JP5703464B2 - Flame retardant polyester resin composition, flame retardant polyester fiber, flame retardant material and method for producing flame retardant polyester fiber - Google Patents

Description

  The present invention relates to a flame retardant polyester resin composition having high flame retardancy and good physical properties, and a flame retardant fiber obtained using the flame retardant polyester resin composition. More specifically, a flame retardant polyester resin composition containing a flame retardant aid composed of a 1,2-diphenyl derivative and / or a diisopropylbenzene oligomer in addition to the inorganic phosphorus flame retardant, and being substantially halogen-free, The present invention relates to a flame retardant polyester fiber, a flame retardant material, and a method for producing a flame retardant polyester fiber.

  Thermoplastic polyesters, especially polyethylene terephthalate (PET), have excellent balance of mechanical properties, heat resistance, moldability, chemical resistance, etc. and are inexpensive, so molded products represented by fibers, films, and PET bottles. And has a very wide application as a packaging material. Furthermore, in recent years, from the viewpoint of resource reuse, recycled polyester resins obtained by collecting polyester products after use or polyester waste generated in the molding process have been reused as raw materials for fibers and PET bottles. I came.

  As such demand increases, thermoplastic polyesters have the disadvantage that they are easily combusted. In recent years, with the increasing awareness of fire and the environment, environmentally friendly flame retardant is strongly demanded. Conventionally, combined use with brominated flame retardants and antimony trioxide has been widely used due to its high flame retardant efficiency. However, there are concerns about environmental impacts such as residual contamination and dioxin formation. Non-brominated flame retardants are being developed and replaced. However, the flame retardant system centered on phosphorus compounds differs from the brominated flame retardant and antimony trioxide combined system, which show effective flame retardant effect in the gas phase. Although it is said to exhibit a flame retardant effect, the flame retardant efficiency is inferior to bromine flame retardants. There is an urgent need to develop more highly flame retardant flame retardant than environmentally friendly.

  Various attempts have been made to make flame retardants for thermoplastic polyester resins and thermoplastic polyester fibers. In particular, in the case of fibers, it is difficult to achieve both high flame resistance and maintenance of physical properties. Various methods such as a method using a copolymerized polyester obtained by polymerization, a method of kneading a flame retardant into polyester and spinning, and a method of making a fiber product flame retardant by post-processing have been proposed.

  For example, Patent Document 1 discloses a method for producing a flame-retardant polyester fiber obtained by spinning or spinning and stretching using a raw material obtained by mixing a copolymerized polyester obtained by copolymerizing an organic phosphorus compound and a recovered polyester. It is disclosed. Further, Patent Document 2 discloses a polyester resin obtained by adding an organic phosphorus compound such as phosphine oxide, phosphonate, or phosphinate to a regenerated polyester resin and a polyester resin collected in a chip manufacturing process and / or a film manufacturing process. A flame retardant recycled original polyester fiber obtained by melt-mixing a composition and spinning it into a fiber is disclosed.

  Further, for example, Patent Document 3 discloses a flame-retardant polyester fiber obtained by melt spinning a resin composition containing inorganic red phosphorus or resin-coated inorganic red phosphorus, and Patent Document 4 further discloses ammonium polyphosphate. Flame retardant polyester fiber obtained by melt spinning a resin composition containing Separately, Patent Document 5 discloses a flame-retardant fiber product in which an ammonium polyphosphate-containing material coated with a thermoplastic resin is contained in a fiber product after spinning in a treatment step.

  On the other hand, 1,2-diphenylethane derivatives and / or diisopropylpropylbenzene oligomers are mainly used in the production of plastic molded products, and are flame retardant aids for thermoplastic resins in combination with brominated flame retardants and organophosphorous flame retardants. In addition, there is a report that it is used as a high-temperature crosslinking agent for engineering resins. For example, Patent Document 6 discloses a flame retardant resin composition comprising an aromatic polyester resin, a specific organic phosphorus compound, a specific biscumyl compound (1,2-diphenylethane derivative), a flame retardant improving resin and a filler, and The resulting molded article is disclosed, and Patent Document 7 discloses a flame retardant composition for plastics containing a brominated flame retardant, a 1,2-diphenylethane derivative and a phthalocyanine complex or a naphthalocyanine complex. Patent Document 8 discloses a polyester resin, a radical generator of a 1,2-diphenylethane derivative and / or a diisopropylbenzene oligomer, and a polyfunctional monomer having at least two carbon-carbon double bonds in the molecule. And a cross-linked polyester resin obtained by heating and cross-linking it at a temperature of 220 to 320 ° C. are disclosed.

JP 2002-54026 A JP 2007-254905 A JP 2001-279073 A JP 2008-202152 A JP 2001-262466 A JP 2003-34749 A JP 2006-70138 A Japanese Patent Laid-Open No. 2001-19835

  The method of using a copolyester shown in Patent Document 1 and the method of kneading and spinning an organophosphorus compound shown in Patent Document 2 use an organophosphorus compound as a flame retardant, compared to brominated flame retardants. Flame retardant efficiency is extremely low, and when used in large quantities, the degradation of physical properties of the resin and fiber due to the organic phosphorus compound being compatible with the thermoplastic polyester resin, and precipitation of the flame retardant on the surface of the resin and fiber becomes a problem. . In particular, the copolyester deteriorates the physical properties of the polyester itself because the flame retardant component is incorporated into the basic skeleton of the polyester. In addition, inorganic phosphorus flame retardants such as inorganic red phosphorus shown in Patent Document 3 and ammonium polyphosphate shown in Patent Document 4 have poor compatibility and uniform dispersibility with the resin, compared to organic phosphorus compounds, Although the flame retardancy efficiency is high, a satisfactory one has not yet been obtained for applications requiring spinnability, stable flame retardancy and high quality.

  In addition, as shown in Patent Document 5, the method of flame-retarding after spinning polyester fibers is complicated or uneven, makes the texture of the fibers rough, and is difficult to wash. It has various drawbacks such as reduced flammability. If the flame retardancy is not uniform, it is not possible to obtain a sufficient flame retardant effect and a long-term stable fiber product, which also hinders safety and quality during use. In particular, when used as an automobile interior material, since a binder and a large amount of flame retardant must be used, fuel consumption increases due to an increase in the weight of the automobile. In addition, when the polyester fiber product after use is reused, there arises a problem of separation of different polymers used as a flame retardant binder.

  When a flame retardant is added to a resin composition to develop flame retardancy by a kneading method, it is necessary to increase the amount of flame retardant used to obtain flame retardant fibers with satisfactory performance. However, when a large amount of flame retardant is added to the raw material resin composition, yarn formation becomes difficult at the melt spinning stage, flame retardant precipitates on the surface of the fiber during the melt spinning and drawing process, and the yarn Many undesired problems and phenomena such as frequent breakage and a significant decrease in productivity, and a failure to obtain satisfactory fiber properties due to significant deterioration of the inherent properties of the fiber resin component occur, Limited.

  For example, when polyethylene terephthalate is melt-spun and the draw ratio is set to 4 to obtain a fiber having a single yarn fineness of 2 to 220 dtex, the fiber diameter of the undrawn yarn is 28 to 280 μm, and the fiber diameter of the drawn yarn is 14 to 140 μm. Since the fiber diameter is very thin, the flame retardant used in the kneading method has not only flame retardancy but also solubility and dispersibility in the fiber resin component in the spinning process, and the fiber surface. More stringent performance is required than plastic molding, such as non-precipitating properties and stretchability in the stretching process. Further, since the surface area in contact with oxygen is remarkably increased as compared with a plastic molded article, it becomes easy to burn and requires a more highly active flame retardant system. The same applies to thin molded articles such as plastic sheets and films.

  Patent Document 6 discloses that a 1,2-diphenylethane derivative is effective as a flame retardant aid in plastic molding when used in combination with a specific organophosphorus compound. , 2-diphenylethane derivatives are effective in combination with brominated flame retardants, and Patent Document 8 further discloses that 1,2-diphenylethane derivatives and / or diisopropylbenzene oligomers are crosslinked in combination with crosslinking aids. It has been shown to be effective as an agent. Thus, these patent documents show that 1,2-diphenylethane derivatives and / or diisopropylbenzene oligomers are effective in combination with organic phosphorus compounds and brominated flame retardants. There is no description of enhancing the flame retardant effect by expressing the flame retardant action in both the solid phase and the gas phase, particularly effective in combination with an inorganic phosphorus flame retardant.

  In the plastic molding field, environmentally friendly phosphorus-based flame retardants are being developed and replaced as substitutes for brominated flame retardants and antimony combined flame retardants, which have a large environmental impact, but fibers, films, sheets, etc. In the field of thin molded articles, satisfactory products have not been obtained. In particular, inorganic phosphorous flame retardants have high flame retardant efficiency, but they are expected to have poor compatibility with resins. However, it is important to activate inorganic phosphorous flame retardants with poor compatibility. Flame retardant systems are strongly demanded.

