not in the temperature range of around 130 ° C under pressure. As shown in Examples 1 to 11, when the tannic acid that is a polyphenol is contained in the flame retardant, the polyester fiber product is usually under conditions of 130 ° C. under pressure. Since it became clear that excellent flame retardancy could be easily imparted even under the condition of 95 ° C. under pressure, the possibility of flame retardancy was also examined for polyester films.

As shown in Table 1, HF-77 as a flame retardant, N7000 as an emulsifier, tannic acid as a sticking agent, acetic acid and ammonium acetate as other components, a flame retardant bath composed of acetic acid and ammonium acetate at 95 ° C. for 40 minutes, thickness 50 μm The flame retardant treatment of the polyester film was performed. As a result, the flame contact number after the flame retardant treatment and the L-5 treatment is 4 or more, the classification by the carbonization area method is 3, and it is clear that the film obtained in any value has high flame retardancy. Became.
<Example 13>
The film was flame-retarded under the same conditions as in Example 12 except that the fixing agent was FK-707 and the flame retardant bath composition did not contain other components. Also in this case, the flame contact number after the flame retardant treatment and after the L-5 treatment is 4 or more, the classification by the carbonization area method is 3, and the film obtained in any value may have high flame retardancy. It was revealed.

  In the conventional technology, flame retardancy of a film is obtained by melting and kneading a flame retardant into a polyester resin and molding it into a film. By including a flame retardant, film physical properties are reduced and expensive flame retardancy is caused. Although there was a problem that the polyester had to be contained, from the results of Examples 12 and 13, the technology of the present invention that can directly flame-retardant a commercially available polyester film without flame retardancy is excellent. I have proved that.

(7) Examples of simultaneous dyeing and flame retardant treatment As described above, the technology of the present invention enables flame retardant treatment of not only various polyester fiber products but also films, From the viewpoint of the processing technology of polyester products, dyeing and flame retardancy should be performed simultaneously in one treatment agent bath under pressure and at a temperature of around 130 ° C, as well as under normal pressure (simultaneous dyeing and flame retardancy). The range of application of the technique of the present invention is further widened. Then, as shown in Table 2, Examples 14-17 demonstrates the flame retardance of the polyester product by simultaneous dyeing | staining and a flame-retarding process.
<Example 14>
The undyed cloth 1 (tropical cloth) was subjected to simultaneous dyeing / flame retardant treatment at 95 ° C. for 60 minutes in a flame retardant bath substantially the same as in Example 10 containing the dye 1. As a result, the number of flame contact after the flame retardant treatment and after the L-5 treatment is 3 or more, the classification by the carbonization area method is 3, and the simultaneous dyeing / flame retardant treatment product obtained in any value is highly difficult. It became clear that it had flammability.

In addition, with respect to the degree of dyeing, with respect to the cloth subjected to the above-mentioned simultaneous dyeing / flame retardant treatment, the dye concentration of the cloth dyed under the same conditions except that the flame retardant and the fixing agent are excluded is the SICOMUC20 spectrophotometer. When it was used and measured, it was 98.4%, and the color tone of the both could not be distinguished visually. This result shows that the simultaneous dyeing and flame retardant treatment technology of the present invention is an excellent technology that can simultaneously dye polyester and flame retardant without substantially affecting the dyeability of the undyed fabric. Yes.
<Example 15>
The undyed fabric 2 (polyester organdy) was subjected to simultaneous dyeing and flame retarding treatment at 95 ° C. for 60 minutes in a flame retardant bath containing the dye 1 in substantially the same manner as in the flame retardant bath. As in Example 14, the evaluation of flame retardancy and dyeability was good.
<Examples 16 to 17>
Each of the undyed cloth 2 and the film was treated in a flame retardant bath containing the dye 2 having the composition shown in Table 2.

  The evaluation of flame retardancy and dyeability was good.

(8) Comparative Example The excellent effect of the present invention will be further clarified by showing a comparative example.
<Comparative Examples 1-8>
It processed using the flame retardant which does not contain a sticking agent as shown in Table 3, and evaluated the flame retardance.

  As shown in Table 3, it was confirmed that the number of times of flame contact was significantly lower than that of the above example.

