JP2009179712A - Fiber-reinforced flame-retardant resin molded article and method for molding the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fiber-reinforced flame-retardant resin molded article having improved strength such as impact resistance, securing high flame retardancy by the addition of a small amount, and obtained by using a biomass material as a main raw material. <P>SOLUTION: The fiber-reinforced flame-retardant resin molded article is composed of a fiber-reinforced flame-retardant resin composition comprising a thermoplastic polyester resin, a flame retardant and a thermoplastic polyester fiber. The thermoplastic polyester resin contains one or more kinds of an aliphatic polyester resin and an aromatic polyester resin wherein at least a part of the raw materials includes a biomass material. The aliphatic polyester resin includes a polylactic acid resin, or one or more kinds of a microorganism-produced resin (polyhydroxyalkanoate), a polybutylene succinate, a polyethylene succinate and a polytrimethylene terephthalate, and the melting point of the thermoplastic polyester fiber is lower than the decomposition point of the thermoplastic polyester resin. The thermoplastic polyester fiber has a structure interwoven into the inside of the molded article in a network shape. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a flame retardant resin composition containing a thermoplastic polyester resin, in particular, an aliphatic polyester resin containing a biomass material as a raw material, such as image output devices such as copying machines, laser printers, and ink jet printers, and home appliances. It is effective for use in parts and products using thermoplastic polyester resin as a material in parts that require flame retardance, such as internal parts of electrical and electronic equipment and automobile products.

  As a prior art of the present invention, there is an invention described in Japanese Patent Application Laid-Open No. 2006-111858, “resin composition and molded article comprising the same”. An object of this conventional technique is to provide a resin composition having an excellent impact strength and a white appearance without pearl luster, a resin composition exhibiting high flame retardancy, and a molded product comprising the same. And 10 to 75 parts by weight of one or more resins selected from polylactic acid resins and cellulose esters, 25 to 90 parts by weight of aromatic polycarbonate resins, and a fragrance with one or more resins selected from polylactic acid resins and cellulose esters. 1 to 50 parts by weight of a resin composition obtained by adding 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of the polycarbonate resin, the resin composition containing a flame retardant, and the resin composition containing a fluorine compound, The above resin composition containing an epoxy compound, and a molded product comprising the same.

  Further, as another conventional technique, there is an invention described in Japanese Patent Application Laid-Open No. 2007-130868, “Method for producing resin molded product”. This prior art is a method for producing a flame-retardant resin molded product containing plant fibers as a filler, and a method for producing a resin molded product capable of stably obtaining a resin molded product having the desired characteristics. The first step is to provide a plant fiber containing at least one of boric acid and a boric acid compound to make the plant fiber flame retardant, and to obtain a flame retardant treatment obtained in the first step. A second step of directly feeding each of the plant fiber, the matrix resin, and the metal hydroxide into an injection molding machine, the plant fiber flame-treated with the injection molding machine, and the matrix resin. And a third step of injection-molding a plasticized resin composition by kneading the metal hydroxide with heating.

  Furthermore, as another prior art, there is an invention described in JP-T-2007-51803, “halogen-free flame-retardant polyester composition”. This prior art comprises a polymer composition comprising 30 to 67% by weight of at least one thermoplastic polyester polymer and 0 to 15% by weight of other polymers, of which 0 to 0.3% by weight is a fluoropolymer, A flame retardant system comprising 55% by mass of melamine cyanurate, 0 to less than 2% by mass of phosphorus-containing flame retardant containing no elemental phosphorus, and 0 to 5% by mass of inorganic flame retardant synergist not containing phosphorus; It is a halogen-free flame-retardant thermoplastic polyester molding composition comprising 10 to 10% by mass of other additives (of which 0 to 5% by mass is a fibrous reinforcing agent). The invention is also a molded part for use in electrical or electronic applications comprising the polyester composition.

  As another conventional technique, there is an invention described in Japanese Patent Application Laid-Open No. 2007-056247, “Flame-retardant resin composition and molded product made thereof”. This prior art is intended to provide a flame-retardant resin composition excellent in appearance and surface impact of a molded article having no pearly luster, and a molded article comprising the same. A high amount of acrylic resin or styrene resin unit by grafting with respect to a total of 100 parts by weight of the aromatic polycarbonate resin 5 to 95% by weight and the polylactic acid resin 5 to 95% by weight and the aromatic polycarbonate resin 5 to 95% by weight. A resin composition comprising 0.1 to 50 parts by weight of a molecular compound and 0.1 to 50 parts by weight of a flame retardant.

  Furthermore, as another conventional technique, there is an invention described in Japanese Patent Application Laid-Open No. 2004-099703, “a flame retardant resin composition and a flame retardant molded article”. This prior art aims to provide a resin composition containing a lactic acid resin that imparts flame retardancy and suppresses a decrease in molecular weight, and a molded product obtained from this resin composition. A flame retardant resin composition in which a non-halogen nonionic flame retardant and / or a nitrogen flame retardant is added to a resin composition containing a lactic acid resin as a main component is used.

  Furthermore, as another conventional technique, there is an invention described in JP-T-2006-502888, "an article containing a fiber-reinforced thermoplastic polymer composition". This prior art is a method for producing a fiber reinforced thermoplastic polymer composition and a secondary processed article therefrom, in which a thermoplastic polymer, a masterbatch containing an elastomer and a reinforcing fiber material are compounded and extruded. , And immediately formed into a secondary processed product. And this secondary processed product is made by compression molding, vacuum molding, thermoforming, injection molding, blow molding, profile extrusion, or a combination thereof.