  As a result of detailed investigations for a flame retardant system that has high flame retardant efficiency and is environmentally friendly by combining with an inorganic phosphorus flame retardant, the present inventors have found that inorganic phosphorus exhibiting a remarkable flame retardant effect in the solid phase. Expressing excellent flame retardancy by using a specific 1,2-diphenylethane derivative and / or diisopropylbenzene oligomer in combination with a specific flame retardant as a flame retardant aid in the gas phase As a result, the present invention has been completed. That is, the present invention provides the following (1) to (16).

  (1) at least one inorganic phosphorus flame retardant selected from the group consisting of a thermoplastic polyester resin, inorganic red phosphorus, an inorganic phosphorus-nitrogen compound, and an organic metal phosphate, and the following general formula (1);

(Wherein R _{1 to} R ₄ are an alkyl group having 1 to 3 carbon atoms, and R ₅ is a hydrogen atom or an alkyl group having 1 to 7 carbon atoms), and a 1,2-diphenylethane derivative represented by The following general formula (2);

(Wherein n is an average value of 2 to 50), a flame retardant polyester resin composition containing at least one flame retardant auxiliary of diisopropylbenzene oligomer,
The content of the inorganic phosphorus flame retardant is 0.1 to 12% by mass based on the total weight of 100% by mass of the thermoplastic polyester resin composition, and a 1,2-diphenylethane derivative and / or diisopropylbenzene oligomer The flame retardant polyester is characterized in that the content of the flame retardant aid represented by the formula is 0.05 to 5% by mass and the content of the thermoplastic polyester resin is 83 to 99.85% by mass. Resin composition.

  (2) The content of the inorganic phosphorus flame retardant is 0.5 to 8% by mass based on 100% by mass of the total weight of the thermoplastic polyester resin composition, and 1,2-diphenylethane derivative and / or The flame retardant polyester resin composition according to the above (1), wherein the content of the flame retardant aid represented by diisopropylbenzene oligomer is 0.1 to 4% by mass.

  (3) The content of the inorganic phosphorus-based flame retardant is 0.6 to 5% by mass based on the total weight of 100% by mass of the thermoplastic polyester resin composition, and a 1,2-diphenylethane derivative and / or The content of the flame retardant aid represented by diisopropylbenzene oligomer is 0.12 to 4% by mass, and the total content of inorganic phosphorus flame retardant and flame retardant aid is 1.5 to 6% by mass. The flame-retardant polyester resin composition as described in (1) or (2) above,

  (4) The decomposition peak temperature of the flame retardant aid represented by 1,2-diphenylethane derivative and / or diisopropylbenzene oligomer is 200 ° C. or higher and the boiling point of the decomposition fragment is 400 ° C. or lower ( The flame-retardant polyester resin composition according to any one of 1) to (3).

  (5) The inorganic phosphorus-nitrogen compound is at least one selected from the group consisting of ammonium polyphosphate, melamine polyphosphate, and phosphazenes, and the organic phosphate metal salt is tris (diethylphosphinic acid) aluminum. The flame-retardant polyester resin composition according to any one of the above (1) to (4).

  (6) The flame retardant polyester resin composition according to any one of (1) to (5), wherein the thermoplastic polyester resin includes a regenerated polyester resin.

  (7) The flame retardant polyester resin composition according to any one of (1) to (6), wherein the flame retardant aid is 2,3-dimethyl-2,3-diphenylbutane and / or diisopropylbenzene oligomer. object.

  (8) Any of (1) to (7) above, wherein the phosphazenes are linear compounds having at least one selected from the group consisting of phenoxyphosphazene, propoxyphosphazene and diaminophosphazene as a basic skeleton. The flame-retardant polyester resin composition described in 1.

  (9) Obtained by melt-mixing a flame-retardant polyester resin composition containing the thermoplastic polyester resin, the inorganic phosphorus flame retardant and the flame retardant aid described in (1) to (8), and then melt spinning. Flame retardant polyester fiber characterized by.

  (10) The flame-retardant polyester fiber according to (9), wherein the decomposition temperature of the inorganic phosphorus-nitrogen compound according to (1) to (8) is 270 ° C. or higher.

  (11) The flame retardant polyester fiber according to any one of (9) and (10), wherein the inorganic phosphorus flame retardant according to (1) to (8) is a powder having an average particle size of 30 μm or less.

  (12) The flame-retardant polyester fiber according to any one of (9) to (11), wherein the single-fiber fineness of the flame-retardant polyester fiber is 2.0 to 220 dtex.

  (13) Melt-mixing a flame retardant polyester resin composition comprising a master batch containing the inorganic phosphorus flame retardant described in (1) to (7) above, a master batch containing a flame retardant aid, and a thermoplastic polyester resin And then melt spinning, a method for producing a flame-retardant polyester fiber.

  (14) Melt-mixing a flame retardant polyester resin composition comprising a master batch containing the inorganic phosphorus-based flame retardant described in (1) to (7) above, a master batch containing a flame retardant aid, and a thermoplastic polyester resin The method for producing a flame-retardant polyester fiber according to (13), wherein melt spinning is performed at a take-up speed of 300 to 1,000 m / min and a spinning temperature of 200 to 300 ° C. by a dry method.

  (15) The flame retardant polyester fiber according to any one of (9) to (12) above or the flame retardant polyester fiber obtained by the production method according to any one of (13) or (14) above Flame retardant containing 100% by mass.

  (16) An automobile interior material using the flame retardant according to (15).

  According to the present invention, a specific 1,2-diphenylethane derivative and / or diisopropylbenzene oligomer is used as a flame retardant aid in an inorganic phosphorus flame retardant and mixed together with a thermoplastic polyester resin. By kneading as a composition and then melt spinning, a flame retardant fiber and a flame retardant excellent in spinnability, flame retardancy, colorability, light resistance, durability and the like are obtained without impairing the physical properties of the fiber. In particular, when the amount of the flame retardant used in the thermoplastic polyester resin composition increases, fiber physical properties are often deteriorated and spinning becomes difficult in many cases. In the present invention, flame retardant exhibiting an effective flame retardant effect in the gas phase. By adding a small amount of auxiliary agent, a synergistic effect with the flame retardant can be obtained, and the amount of flame retardant used can be reduced. Furthermore, the use range can be expanded by using recycled polyester resin as a raw material. Moreover, the flame-retardant polyester resin composition of the present invention can be used not only for the production of fibers but also for the production of plastics. In particular, it is difficult to add a large amount of a flame retardant such as a sheet or a film, and it is useful for the production of a thin article which is easy to burn.

  The 1,2-diphenylethane derivative, diisopropylbenzene oligomer, a combination system of an inorganic phosphorus flame retardant and the flame retardant aid, and products obtained using these flame retardant aids used in the present invention are toxic. It is low and environmentally friendly with little environmental impact, and is an excellent product with little environmental impact even when it is treated as waste in the manufacturing process or after the use of textile products.

2 is a temperature-weight loss curve and a differential curve of 2,3-dimethyl-2,3-diphenylbutane. 2 is a temperature-loss curve and derivative curve of a 30% masterbatch of 2,3-dimethyl-2,3-diphenylbutane.

  The present invention relates to a fiber obtained by melt spinning a flame retardant polyester resin composition containing an inorganic phosphorus flame retardant and a thermoplastic polyester resin, or a thin article such as a sheet or film obtained by molding. TECHNICAL FIELD The present invention relates to a flame retardant polyester resin composition characterized by containing a specific 1,2-diphenylethane derivative and / or diisopropylbenzene oligomer in a resin composition, and a flame retardant polyester fiber and molded article obtained using the same. . Based on the total weight of the flame retardant polyester resin composition, the content of the inorganic phosphorus flame retardant is 0.1 to 12% by mass, and the 1,2-diphenylethane derivative and / or diisopropylbenzene oligomer described above The content of is 5 to 5% by mass, and the content of the thermoplastic polyester resin is 86 to 99.85% by mass. In the present specification, unless otherwise noted, the numerical range indicated by “to” includes an upper limit and a lower limit. For example, “0.1 to 12% by mass” means “0.1 to 12% by mass”.