<Example 18>
As shown in Table 4, the undyed POG cloth (original sample) was dipped (padding) in the flame retardant aqueous solution used in Example 3 for 1 minute, and then the POG cloth was taken out, and the drawing machine (mangle) The excess flame retardant aqueous solution was removed by heating and drying at 180 ° C. for 1 minute (heat setting). Next, this was stirred in an aqueous soaping agent solution as shown in Table 4 at 80 ° C. for 20 minutes to wash off the excess flame retardant, further washed with hot water at 80 ° C. for 20 minutes, and then heated at 180 ° C. for 1 minute. Dried. As a result, the flame contact number after the flame retardant treatment was 4 or more, the flame contact number after the L-5 treatment was 3 or more, the classification by the carbonized area method was 3, and the flame retardant obtained in Example 3 The flame retardant was equal to or better than Further, the flame-retardant polyester obtained by the above method did not show stickiness or flame retardant unevenness that could not be overcome by the conventional technology. Therefore, it has been clarified that if the flame retardant composition of the present invention is used, the flame retardant treatment of polyester can be performed even by the padding method.

Claims (12)

  A polyester flame-retardant composition for fixing a flame retardant on the surface of an undyed or dyed polyester to exhibit flame retardancy, a phosphoric flame retardant, an emulsifier, and tannic acid as a binder A flame retardant composition comprising an aqueous solution containing   A polyester flame-retardant composition for developing flame retardancy by fixing a flame retardant on the surface thereof simultaneously with dyeing of an undyed polyester, a phosphonic flame retardant, an emulsifier, and tannin as a fixing agent A flame retardant composition, which is an aqueous solution containing a dye together with an acid.   The flame retardant composition according to claim 1 or 2, wherein the phosphorus flame retardant is a phosphate ester compound.   The flame retardant composition according to any one of claims 1 to 3, wherein the polyester is a fiber, a woven fabric, a knitted fabric, a nonwoven fabric, or a film. A polyester flame retardant treatment method for developing flame retardancy by fixing a flame retardant to the surface of a polyester undyed or dyed product, comprising a phosphoric flame retardant, an emulsifier, and tannic acid as a binder A flame retardant treatment method comprising immersing an undyed or dyed polyester in a temperature range of 80 ° C. or higher and 140 ° C. or lower in an aqueous solution containing A flame retarding processing method of the polyester for expressing flame retardancy by fixing the flame retardant non-dyeing or dyeing the surface of the polyester, in an aqueous solution containing phosphorus-based flame retardant and emulsifying agents, A polyester undyed or dyed product is immersed in a temperature range of 80 ° C. or higher and 140 ° C. or lower, and then immersed in an aqueous solution containing tannic acid as a fixing agent. Flame retardant treatment method. A method for flame retardant treatment of polyester for fixing a flame retardant on the surface thereof simultaneously with the dyeing of an undyed polyester to exhibit flame retardancy , comprising a phosphorus flame retardant , an emulsifier , and tannin as a binder in an aqueous solution containing a dye with acid, flame retarding processing method characterized by the non-dyeing of polyester, an immersion treatment in a temperature range of 80 ° C. or higher 140 ° C. or less. A method for flame-retarding a polyester for fixing a flame retardant to the surface thereof simultaneously with dyeing of an undyed polyester to exhibit flame retardancy, in an aqueous solution containing a dye together with a phosphorus flame retardant and an emulsifier The polyester undyed product is immersed in a temperature range of 80 ° C. or higher and 140 ° C. or lower, and then immersed in an aqueous solution containing tannic acid as a fixing agent. A flame retardant treatment method comprising: A method for flame-retarding a polyester, wherein the polyester is immersed (padding) in an aqueous solution containing a phosphoric flame retardant, an emulsifier, and a tannic acid as a fixing agent at room temperature, and then the excess aqueous solution is dehydrated. Then , a flame-retarding treatment method characterized by heat-drying treatment . The flame retardant treatment method according to any one of claims 5 to 9, wherein the polyester is a fiber, a woven fabric, a knitted fabric, a nonwoven fabric, or a film . The flame retardant treatment method according to any one of claims 5 to 10 , wherein the flame retardant adhering treatment is subjected to a soaping treatment to wash and remove the excessively attached flame retardant. The phosphorus-based flame retardant, a flame retarding processing method according to any one of claims 5 to 11, characterized in that the phosphoric acid ester compound.