   Furthermore, as another prior art, there is an invention described in Japanese Patent Application Laid-Open No. 2003-232014, “Method for constructing sound insulation panel”. This prior art is light and easy to handle at least during installation, and after installing the outer frame made of fiber reinforced resin that is the basis of the panel, it is possible to adopt a method of filling various things with appropriate unit weight, The purpose is to provide an excellent sound insulation panel that does not require large heavy machinery, is inexpensive, is extremely easy to install, and can be installed in a short period of time. The portion forming the outer frame of the panel is made of a fiber reinforced resin containing at least 5 to 70% by weight of reinforcing fibers made of inorganic fibers and / or organic fibers, and is formed by the fiber reinforced resin. The sound insulation panel made of fiber reinforced resin containing the filler can be molded inside.

   Furthermore, as another conventional technique, there is an invention described in Japanese Patent Application Laid-Open No. 2001-098166, “a flame retardant polymerization composition”. This prior art aims to provide a highly safe and excellent flame retardant composition, and the composition is a flame retardant composition of a polymer composition containing a filler such as glass fiber. And comprising at least one polyphosphate, a sulfur-containing compound, a catalyst and a flame retardant active additive of a nitrogen-containing compound such as melamine.

  The closest prior art to the invention of this application is the invention described in Japanese Patent Application Laid-Open No. 2004-155946, “Modifier for thermoplastic resin, and thermoplastic resin composition and product using the same”. And this prior art aims at providing the modifier for thermoplastic resins which expresses a flame retardance and a molded article appearance when added to a thermoplastic resin, and a thermoplastic resin composition using the same. It is a modifier for a thermoplastic resin comprising polytetrafluoroethylene and a polymer having a glass transition temperature (Tg) of 40 ° C. to 98 ° C., and with respect to 100 parts by mass of the thermoplastic resin. Thus, the thermoplastic resin composition is added with the thermoplastic modifier so that the amount of polytetrafluoroethylene added is 0.001 to 20 parts by mass.

  In particular, regarding the flame retardant, there is also the invention of WO 2007/010786, “Flame-retardant resin composition”. The purpose of this prior art is to provide a flame retardant resin composition that does not contain halogen elements and phosphorus elements, is safe and has no adverse effects on the environment and the human body, and has excellent flame resistance. It is difficult to contain at least one of a polyester-based resin and an organic sulfonic acid compound, an organic carboxylic acid compound, or a metal salt thereof having a content of 0.0002 to 0.8 part by mass with respect to 100 parts by mass of the thermoplastic resin. It is a flammable resin composition.

[Problems of the prior art]
Many resin parts are used in parts used in image output devices using electrophotographic technology, printing technology or inkjet technology such as copiers and laser printers, electrical and electronic equipment such as home appliances, and interior parts of automobiles. However, these products are required to have flame retardancy as a resin material for preventing the spread of fire.
In particular, in a copying machine, there is a fixing unit that becomes hot inside, and a resin material is also used in the vicinity of the fixing unit. In addition, there are units that generate a high voltage, such as a charging unit, and power supply units that are 100 V AC power supply units, and these units have a maximum power consumption of several hundred W to 1500 W, and are composed of units that use a 100 V15 A power supply system. Yes. Such copiers, mainly multi-function printers represented by multi-function printers, are stationary electrical and electronic equipment, and are international standards for flame retardancy of resin materials (IEC 60950), which is one of the safety standards for product equipment. However, it is required to cover an ignition source or a portion that may be ignited with a flame retardant 5 V enclosure component of UL94 standard. The test method related to 5 V of the UL94 standard is defined as “a combustion test with a 500 W test flame” in the international standard IEC60695-11-20 (ASTM D5048). Other than the enclosure parts, the parts to be configured in the copying machine main body are required to be UL94 V-2 or higher for the internal parts in the enclosure.

  In addition, conventional resin materials are made of plastic materials made from petroleum. Recently, biomass-derived resins made from plants and the like have attracted attention. Biomass resources mean that living things such as plants and animals are used as resources, and indicate oils and fats, garbage etc. that can be taken from wood, corn, soybeans and animals. Biomass-derived resins are made from these biomass resources. In general, there are biodegradable resins, but biodegradation refers to a function that is decomposed by microorganisms or the like in a certain environment such as temperature and humidity. In addition, as a biodegradable resin, there is also a resin having a function of biodegrading, not a biomass-derived resin but a petroleum-derived resin. Biomass-derived resins include polylactic acid: PLA (PolyLactic Acid) produced by chemical polymerization using lactic acid fermented with saccharides such as potato, sugarcane, and corn, esterified starch and microorganisms mainly composed of starch. Examples thereof include microorganism-produced resins that are polyesters produced in the body: PHA (PolyHydroxy Alkanoate), 1.3 propanediol obtained by a fermentation method and PTT (Poly Trimethylene Terephthalate) using petroleum-derived terephthalic acid as raw materials.

Currently, petroleum-derived raw materials are used, but in the future, research is being made to shift to biomass-derived resins, and this research is one of the main raw materials for PBS (Poly Butylene Succinate). It aims to produce succinic acid from plants.
Among the biomass-derived resins, products using polylactic acid having a high melting point of around 180 ° C., excellent moldability, and stable supply to the market have begun to be realized. However, polylactic acid has a low glass transition point of 56 ° C., so that the heat distortion temperature is around 55 ° C. and its heat resistance is low. In addition, since it is a crystalline resin, the impact resistance is low and the Izod impact strength is ² kJ / m ² or less. For this reason, it is difficult to employ it as a durable member such as an electric / electronic equipment product. Conventionally, physical properties have been improved by polymer alloy with a polycarbonate resin, which is a petroleum resin, as a countermeasure. However, the content ratio of the petroleum resin is increased, and as a result, the content ratio of the biomass-derived resin is 50%. Around%. For this reason, the effect of reducing fossil usage and carbon dioxide emissions for reducing environmental impacts such as global warming countermeasures is halved.