  Specific 1,2-diphenylethane derivatives used as the flame retardant aid of the present invention include the following general formula (1):

(Wherein R _{1 to} R ₄ are an alkyl group having 1 to 3 carbon atoms, and R ₅ is a hydrogen atom or an alkyl group having 1 to 7 carbon atoms) and diisopropylbenzene oligomer, The following general formula (2):

(Where n is an average value of 2 to 50). Significant C-C bond cleavage occurs at a temperature of 350 to 400 [deg.] C. at which combustion starts, and decomposed fragments are gasified. The decomposition peak temperature of the 1,2-diphenylethane derivative and the isopropylbenzene oligomer is 200 ° C. or higher, preferably 220 to 350 ° C., and the boiling point of the decomposition fragment is 400 ° C. or lower, preferably 0 to 350 ° C. If the decomposition peak temperature is less than 200 ° C, remarkable decomposition occurs during kneading and melt spinning, and if the boiling point of the decomposition fragment exceeds 400 ° C, it is difficult to gasify when combustion starts up, so the flame-retardant effect in the gas phase cannot be exhibited. . The upper limit of the decomposition peak temperature is not particularly limited, but when it exceeds 350 ° C., the flame retardant component (decomposition fragment) concentration in the gas phase is too low to exhibit a sufficient flame retardant effect. Can not. The lower limit value of the boiling point of the decomposition fragment is not particularly limited, and is determined by combining with the decomposition peak temperature. That is, it is necessary that a flame retardant component (decomposed fragment) having an appropriate concentration exists in the gas phase at a temperature of 350 to 400 ° C. at which combustion starts. Therefore, the lower limit of the boiling point is -12 ° C. of isobutane, which is a tertiary hydrocarbon having the smallest number of carbon atoms, but preferably 0 ° C. in order to maintain a certain concentration in the gas phase.

  In the flame retardant aid of the present invention, examples of the compound represented by the general formula (1) include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylbutane, 2,3 -Dimethyl-2,3-di (p-methylphenyl) butane, 2,3-diethyl-2,3-di (p-methylphenyl) butane, 2,3-dimethyl-2,3-di (p-chlorophenyl) ) Butane, and examples of the compound represented by the general formula (2) include m-diisopropylbenzene oligomer, p-diisopropylbenzene oligomer, m- and p-mixed diisopropylbenzene oligomer. These compounds are generally composed of organic peroxides such as di-t-butyl peroxide and aromatic hydrocarbons having tertiary hydrogen at the α-position carbon atom of the aromatic ring such as cumene and diisopropylbenzene. Although it is obtained by oxidative recombination (see Patent Document 8), it is not limited thereto, and other known methods can be used.

  The decomposition peak temperature of the flame retardant aid of the present invention is the weight loss peak temperature obtained by differentiating the temperature-weight loss curve in the thermogravimetric analysis of the flame retardant aid and the decomposition reaction of the following general formulas (3) and (4);

From the difference in the standard heat of formation, the following formulas (5) and (6);

(Where E _d is the difference in the standard heat of formation in the decomposition of the flame retardant aid to be determined, E _s is the difference in the standard heat of formation of the standard flame retardant aid, T _d is the decomposition temperature of the flame retardant auxiliary to be determined, T _s is the standard decomposition temperature of the flame retardant aid). The boiling point of the decomposed fragment is the actual measured value of the boiling point of the corresponding monocyclic aromatic hydrocarbon, or the following formula (7);

(Where t _b is the normal boiling point (° C.), n is the number of carbon atoms of the aromatic hydrocarbon, a and k are constants, and in the case of monocyclic aromatic hydrocarbons, a = 680, k = −614. .4)). As the decomposition peak temperature of the compound represented by the general formula (1) (30% masterbatch) and the boiling point of the decomposition fragment, for example, 2,3-dimethyl-2,3-diphenylbutane (decomposition peak temperature: measured value 233 ° C., Boiling point of decomposition fragment (cumene): measured value and estimated value 152 ° C., 2,3-diethyl-2,3-diphenylbutane (decomposition peak temperature: estimated value 202 ° C., boiling point of decomposed fragment: estimated value 193 ° C.), 2,3-Dimethyl-2,3-di (p-methylphenyl) butane (decomposition peak temperature: estimated value 240 ° C., boiling point of decomposed fragment: estimated value 173 ° C.), 2,3-diethyl-2,3-di (P-methylphenyl) butane (decomposition peak temperature: estimated value 210 ° C., boiling point of decomposed fragment: estimated value 211 ° C.), and the decomposition peak temperature of the diisopropylbenzene oligomer of the general formula (2) is 2 1 ° C. (estimated value) and 265 ° C. (measured value), the boiling point of the proteolytic fragments (diisopropylbenzene) is 211 ° C. (estimated value). Here, when both the estimated value and the actually measured value are obtained and there is a difference between them, the actually measured value is adopted (for details, refer to the reference example described later). Among these, 2,3-dimethyl-2,3-diphenylbutane is particularly preferable because it has a low molecular weight and thus has good flame retardant efficiency per weight and high crystallinity, and also has less blooming on the resin surface. . In addition, since diisopropylbenzene oligomer is a high molecular weight substance, it is decomposed at various sites in the initial stage to generate various decomposed fragments having different boiling points. The decomposition peak temperature is also high, decomposition fragments can be supplied in a wide temperature range, and components effective for flame retardancy in the gas phase can be supplied at a wide range of combustion temperatures. Furthermore, by using together with 2,3-dimethyl-2,3-diphenylbutane, a more excellent flame retardant effect can be exhibited.

  The flame retardant aid used in the present invention causes significant C—C bond cleavage at a temperature of 350 to 400 ° C. at which combustion starts, and at the same time gasifies to generate a stable tertiary carbon radical (see Formulas 3 and 4). ). The stable tertiary carbon radicals that are generated capture the active radicals that continue to develop combustion, stop the combustion chain, and reduce the oxygen concentration in the combustion atmosphere necessary for combustion, etc., inorganic phosphorus flame retardants It exhibits a synergistic effect with the flame retardant effect of char formation in the solid phase. In particular, the decomposed fragments produced by gasification can exhibit an efficient and stable flame retardant effect by adding a small amount by being uniformly dispersed in a wide range of combustion atmosphere.

  The inorganic phosphorus flame retardant of the present invention is composed of inorganic red phosphorus, an inorganic phosphorus-nitrogen compound, and an organic phosphate metal salt, and has a higher phosphorus atom concentration that exhibits flame retardancy than an organic phosphorus compound. In addition, since the compatibility with the thermoplastic polyester resin is poor, the physical properties of the resin itself due to dissolution do not deteriorate.

  As inorganic red phosphorus, inorganic red phosphorus generally used as a flame retardant such as a synthetic resin can be used. In general, inorganic red phosphorus is obtained by heat-treating yellow phosphorus for several days in a reaction vessel called a conversion kettle. It is obtained by pulverizing and pulverizing the resulting mass. However, powdered red phosphorus treated in this way can be unstable to external stimuli such as heat, friction, impact, etc., by applying a physical or chemical surface treatment, or from yellow phosphorus It can be stabilized by using a dispersant during thermal conversion. Although all these forms of inorganic red phosphorus can be used in the present invention, the average particle size of the inorganic red phosphorus powder is 10 μm or less, preferably 0, in order to obtain stable flame-retardant fibers and thin molded articles. It is preferable that it is 5-10 micrometers, and 80 mass% or more is comprised with the particle size of 20 micrometers or less. The particle size and average particle size of the inorganic red phosphorus powder are measured using a method using a viscosity distribution measuring device such as a dynamic light scattering method, a laser diffraction / scattering method, or a known method such as sieving with an air jet sieve. Or can be calculated. The mass ratio (mass%) of the particles having a particle size of 20 μm or less of the inorganic red phosphorus powder can be calculated using, for example, a mesh sieve through which particles of 20 μm or less pass. Furthermore, inorganic red phosphorus can be coated with a resin to increase the compatibility with the thermoplastic polyester resin, thereby improving the safety and stability during production and the reliability of the textile product. As such a resin coating method, a known method such as a synthetic resin can be used.

  As the inorganic red phosphorus used in the present invention, not only those obtained by a production method such as publicly known literature as described above can be used, but also commercially available products can be used. Examples of the commercially available products include Nobaret (product name, manufactured by Phosphor Chemical Industry Co., Ltd.) and Hishiguard (product name, manufactured by Nippon Chemical Industry Co., Ltd.).

  The inorganic phosphorus-nitrogen compounds used as the inorganic phosphorus flame retardant of the present invention include polyphosphates such as ammonium polyphosphate and melamine polyphosphate and phosphazenes, which can be used alone or in combination. it can.

  The ammonium polyphosphate used in the present invention has the following general formula (8);

In the formula, n is an integer of 10 or more, preferably 300 or more, more preferably 500 or more, and particularly preferably 1,000 to 10,000. There are six known crystal structures of type VI. In the present invention, any of these I-VI ammonium polyphosphates can be used, but type II ammonium polyphosphate having a high decomposition temperature is more preferred. A polymerization degree (n) of 10 or more is preferable because the decomposition temperature does not decrease significantly. The upper limit of the degree of polymerization (n) is not particularly limited. However, when the degree of polymerization is too large, it is difficult to produce, and branching increases, which is unfavorable for uniform dispersion in the fiber resin component. In general, ammonium polyphosphate is obtained by adding an amide compound such as urea or ammonium carbonate to phosphoric acid, ammonium phosphate, or ammonium amidophosphate as a dehydrating condensing agent or an ammoniating agent, and reacting them.

  The melamine polyphosphate used in the present invention means a melamine adduct formed by substantially equimolar reaction of melamine with orthophosphoric acid, pyrophosphoric acid, or polyphosphoric acid. The production method of melamine polyphosphate includes various methods such as heating, baking, and condensing melamine orthophosphate, obtaining from polyphosphoric acid and melamine, obtaining from orthophosphoric acid and melamine, and obtaining from melamine, ammonium phosphate and urea. Methods have been proposed and are described in detail in Japanese Patent Application Laid-Open Nos. 2004-010649 and 2004-155564. Among the melamine polyphosphates, a reactive product with pyrophosphoric acid is particularly distinguished by being called melamine pyrophosphate, which is also included.

  As the phosphazenes used in the present invention, conventionally known phosphazenes can be used without particular limitation as long as they have a phosphazene skeleton. For example, there are cyclic phosphazene compounds and chain phosphazene compounds, specifically, cyclic and chain phenoxyphosphazenes, propoxyphosphazenes, diaminophosphazenes, etc. Among these phosphazenes, linear compounds are used as the basic skeleton. The phosphorus atom concentration is 10% by mass or more, preferably 10 to 50% by mass. In particular, phosphazenes generally have a low melting point, poor compatibility and / or dispersibility with thermoplastic polyester resins, are difficult to mix uniformly during spinning, and may cause bleeding problems. For this reason, it is preferable to use it as a masterbatch or to use it in combination with other flame retardants.

  The production method of these phosphazenes is not particularly limited, and a conventionally known method can be used. For example, the cyclic phosphazene compound and the chain phosphazene compound can be produced from a dichlorophosphazene compound according to a conventionally known method. The dichlorophosphazene compound is prepared by reacting ammonium chloride and phosphorus pentachloride (or ammonium chloride, phosphorus trichloride and chlorine) at about 120 to 130 ° C. and dehydrochlorinating the reaction product using chlorobenzene as a solvent. What is necessary is just to refine.

As the inorganic phosphorus-nitrogen compound used in the present invention, not only those obtained by production methods such as known literature as described above can be used, but also commercially available products can be used. Examples of the commercially available products include Terrage (product name, manufactured by Budenheim Iberica), FR CROS (product name, manufactured by Budenheim Iberica), Fire Cut P-770 and P-760 (
Product name, manufactured by Suzuhiro Chemical Co., Ltd., Pekoflam TC204 and TC-CS (product name, manufactured by Clariant), M-PPA (product name, manufactured by Sanwa Chemical Co., Ltd.), Budit (product name, manufactured by Clariant) ), Fire Cut CLMP (product name, manufactured by Suzuhiro Chemical Co. , Ltd. ), cyclic cyclophosphazene oligomer (product name, manufactured by Otsuka Chemical Co., Ltd.), linear polyphosphazene (product name, Otsuka Chemical ( Etc.).

  Among the inorganic phosphorus-nitrogen compounds used in the present invention, the decomposition of polyphosphate is accompanied by the generation of ammonia and the like at a relatively low temperature, and the decomposition temperature of the inorganic phosphorus-nitrogen compound such as polyphosphate is It can be obtained by thermal analysis using a differential scanning calorimeter, a differential thermal analyzer, a thermogravimetric measuring device or the like. Specifically, the decomposition temperature is a temperature at which a 5% weight loss due to gas generation occurs, and the intersection temperature between the baseline and endothermic peak rise at the corresponding endothermic peak based on gas generation. The decomposition temperature of the inorganic phosphorus-nitrogen compound used in the present invention is a temperature higher than the melting point of the thermoplastic polyester resin, usually 250 ° C. or higher, particularly preferably 270 ° C. or higher. The upper limit of the decomposition temperature is not particularly limited, but it is generally known that the decomposition temperature increases with the degree of polymerization and crystallinity, and those having a high degree of polymerization and good crystallinity are preferred.

  The inorganic phosphorus-nitrogen compound used in the present invention is usually a powder, and the average particle diameter of the powder is preferably 30 μm or less, more preferably the average particle diameter of the powder is 10 μm or less, particularly preferably. It is in the range of 0.5 to 10 μm. If the average particle size of the powder is 30 μm or less, the inorganic phosphorus-nitrogen compound can be directly mixed with the thermoplastic polyester resin and dispersed uniformly. In this case, the smaller the particle size, the better the dispersibility. Therefore, the lower limit of the average particle diameter of the powder is not particularly limited. However, if it is 0.5 μm or more, it is preferable because it is difficult to be dusted, it is easy to handle, and it is easy to monodisperse by preventing aggregation of powders. The particle size and average particle size of the inorganic phosphorus-nitrogen compound powder may be determined by a method using a viscosity distribution measuring device such as a dynamic light scattering method or a laser diffraction / scattering method, or a known method such as sieving with an air jet sieve. It can be used for measurement or calculation. In addition, it is desirable that the powder has a uniform particle size distribution, and by sieving or the like, a powder having a predetermined particle size, for example, using two types of mesh size, has a narrow particle size distribution and a uniform particle size. You may use what was adjusted. Moreover, what coated the particle | grain surface of the inorganic phosphorus- nitrogen type compound with resin, such as a melamine and a silicon | silicone, can be used. This not only improves the compatibility and dispersibility with the resin, but can also suppress hydrolysis and thermal decomposition, especially in the case of polyphosphates, significantly improving spinning performance and flame retardancy. Can be.

  Since the inorganic phosphorus-nitrogen compound used in the present invention is usually a colorless or white powder, it does not adversely affect the coloration of fibers and thin molded articles by the colorant. In addition to inorganic phosphorus functional groups, nitrogen functional groups are also included as functional groups that exhibit flame retardancy. Nitrogen functional groups can exhibit flame retardant effects that cannot be achieved with phosphorus functional groups alone, and phosphorus compounds alone are insufficient. It can supplement the flame retardant performance.

  Examples of the organic phosphate metal salt used in the present invention include a metal salt of a dialkylphosphinic acid. These compounds react dialkylphosphinic acids and / or their alkali metal salts by reacting alkyl sulphonous acid and / or phosphinic acid and / or their alkali metal salts with olefins in the presence of a free radical initiator, Furthermore, it is made to react with metal compounds, such as magnesium, calcium, aluminum, titanium, zinc, iron, and the dialkyl phosphinic acid salt of these metals is obtained. Specifically, tris (diethylphosphinic acid) aluminum, tris (methylethylphosphinic acid) aluminum, tris (diphenylphosphinic acid) aluminum, bis (diethylphosphinic acid) zinc, bis (methylethylphosphinic acid) zinc, bis (diphenyl) Phosphinic acid) zinc, bis (diethylphosphinic acid) titanyl, tetrakis (diethylphosphinic acid) titanium, bis (methylethylphosphinic acid) titanyl, tetrakis (methylethylphosphinic acid) titanium, bis (diphenylphosphinic acid) titanyl, tetrakis (diphenyl) (Phosphinic acid) titanium and the like can be mentioned, but not limited thereto, known ones (compounds described in JP-A-2005-325358, JP-A-2009-149862, etc.), or commercially available ones For example, it is possible to use Pekoflam STC (product name, manufactured by Clariant). Among these flame retardants, tris (diethylphosphinic acid) aluminum is particularly preferable since it has a high phosphorus content and a high proportion of incombustible components including aluminum.

  The organophosphate metal salt used in the present invention is usually a powder, and the average particle size of the powder is preferably 30 μm or less, more preferably the average particle size of the powder is 10 μm or less, and particularly preferably. It is in the range of 0.5 to 10 μm. If the average particle size of the powder is 30 μm or less, the organophosphate metal salt can be directly mixed with the thermoplastic polyester resin and dispersed uniformly. In this case, the smaller the particle size, the better the dispersibility. Therefore, the lower limit of the average particle diameter of the powder is not particularly limited. However, if it is 0.5 μm or more, it is preferable because it is difficult to be dusted, it is easy to handle, and it is easy to monodisperse by preventing aggregation of powders. The particle diameter and average particle diameter of such metal phosphates are obtained by using a method using a viscosity distribution measuring device such as a dynamic light scattering method or a laser diffraction / scattering method, or a known method such as sieving with an air jet sieve. Can be measured or calculated.

  Flame retardants and flame retardant aids are recognized as foreign substances for thermoplastic polyester resins, and in the production of thin molded articles during the molding process, or in the formation of yarns during the spinning and drawing processes, further thin molded articles or textile products It has a significant adverse effect on the physical properties. In particular, in order to impart sufficient flame retardancy, it is necessary to use a considerable amount of flame retardant with respect to the resin component. For this reason, the influence of flame retardants is large. Compared to ordinary plastic molding, flame retardants for thin molded articles and fibers require more stringent conditions for flame retardants. Certain flame retardants and flame retardant systems are desired.