  As a material with high biomass that can be expected to reduce the environmental burden, plant fiber reinforced polylactic acid material with plant fiber added to polylactic acid has been developed. The impact resistance improvement effect by this is twice that of polylactic acid. The above can be expected. However, on the other hand, it is very difficult to ensure the flame retardancy described later. Plant fibers themselves are very flammable, and it is very difficult to make plant fibers flame retardant. In addition, it is difficult to flame retardant the same mechanism as that for making a polylactic acid resin flame retardant, and therefore a technology for simultaneously flame retardant the resin and plant fiber has not been developed.

  As a high biomass material that has high heat resistance and can be expected to reduce the environmental burden, a material that has been improved in crystallinity and crystallization speed by adding a crystallization nucleating agent to polylactic acid has been developed. However, since about 2 minutes are required for crystallization, and a crystallization temperature is around 100 to 110 degrees, a high temperature mold is required. Therefore, a cycle time of 30 to 60 seconds in an injection molded product of petroleum resin, It is difficult to achieve a mold temperature of 30 to 40 degrees, and therefore productivity is very low.

  On the other hand, resin parts used in image output equipment such as copiers and printers, and electrical and electronic equipment such as home appliances, in addition to the above-mentioned heat resistance and impact resistance mechanical properties, ensure high flame resistance. Although it is necessary to do so, polylactic acid, which is a biomass-derived resin, is flammable in the same manner as conventional petroleum resins, and it has been conventionally practiced to ensure flame retardancy by blending a flame retardant. There are many types of flame retardants that can be applied to resin materials, and bromine / halogen flame retardants, phosphorus flame retardants, nitrogen compound flame retardants, silicone flame retardants, and inorganic flame retardants are used. The effects of these flame retardants are known in several documents. Here, three types of flame retardants that are widely used as flame retardant resins are introduced.

The first is a halogen compound typified by a brominated flame retardant. This is to reduce the combustion rate by making the halogen-based compound act as an oxidation reaction negative catalyst for the burned flame.
The second is a phosphorus flame retardant or a silicone flame retardant. This is because a silicone-based flame retardant is bleed on the surface of the resin during combustion, or a phosphoric acid-based flame retardant is caused to undergo a dehydration reaction in the resin, thereby generating char on the surface to form a heat insulation film. Stop the combustion.
The third is an inorganic flame retardant such as magnesium hydroxide or aluminum hydroxide. This is to stop the combustion by, for example, cooling the whole resin by an endothermic reaction when these compounds are decomposed by the combustion of the resin, or by the latent heat of vaporization of the generated water.

However, it is necessary to add a large amount of these flame retardants in order to obtain the effect thereof, and it is necessary to add 10 to 30 parts by weight of the flame retardant with respect to 100 parts by weight of the resin, and 50 parts by weight at most. . Since many of these flame retardants are made by chemical synthesis using fossil resources as raw materials, the effect is reduced even if biomass-derived resins are used to reduce environmental impact.

  In addition, many of these flame retardants have been pointed out as harmful. For example, it is a well-known fact that brominated flame retardants generate harmful dioxins due to thermal decomposition during incineration. In addition, some phosphorus-based flame retardants are suspected to be associated with chemical sensitivity (allergy), and there is an aspiration for the development of flame retardants that are safe and can provide flame retardant effects with a small amount of addition. Has been.

  Japanese Patent Application Laid-Open No. H10-260260 discloses a conventional technique for achieving both of these mechanical properties such as flame retardancy, heat resistance and impact resistance. In this product, biomass-derived resin and polycarbonate are the main raw materials, and the appearance excellent in impact strength and whiteness cannot be satisfied only by biomass-derived resin. Therefore, polycarbonate is alloyed with biomass-derived resin, impact strength, white The properties depend on the properties of the petroleum-derived polycarbonate. However, since the petroleum-derived resin depends on mechanical properties and the like, the polycarbonate must be at least 25% by weight and the content of the phosphorus flame retardant must be 15% by weight. It is impossible to further improve the biomass degree of the resin by this method.

  Although the thing of patent document 2 includes a boric acid compound in a plant fiber filler to make the plant fiber itself flame-retardant, it provides a resin composition in which a polylactic acid resin and a metal hydroxide are kneaded. The result of the V flammability test according to the flame retardant standard is V-2 level, which does not reach 5V, which is a necessary level for office equipment such as copying machines, and both the addition amount of boric acid compounds and metal hydroxides. Even if it increases, it is very difficult to clear the 5V flame retardant level. In addition, although not described in the description of Examples in Patent Document 2, impact resistance can be expected to be improved only about twice even if only plant fiber filler is dispersed and added. A special effect cannot be expected only by adding a fiber filler.

  Patent Document 3 is a halogen-free flame retardant thermoplastic polyester molding composition containing a thermoplastic polyester and melamine cyanurate, a phosphorus-containing flame retardant containing no element phosphorus, and an inorganic flame retardant cooperation containing no phosphorus It is a flame retardant resin composed of an additive and other additives including a fibrous reinforcing agent. The thermoplastic polyester includes poly (alkylene terephthalate), poly (butylene terephthalate), and poly (ethylene terephthalate), and is not polylactic acid. However, even if the same flame retardant effect is estimated for polylactic acid, the addition of 33 to 55% by mass of melamine cyanurate cannot be expected to improve the degree of biomass, and an environmental load reduction effect cannot be expected.

  The thing of patent document 4 cannot satisfy the appearance excellent in impact strength and whiteness only by the biomass-derived resin, so the polycarbonate is alloyed with the resin derived from biomass, and the impact strength and whiteness are characteristics of the polycarbonate derived from petroleum. Depends on. However, since it is necessary to add 15% by weight or more of the phosphorus-based flame retardant, it is not possible to expect an environmental load reduction effect by improving the biomass degree.