  In addition, the action mechanism of the flame retardant during combustion is various, and the flame retardant action in the gas phase and the flame retardant action in the solid phase are completely different. In the gas phase, those that stop the chain of combustion and those that reduce the oxygen concentration required for combustion are preferred as flame retardants. On the other hand, in the solid phase, those that cover the surface of the combustion component by char formation and those that reduce the thermal conductivity at the time of combustion by the formation of intomesent (surface expansion layer) are desired as flame retardants. The inorganic phosphorus-based flame retardant used in the present invention forms a char composed of a network-like phosphate ester in the solid phase and exhibits remarkable flame retardancy. Furthermore, the inorganic phosphorus-nitrogen compound used in the present invention generates a gas based on a nitrogen component by being decomposed during combustion. For this reason, it is useful for char formation in the solid phase and becomes an excellent flame retardant, and also promotes flame retardant by stopping the combustion chain and reducing the oxygen concentration in the gas phase. On the other hand, inorganic red phosphorus and organic phosphoric acid metal salts are poor in the generation of gas that acts effectively in the gas phase, and the combined use of the flame retardant aid used in the present invention is particularly effective.

  The phosphorus atom content, nitrogen atom content, and the amount of nonflammable components such as metal atoms in the flame retardant are important because they greatly affect the flame retardant performance. The theoretical values of the phosphorus atom content and nitrogen atom content of the main flame retardant components used in the present invention are shown as follows: 31.9% and 14.4% for ammonium polyphosphate and 15% for melamine polyphosphate, respectively. 0.04% and 40.8%; for melamine pyrophosphate, 14.4% and 39.1%; for phenoxyphosphazene, 13.4% and 6.1%, respectively; for propoxyphosphazene, 19.0% and 8.6% and diaminophosphazene are 40.2 and 54.6%, respectively. In addition, since inorganic red phosphorus is formed of only phosphorus atoms, the phosphorus atom content is 100% and the nitrogen atom content is 0%. The phosphorus atom content of tris (diethylphosphinic acid) aluminum is 23. 8% and the aluminum atom content is 6.9%. For this reason, it turns out that the phosphorus atom content of inorganic red phosphorus shows a remarkably high value, and is a flame retardant excellent in the flame retardant effect. Next, diaminophosphazene, ammonium polyphosphate and tris (diethylphosphinic acid) aluminum have a high phosphorus content and are excellent in the flame-retardant effect per use amount. In particular, ammonium polyphosphate is a white powder that is easy to handle, has a good balance of phosphorus atom content and nitrogen atom content, and tris (diethylphosphinic acid) aluminum has a high decomposition temperature and is excellent in heat resistance and water resistance. Therefore, it can be said that these inorganic phosphorus flame retardants are the flame retardants superior to inorganic red phosphorus.

  Furthermore, in addition to flame retardancy, the flame retardant is required to be uniformly dispersed in the thermoplastic polyester resin component and not to cause significant degradation. The acid group produced by decomposition acts as a catalyst in various reactions such as hydrolysis and thermal decomposition of ester compounds, dehydration reaction, transesterification reaction, etc. Should be careful. In particular, inorganic phosphorous flame retardants have poor compatibility with thermoplastic polyester resins, so that precipitation on the resin surface and formation of protrusions are problematic. As for the protrusions on the resin surface, the shape at the time of molding is important even if the particle size of the flame retardant is the same, and those that are easily deformed because the flame retardant itself has a flexible structure at the time of molding are preferable. For this reason, in addition to phosphorus atom content, nitrogen atom content and incombustible component content, flame retardants are selected in terms of decomposition temperature, molecular weight, particle size, particle size distribution, and shape during molding (linear, branched and crosslinked). And the compatibility and dispersibility with the resin are important factors.

  Next, the thermoplastic polyester resin used in the present invention will be described. There is no restriction | limiting in particular as a thermoplastic polyester resin used by this invention, Any polyester resin can be used regardless of the structural component, if it is thermoplastic. The present invention has been found that extremely excellent flame retardancy can be imparted to a resin by using a flame retardant aid in combination with an inorganic phosphorus flame retardant. Therefore, as long as it can be molded using the obtained flame-retardant polyester resin composition, or can be produced by spinning and drawing, not only wet and dry methods, but also known methods can be used. Moreover, the reason for limiting to the thermoplastic polyester resin is that the waste polyester can be reused if it is thermoplastic.

  Examples of the dicarboxylic acid component constituting such a thermoplastic polyester resin include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, bis- ( 4-carboxyphenyl) sulfone, bis (4-carboxyphenyl) ether, 1,2-bis (4-carboxyphenyl) ethane, 5-sodium sulfoisophthalic acid, diphenyl-p, p'-dicarboxylic acid, p-phenylenedi Examples include acetic acid and trans-hexahydroterephthalic acid and their alkyl esters, aryl esters, and ethylene glycol esters. On the other hand, as glycol components, ethylene glycol, butylene glycol, 1,2-propylene glycol, 1,4-butanediol, trimethylene glycol, 1,6-hexanediol, 1,4-cyclohexanediol, neopentyl glycol 1,4-cyclohexanedimethanol, bisphenol A, bisphenol S and ethylene glycol, polyethylene glycol adducts thereof, diethylene glycol, and polyethylene glycol. Further, a condensation type polyester resin of hydroxycarboxylic acid such as polylactic acid can be used. Among these, as the thermoplastic polyester resin of the present invention, polyethylene terephthalate and polybutylene terephthalate which are used in large quantities and can be obtained at low cost are preferable. Moreover, these thermoplastic polyester resins may be used alone or in combination.

  The number average molecular weight of the thermoplastic polyester resin is not particularly limited, but is preferably 1,000 to 100,000, and more preferably 5,000 to 50,000. If it is 1,000 or more, yarn formation is possible, and if it is 100,000 or less, an increase in viscosity can be suppressed, so that melt spinning is easy. In addition, said number average molecular weight can be measured by a gel permeation chromatography (GPC), for example. Usually, the above-mentioned number average molecular weight can be substituted by an intrinsic viscosity which is easy to measure, and the intrinsic viscosity is 0.05 to 2.53, preferably 0.19 to 1.40.

  Moreover, in this invention, the discarded material after using as this thermoplastic polyester and the end material at the time of manufacturing an industrial product can also be utilized. That is, the thermoplastic polyester resin of the present invention includes a recycled polyester resin. In the present invention, the discarded polyester resin includes a wide range of polyester resins other than products, such as used polyester resins, pre-use but non-standard products, and not used as products. Examples of such waste polyester resins include synthetic resin manufacturers, film manufacturers, PET bottle manufacturers, polyester materials produced by polyester polymerization manufacturers, polyester resins that are below the standard grade, and polyester resins obtained by the general waste container packaging recycling method. it can. This makes it possible to material-recycle waste materials that should be discarded or subject to incineration, contributing to environmental conservation and economically advantageous.

  In the flame retardant polyester resin composition used in the present invention, all the flame retardant polyester resins may be such waste polyester resins. Rather, if all of the thermoplastic polyester resin is used, the waste material can be used effectively as a raw material component, and it is not necessary to incinerate what is originally incinerated. Can contribute.

  In the flame-retardant polyester resin composition used in the present invention, the content of the inorganic phosphorus flame retardant is 0.1 to 12% by mass, preferably 0.5 to 8% by mass, based on the total weight of the polyester resin composition. %, More preferably 0.6 to 5% by mass, and the flame retardant auxiliary content is 0.05 to 5% by mass, preferably 0.1 to 4% by mass, more preferably 0.12 to 4% by mass, Particularly preferably 0.3 to 4% by mass, and particularly preferably 0.3 to 3% by mass, and the content of the thermoplastic polyester resin is 83 to 99.85% by mass, preferably 88 to 99.4% by mass. More preferably, it is 91-99.28 mass%. If the inorganic phosphorus flame retardant and the flame retardant auxiliary are less than 0.1 and 0.05% by mass, respectively, it becomes difficult to impart sufficient flame retardancy to the resin, and if it exceeds 10 and 5% by mass, spinning is performed. This is because the physical properties of the thin molded article and the physical properties of the yarn are significantly reduced. further. In addition to the content of each component of the composition, the total content of the inorganic phosphorus flame retardant and the flame retardant aid is preferably in the range of 1.05 to 9% by mass, more preferably 1.5 to 6% by mass. It is desirable that

  In the flame retardant polyester resin composition used in the present invention, the ratio of the inorganic phosphorus flame retardant and the flame retardant aid to the thermoplastic polyester resin should satisfy the above ratio. In addition to this, other additives may be further added as long as the moldability and the properties of thin molded articles, or the spinnability and fiber characteristics are not impaired. Additives that can be included in the inorganic phosphorus flame retardants of the present invention include other organic phosphorus compounds, brominated flame retardants, aluminum hydroxide, magnesium hydroxide, antimony oxide, sodium carbonate, and mixtures thereof. Examples include flame retardants. Examples of additives that can be contained in the resin composition of the present invention include organic, inorganic pigments and other colorants, calcium carbonate, talc and other flame retardants, phthalates, phosphates, aliphatic carboxylic acids, and the like. There are stabilizers such as plasticizers, inorganic salts and metal soaps, antioxidants such as alkylphenols and alkylenebisphenols, UV absorbers such as salicylic acid esters, benzotriazoles and hydroxybenzophenones.