  The thing of patent document 5 is a flame retardant resin composition which added the halogen-free nonionic flame retardant and / or the nitrogen flame retardant to the resin composition which has a lactic acid resin as a main component. In both the non-halogen-based nonionic flame retardant and the nitrogen-based flame retardant, 20 to 65 parts by weight of the flame retardant is added to 100 parts by weight of the resin composition, and an improvement in the degree of biomass cannot be expected. Further, even in the oxygen index showing the flame retardant effect, the polylactic acid to which no flame retardant is added is about 17 parts by weight, and in the examples, it is 20 to 25 parts by weight. In order to ensure 25 or more with no continuous combustion, the flame retardancy required for the above is only an example in which 65 parts by weight is added, and it cannot be said that the flame retardancy is high.

  Although the thing of patent document 6 is not a biomass origin resin, it is invention regarding the manufacturing method of a fiber reinforced thermoplastic polymer composition and a secondary processed article from it, Disperse | distributing glass fiber in a thermoplastic polymer, It extrudes with an extruder. This is a technique for obtaining a molded product by compression molding. Glass fiber is added as much as 30%, and even when trying to improve the strength of the polylactic acid resin by the same technique, it is not expected to improve the biomass degree because glass fiber is added as much as 30%.

  Further, regarding flame retardancy, although not described in the description of Examples, halogenated hydrocarbons, halogenated carbonate oligomers, halogenated diglycidyl ethers, organic phosphorus compounds such as mono-, di- or oligomeric phosphates, fluorine Addition of flame retardants such as fluorinated olefins, antimony oxides and aromatic sulfur metal salts, but with such conventional flame retardants, it is necessary to add about 20 parts by weight in order to ensure the flame retardant effect Become. Therefore, physical property deterioration and biomass degree improvement are inhibited.

  The thing of patent document 7 is the product made from the fiber reinforced resin which contains the reinforcement fiber which consists of an inorganic fiber and / or an organic fiber by weight content at least 5-70%, and uses the organic fiber reinforced resin similar to this invention It is a sound insulation panel using technology including this. As the matrix resin of the war record fiber reinforced resin part, for example, thermoplastic resin such as polyethylene, polypropylene, nylon, ABS, PEEK, polyimide, or thermosetting resin such as epoxy resin, unsaturated polyester resin, vinyl ester resin phenol resin, etc. In particular, biomass-derived resins are not the target technology, but it is also possible to use biomass-derived resins such as polylactic acid as well. However, since the strength of the panel is maintained by taking the fiber reinforcement and the rib structure, this is a technique in which the rib effect is greater than the fiber reinforcement effect. Regarding the flame retardancy, the addition of aluminum hydroxide, bromine, inorganic powder, etc. can improve the flame retardancy, but the addition amount needs to be around 20 parts by weight, thus causing deterioration of physical properties, , The improvement of the biomass degree is hindered.

  Patent Document 8 discloses a resin composition containing 40% or less of at least one polyphosphate, a sulfur-containing compound, a catalyst, and a flame retardant effective additive of a nitrogen-containing compound such as melamine, and a reinforcing agent. This is a technique using glass fiber, carbon fiber, thermochromic polyester fiber, aramid fiber, Spectra fiber, lignocellulose fiber, wollastonite, mica, gypsum, talc and low-temperature glass. Although there is no description of biomass-derived resins such as polylactic acid with respect to the resin matrix, the flame retardant is added at about 20% even if it can be expected to improve strength when added to the polylactic acid material. It is described in the Examples that the effect is obtained, and the amount added is increased as in the case of the conventional flame retardant, and the improvement of the biomass degree is not expected. Therefore, the effect of reducing the environmental load cannot be obtained.

  On the other hand, there is a conventional technique described in Patent Document 9 as a conventional technique that exhibits a flame-retardant effect with a small amount of flame retardant. In this, a heat composed of polytetrafluoroethylene and a copolymer obtained by emulsion polymerization of a vinyl monomer selected from a C1-C4 (meth) acrylic acid alkyl ester and an aromatic alkenyl compound. There has been proposed a thermoplastic resin composition which is a plastic resin modifier and is further added with a flame retardant by external addition when added to the thermoplastic resin. As the flame retardant, conventional halogen compounds, phosphorus compounds such as phosphate esters, metal hydrates, and the like have been proposed, and the use of alkali (earth) metal salts of organic sulfonic acids has been proposed. In particular, for alkali (earth) metal salts of organic sulfonic acids, 0.07 parts by mass of sodium perfluorobutane sulfonate was externally added in the examples, and flame retardant UL94 standard V- 0 is realized. However, this conventional technique does not show a special flame retardant effect on the biomass-derived resin.

  Moreover, the prior art of patent document 10 contains at least one of 0.0002 to 0.8 parts by mass of an organic sulfonic acid compound, an organic carboxylic acid compound, and a metal salt thereof with respect to 100 parts by mass of the thermoplastic polyester resin. A flame retardant resin composition has been proposed. And what is described as an Example in patent document 10 WHEREIN: In the flame-retardant resin composition which added 0.01-0.05 mass part of camphorsulfonic acid which is an aliphatic sulfonic acid compound as a flame retardant, it is UL94 specification. The flame retardant effect of V-2 to V-0 is expressed. However, it is not clear whether this conventional technique has a special flame retardant effect on the biomass-derived resin.

: JP 2006-111858 A : JP 2007-130868 A : Special Table 2007-519833 : JP 2007-056247 A : JP 2004-099703 A : Special table 2006-502888 : JP 2003-232014 A : JP 2001-098166 A : JP 2004-155946 A : WO 2007/010786

  Accordingly, the object of the present invention is to provide a fiber-reinforced flame-retardant resin molded body mainly composed of a biomass material that improves strength such as impact resistance and ensures high flame retardancy with a small amount of addition. It is what.

[Means for Invention of Claim 1]
The invention according to claim 1 is a molded body composed of at least a thermoplastic polyester resin, a flame retardant, and a fiber reinforced flame retardant resin composition containing thermoplastic polyester fibers, and the thermoplastic polyester resin is At least a part of the raw material contains at least one of an aliphatic polyester resin and an aromatic polyester resin containing a biomass material, and the aliphatic polyester resin is a polylactic acid resin or a microorganism-produced resin (polyhydroxy). Alkanoic acid), polybutylene succinate, polyethylene succinate, polytrimethylene terephthalate, one or more, and the flame retardant is an aliphatic sulfonic acid compound, aromatic sulfonic acid compound, aliphatic Of carboxylic acid compounds, aromatic carboxylic acid compounds and their metal salts Any one is used, and the melting point of the thermoplastic polyester fiber is higher in the range of 40 to 160 ° C. than the melting point of the thermoplastic polyester resin, and lower than the decomposition point of the thermoplastic polyester resin, And the said thermoplastic polyester fiber is a fiber reinforced flame-retardant resin molding characterized by being comprised by the structure woven in mesh shape inside the molding.

[Means for Invention of Claim 2]
The invention according to claim 2 is a fiber-reinforced flame-retardant resin molded product in which the thermoplastic polyester fiber has a cross-sectional diameter in the range of 50 μm to 200 μm.

[Means for Invention of Claim 3]
The invention according to claim 3 is a fiber-reinforced flame-retardant resin molded article characterized in that the interval of weaving the thermoplastic polyester fiber is in the range of 1 to 3 times the diameter of the thermoplastic polyester fiber. . Here, the interval in which the thermoplastic polyester fiber is woven is the interval between the end surfaces of adjacent fibers, and the fiber-reinforced flame-retardant resin molded article in which the void portion of the network structure is composed of 1 to 3 times the fiber diameter. It is.

[Means for Invention According to Claim 4]
The invention according to claim 4 is characterized in that a phosphate containing at least one of melamine phosphate, melamine pyrophosphate, melamine polyphosphate, and ammonium polyphosphate is used as an additive in combination with the flame retardant. It is a fiber reinforced resin molded product.

[Means for Invention of Claim 5]
The invention according to claim 5 is characterized in that when the weight of the thermoplastic polyester resin and the thermoplastic polyester fiber is 100 parts by weight, the flame retardant is 0.001 to 1 part by weight. It is a fiber reinforced resin molded product.

[Means for Invention of Claim 6]
The invention according to claim 6 is characterized in that the additive is 0.1 to 5 parts by weight when the weight of the thermoplastic polyester resin and the thermoplastic polyester fiber is 100 parts by weight. It is a fiber reinforced resin molded product.

[Means for Invention of Claim 7]
The invention according to claim 7 is a method for producing the fiber reinforced flame retardant resin composition, wherein 0.001 to 1 part by weight of a flame retardant with respect to 100 parts by weight of the thermoplastic polyester resin constituting the thermoplastic polyester fiber. A process for producing flame retardant resin fibers from a resin composition previously containing 0.001 to 1 part by weight of a flame retardant with respect to 100 parts by weight of a thermoplastic polyester resin, and a thermoplastic polyester resin It is a manufacturing method of the fiber reinforced flame-retardant resin composition characterized by having the process of containing 0.1-5 weight part of additives with respect to 100 weight part which match | combined the thermoplastic polyester fiber.

[Means for Invention of Claim 8]
The invention according to claim 8 is a method for producing the fiber-reinforced flame retardant resin composition, wherein 0.001 to 1 part by weight of a flame retardant is 100 parts by weight of the thermoplastic polyester resin constituting the thermoplastic polyester fiber. And a step of producing a flame retardant resin fiber from a resin composition containing 0.1 to 5 parts by weight of an additive in advance, and 0.001 to 1 part by weight of a flame retardant with respect to 100 parts by weight of a thermoplastic polyester resin And a process for containing 0.1 to 5 parts by weight of an additive. A method for producing a fiber-reinforced flame-retardant resin composition.

[Means for Invention of Claim 9]
The invention according to claim 9 is a method for molding a fiber reinforced flame retardant resin molded article, wherein the flame retardant resin composition containing the thermoplastic polyester resin and the flame retardant is injected using an injection molding machine. In this case, the flame retardant resin composition is filled in a state in which a fiber structure woven in advance with the thermoplastic polyester fiber in the mold is simultaneously tensioned in at least two directions. It is the shaping | molding method of the fiber reinforced flame-retardant resin molding of the invention which concerns on any one of Claims 1-10.

The effects of the invention according to each claim are as follows.
(1) Effect of the invention according to claim 1 At least a thermoplastic polyester resin, a flame retardant, and a molded article composed of a fiber reinforced flame retardant resin composition containing thermoplastic polyester fibers, the thermoplastic polyester The resin contains at least one of an aliphatic polyester resin and an aromatic polyester resin in which at least a part of the raw material contains a biomass material, or the aliphatic polyester resin is a polylactic acid resin or a microorganism-producing resin. (Polyhydroxyalkanoic acid), polybutylene succinate, polyethylene succinate, polytrimethylene terephthalate, one or more, and the flame retardant contains an aliphatic sulfonic acid compound, aromatic Aromatic sulfonic acid compounds, aliphatic carboxylic acid compounds, aromatic carboxylic acid compounds And the thermoplastic polyester fiber has a melting point higher than the melting point of the thermoplastic polyester resin in a range of 40 ° C. to 160 ° C., and the thermoplastic resin. It is characterized by being lower than the decomposition point of the polyester resin, and the thermoplastic polyester fiber is constituted by a structure woven in a mesh shape inside the molded body,

  The amount of flame retardant added is small and a high flame retardant effect is obtained, and a thermoplastic polyester resin fiber having a higher melting point is formed in the molded body without melting during injection molding. Fiber reinforced flame retardant resin with high biomass that can reduce the impact on the environment by reducing oil consumption and reducing carbon dioxide emissions in response to the fossil resource depletion problem. A molded body can be provided.