  As the colorant used in the present invention, known ones such as organic pigments and inorganic pigments can be used. For example, organic pigments made of azo, anthraquinone, quinacridone, cyanine green and cyanine blue, dioxazine, phthalocyanine, α-phthalocyanine and β-phthalocyanine, perinone, berylene, and polyazo And titanium yellow, ultramarine, iron oxide, petal, zinc white, titanium oxide based on anatase titanium and rutile titanium oxide, and carbon inorganic pigments composed of carbon black, graphite, spirit black, channel black and furnace black However, it is not limited to these. Usually, by selecting a plurality of appropriate pigments from these colorants and mixing and using appropriate amounts, the flame-retardant molded articles and fibers can be colored as desired. In particular, in the case of fibers, light resistance can be imparted to the spun fibers by directly blending the colorant with the raw material as a resin composition. When used in automobile interior materials as a flame retardant, light resistance is an extremely important factor because it is always susceptible to deterioration by light.

  In order to prepare the resin composition used in the present invention, it is preferable to use a master batch of an inorganic phosphorus flame retardant, a flame retardant aid and a colorant. For example, a master batch containing an inorganic phosphorus-based flame retardant, a flame retardant aid and / or a colorant is prepared in advance on a master batch base material, these are mixed, and a thermoplastic polyester resin is further mixed and melted. In order to melt and mix the masterbatch and the thermoplastic polyester resin, it is not necessary to employ a special method, and a conventionally known method may be employed. For example, the chips before melting may be mixed and then melted, or both may be melted separately and then statically mixed using a static mixer or the like immediately before spinning. However, the inorganic phosphorus flame retardant, flame retardant aid and colorant may be melt mixed without using a masterbatch. In particular, in the case of using a resin-coated flame retardant, it is not necessary to use a masterbatch in particular because it is excellent in compatibility with the polyester resin, and can be directly mixed and melted in the polyester resin.

  In addition, when using a masterbatch containing an inorganic phosphorus flame retardant and / or a flame retardant aid, the inorganic phosphorus flame retardant and / or flame retardant aid is contained in the master batch in an amount of 5 to 70% by mass, More preferably, it is preferable to contain 10-50 mass%. If the amount is 5% by mass or more, the amount of the inorganic phosphorus flame retardant and / or flame retardant aid is sufficient, so that it is meaningful to use a masterbatch. The preparation of the batch itself can be adjusted well without difficulty.

  The masterbatch base material used for the masterbatch of inorganic phosphorus flame retardant and / or flame retardant aid is a thermoplastic resin that loses the properties of the resin composition after blended into the polyester resin composition. It can be used without particular limitation as long as it is not present. Specifically, at least one selected from the group consisting of a thermoplastic polyester resin and a polypropylene resin is preferable. Among them, a polyethylene terephthalate polyester or a polybutylene terephthalate polyester as a main component, polypropylene, ethylene -A propylene block copolymer etc. are preferable. In addition, such a master batch can use a commercial item.

  In the master batch of the colorant, the colorant is contained in the master batch in an amount of 1 to 60% by mass, more preferably 10 to 35% by mass, and particularly preferably 20 to 30% by mass. If it is 1% by mass or more, a desired color can be obtained by blending the colorant, while if it is 60% by mass or less, the colorant can be mixed uniformly. The resin used for the masterbatch (masterbatch base material) is the same as that used for the inorganic phosphorus flame retardant and / or flame retardant aid, that is, a thermoplastic resin that is blended in the polyester resin composition. Can be used without particular limitation as long as it does not lose the properties of the resin composition, and the most preferable one is at least one selected from the group consisting of thermoplastic polyester resins and polypropylene resins. it can.

  In addition, when using a master batch of an inorganic phosphorus flame retardant, a flame retardant aid and a colorant as a raw material of the flame retardant original polyester fiber, it is preferable to manufacture each master batch separately and mix them during spinning. . In particular, inorganic phosphorus-based flame retardants and colorants are often highly reactive, and tend to react with each other and cause deterioration and discoloration at high temperatures and high concentrations that produce a masterbatch. For this reason, it may hinder the expression of subtle colors, especially in textile products, and may cause quality troubles. In addition, the masterbatch base material used for the masterbatch is the same as the thermoplastic resin used for the thin product and fiber as much as possible in order to stably maintain the physical properties of the thin product and the fiber product and to improve recyclability. It is preferable to use a single material.

  Further, the flame retardant thin molded article and the flame retardant polyester fiber can be obtained by fiberizing the flame retardant resin composition by a known molding method and melt spinning method. The shape in that case is arbitrary, and in particular in the case of fibers, there are round cross-section fibers, irregular cross-section fibers, hollow fibers, and the like.

  The second aspect of the present invention relates to a flame-retardant polyester fiber obtained by melt-mixing a flame-retardant polyester resin composition and then melt-spinning the fiber cotton, such as short fibers or filaments, or the fiber cotton. Can be simply compressed and used as a felt or as it is as a flame retardant filler. At this time, the thickness (single yarn fineness) of the flame-retardant polyester fiber of the present invention is preferably 1.0 to 660 dtex, more preferably 2.0 to 220 dtex, and particularly preferably 3.3 to 3. 17.0 dtex. If the thickness is 1.0 dtex or more (single yarn fineness), the occurrence of yarn breakage can be suppressed. On the other hand, if the thickness is 660 dtex or less, the rigidity does not make processing difficult. Such short fibers or filaments may be used alone or in combination with other fibers to be woven or knitted by a conventionally known method to form a fabric. For example, a satin weave using a flame-retardant polyester fiber yarn as a weft and one ordinary white polyester drawn yarn as a warp, or a double weave with a flame-retardant fiber yarn arranged on one side as a fabric Also good.

  The third aspect of the present invention is an inorganic phosphorus flame retardant or a master batch containing the flame retardant, a flame retardant aid or a master batch containing the flame retardant aid, a master batch containing a colorant, and a thermoplastic polyester resin. Is a method for producing a flame-retardant polyester fiber, characterized by melt-mixing and then melt spinning.

  As described above, melt spinning is not limited to wet and dry methods, and a known method can be used. Preferably, the dry spinning method has a take-up speed of 300 to 1000 m / min, and the spinning temperature is 200 to 300 ° C. It is preferable to carry out under optimum conditions by changing the conditions as appropriate according to the yarn formation state. In particular, from the viewpoint of preventing the decomposition of the inorganic phosphorus flame retardant and the flame retardant auxiliary during melt spinning, the spinning temperature is adjusted so that the inorganic phosphorus flame retardant and the flame retardant auxiliary are not significantly decomposed. It is preferable to set a plurality of temperatures in consideration of the decomposition temperature and thermal history of the system flame retardant and flame retardant aid. In the subsequent stretching step, a conventionally known stretching method can be used, and the stretching ratio is about 1.0 to 6.0.

  A fourth aspect of the present invention is a flame retardant containing 5 to 100% by mass of the flame retardant polyester fiber. As a flame retardant, it can be prepared using the above-mentioned flame retardant polyester fiber, felt, cloth, fiber cotton and the like. Under the present circumstances, it is preferable that this flame-retardant material contains 5-100 mass% of flame-retardant polyester fibers, More preferably, it is 10-50 mass%, Especially 15-30 mass%. Since the flame-retardant polyester fiber of the present invention has a large flame-retardant effect, it can be effectively used as a flame-retardant material when it contains at least 5% by mass. Therefore, it can be blended with the conventional member to impart flame retardancy, and since the blending amount is small, the product price can be reduced, and the flame retardant effect can be achieved without impairing the texture of the conventional member. Can be granted.

  Flame retardant materials containing such flame retardant polyester fibers include, for example, sheets used as interior materials for automobiles, linings such as pyragarnish and rear parcels, floor linings such as mats and carpets, sun visors, package trays, It can be used as parts such as assist grips, filter materials, heat insulating materials, various sound insulating materials and vibration isolating materials.