(2) The effect of the invention according to claim 2 The fabric structure in which the thermoplastic polyester fiber has a cross-sectional diameter in the range of 50 μm to 200 μm and is woven into a network structure with sufficient strength inside the molded body. Can be configured.

(3) The effect of the invention according to claim 3 The gap between the fibers even during the injection molding process by setting the interval for weaving the thermoplastic polyester fiber in the range of 1 to 3 times the diameter of the thermoplastic polyester fiber The thermoplastic polyester resin can be filled into the mold with fluidity by passing through the prepreg-like structure that can be injection-molded, improved in strength such as impact resistance, and fossil resources It is possible to provide a fiber-reinforced flame-retardant resin molded article having a high biomass degree that can achieve the effect of reducing the environmental load of reducing the amount of oil used and the amount of carbon dioxide emission corresponding to the depletion problem.

(4) Effect of the invention according to claim 4 In combination with the flame retardant, a phosphate containing at least one of melamine phosphate, melamine pyrophosphate, melamine polyphosphate, and ammonium polyphosphate as an additive. By using it, the amount of flame retardant added is small, and a high flame retardant effect is obtained while maintaining a high degree of biomass.

(5) Effect of the Invention According to Claim 5 When the weight of the thermoplastic polyester resin and the thermoplastic polyester fiber is 100 parts by weight, the flame retardant is 0.001 to 1 part by weight, By specifying the addition amount range of the flame retardant, a high flame retardant effect can be obtained while maintaining a high degree of biomass with a small amount of addition of the flame retardant.

(6) Effect of the Invention According to Claim 6 When the weight of the thermoplastic polyester resin and the thermoplastic polyester fiber is 100 parts by weight, the additive is 0.1 to 5 parts by weight. By specifying the addition amount range of the additive, the flame retardant is added in a small amount, and a high flame retardancy effect is obtained while maintaining a high degree of biomass.

(7) Effect of the Invention According to Claim 7 Flame retardant from a resin composition containing 0.001 to 1 part by weight of a flame retardant in advance with respect to 100 parts by weight of the thermoplastic polyester resin constituting the thermoplastic polyester fiber. A step of producing a thermoplastic resin fiber, 100 parts by weight of a thermoplastic polyester resin containing 0.001 to 1 part by weight of a flame retardant, and 100 parts by weight of the thermoplastic polyester resin and the thermoplastic polyester fiber combined On the other hand, by including a step containing 0.1 to 5 parts by weight of the additive, the effect of reducing the amount of the flame retardant added to the thermoplastic polyester resin and minimizing the influence of residence during the injection molding process can get.

(8) Effect of the Invention According to Claim 8 0.001 to 1 part by weight of a flame retardant and 0.1 to 5 parts by weight of an additive are previously added to 100 parts by weight of the thermoplastic polyester resin constituting the thermoplastic polyester fiber. A step of producing a flame retardant resin fiber from the resin composition contained, and 0.001 to 1 part by weight of a flame retardant and 0.1 to 5 parts by weight of an additive with respect to 100 parts by weight of a thermoplastic polyester resin By having the process of making it, the effect which reduces the addition amount of the flame retardant with respect to a thermoplastic polyester resin, and minimizes the influence by the residence at the time of an injection molding process is acquired.

(9) The effect of the invention according to claim 9 A method for molding a fiber-reinforced flame-retardant resin molded article, wherein the flame-retardant resin composition containing the thermoplastic polyester resin and the flame retardant is used with an injection molding machine. When injecting, the flame retardant resin composition is filled with the fiber structure woven in advance with the thermoplastic polyester fiber inside the mold in a state where tension is simultaneously applied in at least two directions. By this method, it is possible to form a fiber structure woven inside the molded body while minimizing the influence of deformation due to resin flow during injection molding, and the degree of biomass with improved strength such as impact resistance is high. A fiber-reinforced flame-retardant resin molded product can be provided.

Next, embodiments will be described with reference to the drawings, thereby clarifying the configuration and operation of the present invention in detail.
FIG. 1 shows a schematic diagram of a fiber structure in which thermoplastic resin fibers are woven in a mesh shape.
It is made of a fiber structure in which thermoplastic fibers having a fiber diameter of 200 μm are woven into a mesh shape with a weaving machine or the like. The fiber-to-fiber distance, which is the distance between the woven fiber and the fiber, may be a fiber structure knitted with 1 to 3 times the fiber diameter, but the illustrated one is a fiber structure woven with 1 times the fiber diameter. It is a thing.

Next, a method for installing a fiber structure mold will be described with reference to FIGS.
The fiber structure 1 is placed inside the molding die in the injection molding die 4 shown in FIG. 2, and the fiber tip is fixed to the vertical die slide 3. Similarly, a fiber tip is fixed to a horizontal mold slide (not shown). When the mold 4 is closed and clamped in order to obtain the molded body 2, the mold slide 3 moves simultaneously with the front end of the resin, and accordingly, the front end of the fiber structure 1 moves in the direction of the arrow in the figure. The tension is applied so that the tension is applied. Similarly, the tension is applied in the horizontal direction, and the fiber structure 1 is uniformly tensioned. After the mold clamping is completed, the injection molding machine 5 injects the thermoplastic resin 6 and fills the mold 4 with the resin to form the molded body 2.