  Originally, it is difficult to add a substance that does not dissolve in the thermoplastic polyester resin and spin it into the fiber. Especially, the thermoplastic polyester resin and the inorganic phosphorus flame retardant are incompatible with each other, so that yarn breakage or the like occurs. It was easy. However, in the present invention, by using a master batch, the additive can be easily and uniformly dispersed by a known melt mixing method, and as a result, spinning can be performed without breaking the yarn. In particular, the method of the present invention is characterized in that a conventional melt spinning method can be employed as it is while blending an inorganic phosphorus flame retardant. The melt mixing using this master batch is the same method as described in the preparation of the resin composition of the present invention.

  EXAMPLES Examples, comparative examples and reference examples of the present invention will be described in detail below. However, the scope of the present invention is not limited to these examples. The evaluation was performed by the following method.

  (1) Regarding the spinnability, the spinnability was evaluated based on the following criteria for spinning per 1 t of the yarn when the flame-retardant original polyester fiber yarn was obtained by spinning. A: Yarn breakage is less than 5 times, O: Yarn breakage is 5 times or more and less than 15 times, Δ: Yarn breakage is 15 times or more, X: Not normal yarn and cannot be spun.

  (2) Flame retardancy was measured using a measurement method according to the method described in JP-A-2001-279073 and a 45 ° C. combustion test method according to JIS L1091 D method. In the former, the short fiber bundle is opened, weighed so that the sample becomes 10 g, and loaded into a predetermined combustion test instrument so that the opening direction is aligned. Then, the flame was applied to the test piece for 10 seconds, the way of burning was observed, the time from the application of the flame to ignition was measured, and the average value from 6 tests was obtained. In the latter, 1 g of short fiber bundles are uniformly inserted into the center of the test piece support coil so as to have a length of 100 mm, and the inclination of 45 ° is maintained. Heat until the burner flame comes into contact with the lower end of the test piece and the test piece melts and the combustion is extinguished. Furthermore, flame contact is made again at the lowermost end of the remaining test piece, this operation is repeated, and the number of times of flame contact until melting and burning to a position of 90 mm from the lower end of the test piece is obtained, and an average value from five tests is obtained. Asked.

  (3) Mechanical properties (strength and elongation) were measured with a desktop material testing machine STA-1150 (manufactured by Orientec Co., Ltd.). Ten measurements were made on one sample. It can be said that the higher the strength and elongation, the more excellent the mechanical properties.

  (4) The decomposition temperature of the inorganic phosphorus flame retardant is measured using a DSC device. The decomposition temperature is the intersection temperature between the baseline and endothermic peak rise based on gas generation. Using.

  (5) The decomposition peak temperature of the flame retardant aid was determined by measuring the weight loss peak temperature obtained by differentiating the temperature-weight loss curve in the thermogravimetric analysis of the flame retardant aid using a thermogravimetric analyzer.

  (6) The intrinsic viscosity of the polyethylene terephthalate resin is determined by measuring the relative viscosity η of a solution in which 8 g of a polyethylene terephthalate sample is dissolved in 100 ml of orthochlorophenol using an Ostwald viscometer (25 ° C.). The intrinsic viscosity obtained by the equation is related to the number average molecular weight by the following viscosity equation.

(Examples 1-4)
Mass% ammonium polyphosphate 1 shown in Table 1 (manufactured by Clariant, product name Pekoflam TC204, white powder, average particle size 8 μm, phosphorus atom content 32 mass%, nitrogen atom content 15 mass%, polymerization degree 1000, decomposition Each master batch containing 2,3-dimethyl-2,3-diphenylbutane (manufactured by NOF Corporation, NOFMER BC, decomposition peak temperature 240 ° C., boiling point 152 ° C. of decomposition fragment (cumene)), A polyethylene terephthalate resin (PET resin 1) of mass% shown in Table 1 having an intrinsic viscosity of 0.60 obtained by mixing the polyethylene terephthalate resin from the waste PET bottle and the waste PET film was melt-mixed with an extruder, The flame-retardant polyester resin composition having the ratio shown in 1 was obtained. Subsequently, these were melt-spun by a dry method at a take-up speed of 520 m / min and a spinning temperature of 230 to 285 ° C. to obtain flame-retardant short fibers (flame-retardant fibers 1 to 4) having a single yarn fineness of 6.6 dtex.

  The flame retardancy fibers 1 to 4 thus obtained were examined for spinnability and mechanical properties (strength and elongation). In addition, flame retardant cotton samples (short fiber bundles opened and short fiber bundles) were prepared to examine flame retardancy, and the results are shown in Table 1 as Examples 1 to 4.

(Comparative Examples 1-5)
Spinning is performed in accordance with Example 1 except that polyethylene terephthalate resin (PET resin 1), ammonium polyphosphate 1 and 2,3-dimethyl-2,3-diphenylbutane of mass% shown in Table 1 are used. Short fibers (flame retardant fibers 1 to 7) were obtained. These flame retardant fibers 1 to 5 were examined for spinnability, flame retardancy and mechanical properties (strength and elongation) in the same manner as in Example 1, and the results are shown in Table 1 as Comparative Examples 1 to 5. .

  From Examples 1 to 4 and Comparative Examples 1 to 5, if the content of the flame retardant and / or flame retardant auxiliary used in the present invention exceeds a certain amount, the spinnability is significantly lowered so that spinning becomes impossible. As the amount added increases, the flame retardancy increases, and a synergistic effect of the flame retardant aid is observed. Further, no adverse effect on the mechanical properties due to the increase in the content of the flame retardant aid was observed.

(Examples 5 to 10)
Spinning is performed in accordance with Example 1 except that polyethylene terephthalate resin (PET resin 1), ammonium polyphosphate 1 and 2,3-dimethyl-2,3-diphenylbutane of mass% shown in Table 2 are used. Short fibers (flame retardant fibers 5 to 10) were obtained. These flame-retardant fibers 5 to 10 were examined for spinnability, flame retardancy and mechanical properties (strength and elongation) in the same manner as in Example 1, and the results are shown in Table 2 as Examples 5 to 10. .

(Comparative Example 6)
Except not using 2,3-dimethyl-2,3-diphenylbutane, it spun according to Example 5 and obtained the flame-retardant short fiber (comparative flame-retardant fiber 6). The comparative flame retardant fiber 6 was examined for spinnability, flame retardancy and mechanical properties (strength and elongation) in the same manner as in Example 5. The result was set as Comparative Example 6, and Comparative Examples 2 to 5 were combined. It was shown to.

  From Examples 5 to 10 and Comparative Examples 2 to 6, when the content of the flame retardant and / or flame retardant auxiliary used in the present invention exceeds a certain amount, the spinnability is significantly lowered so that spinning becomes impossible. As the amount added increases, the flame retardancy increases, and a synergistic effect of the flame retardant aid is observed. Further, no adverse effect on the mechanical properties due to the increase in the content of the flame retardant aid was observed.

(Examples 11 to 15)
Spinning is performed in accordance with Example 1 except that polyethylene terephthalate resin (PET resin 1), ammonium polyphosphate 1 and 2,3-dimethyl-2,3-diphenylbutane of mass% shown in Table 3 are used. Short fibers (flame retardant fibers 11 to 15) were obtained. These flame retardant fibers 11 to 15 were examined for spinnability, flame retardancy, and mechanical properties (strength and elongation) in the same manner as in Example 1. The results are shown in Table 3 as Examples 11 to 15. .

(Comparative Example 7)
Except not using 2,3-dimethyl-2,3-diphenylbutane, spinning was performed according to Example 11 to obtain a flame-retardant short fiber (comparative flame-retardant fiber 7). The comparative flame retardant fiber 7 was examined for spinnability, flame retardancy and mechanical properties (strength and elongation) in the same manner as in Example 5. The results were set as Comparative Example 7, and Comparative Examples 2 to 5 were combined. It was shown to.

When the content of the flame retardant and / or flame retardant aid used in the present invention from Examples 11 to 14 and Comparative Examples 2 to 5 and 7 exceeds a certain amount, the spinnability deteriorates so much that spinning becomes impossible. Until then, as the amount added increases, the flame retardancy increases, and a synergistic effect of the flame retardant aid is seen. In addition, although there is no adverse effect on the mechanical properties due to the increase in the content of the flame retardant aid, the mechanical properties are lowered when the content of the flame retardant exceeds a certain amount.
(Examples 15 to 25)
Instead of PET resin 1, ammonium polyphosphate 1 and 2,3-dimethyl-2,3-diphenylbutane, or together with any of these, the mass% of PET resin 2 shown in Table 2 (Mitsubishi Chemical Corporation, product) Name “NOVAPEX”), inorganic red phosphorus, melamine polyphosphate (manufactured by Sanwa Chemical Co., Ltd., product name MPP-A, white powder, average particle size 4 μm, phosphorus content 15 mass%, decomposition temperature 320 ° C.), poly Phenoxyphosphazene (manufactured by Otsuka Chemical Co., Ltd., product name phosphazene, phosphorus content 13 mass%, decomposition temperature 350 ° C. or higher), tris (diethylphosphinic acid) aluminum (manufactured by Clariant, product name Pekoflam STC, phosphorus atom content 23 % By mass, average particle diameter of 4 μm, decomposition temperature of 300 ° C. or higher) and diisopropylbenzene oligomer (Japanese Patent Laid-Open No. 2001-1) M-, p-mixed diisopropylbenzene oligomer synthesized according to Reference Example 1 of No. 835; number average molecular weight 950; average value 5.9 of n in general formula (2); decomposition peak temperature 265 ° C., decomposition fragment Spinning was carried out in accordance with Example 1 except that a boiling point of 211 ° C. was used or used together to obtain flame-retardant short fibers (flame-retardant fibers 15 to 25). These flame retardant fibers 15 to 25 were examined for spinnability, flame retardancy and mechanical properties (strength and elongation) in the same manner as in Example 1, and the results are shown in Table 4 as Examples 15 to 25. .

(Comparative Examples 8-11)
Except not using 2,3-dimethyl-2,3-diphenylbutane, it spun according to Examples 15-18, and obtained the flame-retardant short fiber (comparative flame-retardant fiber 8-11). These comparative flame retardant fibers 8 to 11 were examined for spinnability, flame retardancy, and mechanical properties (strength and elongation) in the same manner as in Examples 15 to 18, and the results are shown in Table 5 as Comparative Examples 8 to 11. It was shown to.

(Example 26)
Flame retardant processed fibers 2, 6, 8, 10, 11, and 13 obtained in Examples 2, 6, 8, 10, 11, and 13 were treated with flame retardant untreated fibers (denoted as untreated fibers in the table). Were blended in the proportions shown in Table 6 to prepare flame retardant cotton (short fiber bundles opened and short fiber bundles), which were designated as flame retardants 1-6. These flame retardancy was investigated. In addition, a flame-retardant processed untreated fiber is an untreated fiber which spun the polyester resin composition prepared like Example 1 except not including a flame retardant and a flame retardant adjuvant as a polyester resin composition. . For the evaluation of the flame retardancy of the flame retardants 1 to 6 (flame retardant cotton), the same method as in Example 1 was adopted. The results are shown in Table 6.

(Reference example)
In order to estimate the decomposition temperature of various flame retardant aids composed of 1,2-diphenyl derivatives and / or diisopropylbenzene oligomers, the following is based on the decomposition temperature of 2,3-dimethyl-2,3-diphenylbutane. Formulas (5) and (6);

(Here, E _d is the difference between the standard heat of decomposition of the flame retardant aid seeking, E _s is the difference between the standard heat on standards become flame retardant aid, T _d is determined decomposition temperature of the flame retardant aid, T _s is the standard decomposition temperature of the flame retardant aid.) The results are shown in Table 7. For the calculation of the standard heat of formation, Winmostar MOPAC AM1 (MOP6W70) (Senda, “Development of Molecular Computation Support System Winmostar”, Idemitsu Technical Report, 49, 1, 106-111 (2006)) was used. In addition, the boiling point of the decomposition fragment is the actual value of the boiling point of the corresponding monocyclic aromatic hydrocarbon, or the following formula (7):

(Where t _b is the normal boiling point (° C.), n is the number of carbon atoms of the aromatic hydrocarbon, a and k are constants, and in the case of monocyclic aromatic hydrocarbons, a = 680, k = −614. .4) and the results are shown in Table 7. The temperature-weight loss curve of 2,3-dimethyl-2,3-diphenylbutane and its derivative curve are shown in FIG. 1, and a 30% masterbatch is shown in FIG. 2, and the decomposition peak temperature was determined. It can be seen that when 30% masterbatch is used, after decomposition of 2,3-dimethyl-2,3-diphenylbutane, recombination occurs due to the solvent effect of the surrounding polymer, and the decomposition peak temperature increases. Therefore, the decomposition peak temperature of the flame retardant aid was determined as the decomposition peak temperature. Similarly, the estimated value of the decomposition peak temperature of the diisopropylbenzene oligomer was 241 ° C., but the actually measured value of the 30% master batch was 265 ° C. In the case of the diisopropylbenzene oligomer, since the molecular weight is significantly lowered in the latter half of the decomposition, it can be seen that the decomposition peak temperature is about 24 ° C. higher than the decomposition peak temperature obtained by calculation.

Claims (15)

A thermoplastic polyester resin, at least one inorganic or organic phosphorus flame retardant selected from the group consisting of inorganic red phosphorus, inorganic phosphorus-nitrogen compounds, and organic metal phosphates, and the following general formula (1);
(Wherein R _{1 to} R ₄ are an alkyl group having 1 to 3 carbon atoms, and R ₅ is a hydrogen atom or an alkyl group having 1 to 7 carbon atoms), and a 1,2-diphenylethane derivative represented by The following general formula (2);
(Wherein n is an average value of 2 to 50), a flame retardant polyester resin composition containing at least one flame retardant auxiliary of diisopropylbenzene oligomer,
Based on the total weight of the thermoplastic polyester resin composition, the content of the inorganic or organic phosphorus flame retardant is 0.1 to 12% by mass, and is a 1,2-diphenylethane derivative and / or diisopropylbenzene oligomer. Melting and mixing the flame retardant polyester resin composition having a content of the flame retardant aid of 0.05 to 5% by mass and a content of the thermoplastic polyester resin of 83 to 99.85% by mass A flame-retardant polyester fiber obtained by melt spinning.   Based on the total weight of the thermoplastic polyester resin composition, the content of the inorganic or organic phosphorus flame retardant is 0.5 to 8% by mass, and is a 1,2-diphenylethane derivative and / or diisopropylbenzene oligomer. The flame retardant polyester fiber according to claim 1, wherein the content of the flame retardant aid is 0.1 to 4% by mass.   Based on the total weight of the thermoplastic polyester resin composition, the content of the inorganic or organic phosphorus flame retardant is 0.6 to 5% by mass, and is a 1,2-diphenylethane derivative and / or diisopropylbenzene oligomer. The content of the flame retardant aid shown is 0.12 to 4% by mass, and the total content of inorganic or organic phosphorus flame retardant and flame retardant aid is in the range of 1.5 to 6% by mass. The flame-retardant polyester fiber according to claim 1 or 2.   The decomposition peak temperature of the flame retardant aid represented by a 1,2-diphenylethane derivative and / or diisopropylbenzene oligomer is 200 ° C or higher, and the boiling point of the decomposed fragment is 400 ° C or lower. The flame-retardant polyester fiber according to any one of the above.   The inorganic phosphorus-nitrogen compound is at least one selected from the group consisting of ammonium polyphosphate, melamine polyphosphate, and phosphazenes, and the metal metal phosphate is tris (diethylphosphinic acid) aluminum. Item 5. A flame retardant polyester fiber according to any one of Items 1 to 4.   The flame-retardant polyester fiber according to any one of claims 1 to 5, wherein the thermoplastic polyester resin includes a recycled polyester resin.   The flame-retardant polyester fiber according to any one of claims 1 to 6, wherein the flame-retardant aid is 2,3-dimethyl-2,3-diphenylbutane and / or diisopropylbenzene oligomer.   The difficulty according to any one of claims 1 to 7, wherein the inorganic phosphorus-nitrogen compound is a linear compound having at least one selected from the group consisting of phenoxyphosphazene, propoxyphosphazene, and diaminophosphazene as a basic skeleton. Flammable polyester fiber.   The flame-retardant polyester fiber according to any one of claims 1 to 8, wherein a decomposition temperature of the inorganic phosphorus-nitrogen compound is 270 ° C or higher.   The flame-retardant polyester fiber according to any one of claims 1 to 9, wherein the phosphorus-based flame retardant is a powder having an average particle size of 30 µm or less.   The flame-retardant polyester fiber according to any one of claims 1 to 10, wherein the fiber has a thickness of 2.0 to 220 dtex. A method for producing a flame retardant polyester fiber according to any one of claims 1 to 11,
The masterbatch containing the phosphorus flame retardant, the masterbatch containing the flame retardant aid, and the flame retardant polyester resin composition comprising the thermoplastic polyester resin are melt-mixed, and then a take-off speed of 520 to 520 by a dry method. A method for producing a flame-retardant polyester fiber, comprising melt spinning at 1,000 m / min.   The masterbatch containing the phosphorus flame retardant, the masterbatch containing the flame retardant aid, and the flame retardant polyester resin composition comprising the thermoplastic polyester resin are melt-mixed, and the take-off speed is 520 to 1 by a dry method. The method for producing a flame-retardant polyester fiber according to claim 12, wherein the melt spinning is performed at 1,000,000 m / min and a spinning temperature of 200 to 300 ° C.   A flame retardant containing 5 to 100% by mass of the flame retardant polyester fiber according to any one of claims 1 to 11 or the flame retardant polyester fiber obtained by the production method according to claim 12 or 13.   An automotive interior material using the flame retardant according to claim 14.