On the other hand, FIG. 3 shows a state in which the tension of the fiber structure 1 is released by the mold opening operation after the injection molding and the part can be taken out. That is, the mold slide 3 moves in accordance with the mold opening operation, and the molded body 2 is released from a state in which tension is applied, and can be taken out.
In addition, although the thing of illustration has comprised the fiber structure 1 with the plane fabric for convenience of explanation, about the distance between fibers, it is the conditions of the invention which concerns on Claim 3, ie, "the interval which weaves a thermoplastic polyester fiber concerned The distance between the thermoplastic polyester fibers is 1 to 3 times the diameter of the thermoplastic polyester fiber, and a structure in which a plurality of the fiber structures are stacked or a structure in which the fibers are woven into a three-dimensional shape is gold. It can also be installed inside the mold.

[Example 1]
(1) Production of thermoplastic resin fiber Polyethylene terephthalate fiber was used as the thermoplastic polyester resin fiber. The polyethylene terephthalate resin pellets were dried at 50 ° C. for 12 hours using a shelf-type hot air dryer, and then drawn and spun into a φ200 μm polyethylene terephthalate filament using a high-temperature melt spinning apparatus, and the spun fibers were mesh-like at intervals of 300 μm. Was woven into a flat fiber structure (woven fabric). And the fiber structure produced in this way was designated as “fiber structure (C1)”. Note that Mitsui PETJ120 manufactured by Mitsui Chemicals, Inc. was used as the polyethylene terephthalate resin constituting the thermoplastic polyester resin fiber.

(2) Preparation of flame retardant resin composition 0.1 part by weight of a flame retardant is added to 100 parts by weight of 80 parts by weight of a thermoplastic thermoplastic polyester resin and 20 parts by weight of a fiber structure (C1). After dry blending, melt-kneading was performed at a kneading temperature of 180 ° C. using a twin-screw kneading extruder to produce a molding pellet of about 3 mm square. This pellet was designated as “pellet (A1)”.
Here, a polylactic acid resin (Lacia H-100J manufactured by Mitsui Chemicals, Inc.) was used as the thermoplastic polyester resin, and camphorsulfonic acid (C10H16O4S, reagent grade 1 manufactured by Kanto Chemical Co., Ltd.) was used as the flame retardant.

(3) Preparation of UL94 vertical combustion test piece The produced pellet (A1) was dried at 50 ° C. for 12 hours using a shelf-type hot air dryer, and using a 50-ton clamping force electric injection molding machine. The mold temperature was set to 40 ° C., the cylinder temperature was set to 180 ° C., the injection speed was 20 mm / sec, the injection pressure was 100 MPa, and the cooling time was set to 60 sec.
Two pieces of the above-mentioned fiber structure (C1) are cut into a size of 125 mm or more in length and 13 mm or more in width to obtain a test piece. When the whole test piece was 100 parts by weight, the component thermoplastic polyester fiber was formed in the mold so as to be 20 parts by weight, and injection molding was performed under the set conditions to prepare a test piece. The size of the prepared strip test piece was 13 mm in width, 125 mm in length, and 1.6 mm in thickness.

(4) UL94 vertical combustion test The prepared test piece was aged at 50 ° C. for 72 hours and then cooled in a desiccator with a humidity of 20% for 3 hours. A combustion test was conducted.
The test method of the vertical combustion test is to clamp the upper end of the test piece, hold it vertically, place absorbent cotton (0.8 g or less, 50 mm square) 300 ± 10 mm below the lower end of the test piece, and drop the melt. It is a method of confirming that it falls on absorbent cotton. The first flame contact with the burner from the lower end of the test piece is performed for 10 ± 1 seconds, the burner is separated from the sample at a speed of about 300 mm / second, and immediately after the combustion has disappeared, the burner is returned to the lower end of the sample. Flame contact was performed for 10 ± 1 seconds.
A set of five test pieces was subjected to flame contact 10 times in total, and the burning time of the test pieces was recorded. The combustion time is the combustion continuation time after flame removal, where the first combustion time is t1, the second combustion time is t2, and the second post-combustion fire type continuation time is t3.

(5) Determination method of UL94 vertical combustion test The determination method of the vertical combustion test based on the UL94 standard is as follows.
(A) V0 if the continuation of combustion after flame release of each test piece is t1 or t2: 10 seconds or less, V-1 or V-2 if 30 seconds or less.
(B) All combustion durations t1 + t2 of five test pieces: V-0 if 50 seconds or less, V-1 or V-2 if 250 seconds or less.
(C) Total combustion duration after the second flame contact and fire type duration t2 + t3: V-0 if 30 seconds or less, V-1 or V-2 if 60 seconds or less.
(D) There is no burning to the clamp.
(E) Ignition of absorbent cotton by burning or falling objects: V-0 or V-1 if there is no ignition, V-2 if there is ignition.
It is determined whether all of the above conditions (a) to (e) V-0, V-1, and V-2 are satisfied.

(6) Preparation of test piece for Izod impact test After the produced pellet (A1) was dried at 50 ° C. for 12 hours using a shelf-type hot air dryer, an electric injection molding machine with a clamping force of 50 tons Were used to prepare Izod impact test specimens at a mold temperature of 40 ° C., a cylinder temperature of 180 ° C., an injection speed of 20 mm / sec, an injection pressure of 100 MPa, and a cooling time of 60 sec. When 8 pieces of the produced fiber structure (C1) are cut to a size of a test piece having a length of 64 mm or more and a width of 12.7 mm or more, and the total test piece is 100 parts by weight, the thermoplastic polyester fiber is 20 weights. The test piece was produced by injection molding under the above conditions. The size of the test piece was a No. 2 A test piece having a length of 64 mm, a width of 12.7 mm, a thickness of 12.7 mm, and an A notch.

(7) Izod impact test An Izod impact test in accordance with JIS K 7110 was performed.

[Example 2]
(1) Production of thermoplastic resin fiber Polyethylene terephthalate fiber was used as the thermoplastic polyester resin fiber. After the polyethylene terephthalate resin pellets were dried at 50 ° C. for 12 hours using a shelf type hot air dryer, the flame retardant was dry blended at a ratio of 0.1 parts by weight with respect to 100 parts by weight of the polyethylene terephthalate resin pellets. This was drawn and spun into a φ200 μm polyethylene terephthalate filament using a high-temperature melt spinning apparatus. And the fiber structure (woven fabric) which comprised the space | interval of the spinning fiber by 300 micrometers and was woven in mesh shape was produced. The fiber structure produced as described above was designated as “fiber structure (C2)”. In addition, camphorsulfonic acid (C10H16O4S, reagent grade 1 manufactured by Kanto Chemical Co., Inc.) was used as the flame retardant, and Mitsui PETJ120 manufactured by Mitsui Chemicals, Inc. was used as the polyethylene terephthalate resin constituting the thermoplastic polyester resin fiber.

(2) Preparation of flame retardant resin composition 0.1 part by weight of the flame retardant is added to 100 parts by weight of the thermoplastic polyester resin, dry blended, and then kneaded using a twin-screw kneading extruder. Melt kneading was performed at a temperature of 180 ° C. to obtain a molding pellet of about 3 mm square. The produced pellet was designated as “pellet (A2)”.
Here, a polylactic acid resin (Lacia H-100J manufactured by Mitsui Chemicals, Inc.) was used as the thermoplastic polyester resin, and camphorsulfonic acid (C10H16O4S, reagent grade 1 manufactured by Kanto Chemical Co., Ltd.) was used as the flame retardant.

(3) Production of UL94 vertical combustion test piece Electric injection by the same method as in Example 1 using the produced pellet (A2) and the fiber structure (C2) as the fiber structure formed inside the mold. Using a molding machine, strip test pieces for UL94 vertical combustion test were prepared.

(4) UL94 Vertical Combustion Test and Determination Method The UL94 vertical combustion test was performed in the same manner as in Example 1 to determine the combustibility.
(5) Preparation of Izod Impact Test Specimen and Izod Impact Test Using the prepared pellet (A2) and the fiber structure (C2) for the fiber structure formed inside the mold, the same method as in Example 1 Then, using an electric injection molding machine, a test piece for an Izod impact test was produced, and an Izod impact test in accordance with JIS K 7110 was performed.

Example 3
(1) Production of thermoplastic resin fiber A mesh-like fiber structure was produced in the same manner as in Example 1 using a melting prevention apparatus.

(2) Preparation of flame retardant resin composition 0.1 part by weight of flame retardant is added to 100 parts by weight of 80 parts by weight of thermoplastic polyester resin and 20 parts by weight of component (C1) fiber structure After dry blending, melt kneading was performed at a kneading temperature of 180 ° C. using a twin-screw kneading extruder to obtain a molding pellet of about 3 mm square. The produced pellet was designated as “pellet (A3)”.
Here, a polylactic acid resin (Lacia H-100J manufactured by Mitsui Chemicals, Inc.) is used as the thermoplastic polyester resin, and sodium dodecylbenzenesulfonate (C12H25C6H4SO3Na, reagent deer grade 1 manufactured by Kanto Chemical Co., Ltd.) is used as the flame retardant. It was.

(3) Production of UL94 vertical combustion test piece Using the produced pellet (A3) and the fiber structure (C3) for the fiber structure formed inside the mold, electric drive was performed in the same manner as in Example 1. A strip test piece for UL94 vertical combustion test was prepared using an injection molding machine.

(4) UL94 Vertical Combustion Test and Determination Method The UL94 vertical combustion test was performed in the same manner as in Example 1 to determine the combustibility.

(5) Preparation of Izod Impact Test Specimen and Izod Impact Test Using the above pellet (A3) and the fiber structure (C1) for the fiber structure formed inside the mold, the same method as in Example 1 was used. A test piece for an Izod impact test was prepared using an electric injection molding machine, and an Izod impact test based on JIS K 7110 was performed on the test piece.

Example 4
(1) Production of thermoplastic resin fiber Polyethylene terephthalate fiber was used as the thermoplastic polyester resin fiber. The polyethylene terephthalate resin pellets were dried at 50 ° C. for 12 hours using a shelf-type hot air dryer, and then the flame retardant was dry blended at a ratio of 0.1 parts by weight with respect to 100 parts by weight of the polyethylene terephthalate resin pellets. . This was drawn and spun into a φ200 μm polyethylene terephthalate filament using a high-temperature melt spinning apparatus. A fiber structure (woven fabric) in which the interval between the spun fibers is 300 μm, which is 1 times the fiber diameter, and is woven in a mesh shape was produced. The fiber structure produced as described above was designated as “fiber structure (C4)”.

  As the flame retardant, sodium dodecylbenzenesulfonate (C12H25C6H4SO3Na, reagent deer grade 1 manufactured by Kanto Chemical Co., Ltd.) is used. The polyethylene terephthalate resin constituting the thermoplastic polyester resin fiber is Mitsui Chemicals, Inc. PETJ120 was used.

(2) Preparation of flame retardant resin composition To 100 parts by weight of the component thermoplastic polyester resin, 0.1 part by weight of the flame retardant is added, and after dry blending, using a twin-screw kneading extruder, Melting and kneading were carried out at a kneading temperature of 180 ° C. to produce molding pellets of about 3 mm square. And the thing pellet was made into "pellet (A4)."
Here, a polylactic acid resin (Lacia H-100J manufactured by Mitsui Chemicals, Inc.) is used as the thermoplastic polyester resin, and sodium dodecylbenzenesulfonate (C12H25C6H4SO3Na, reagent deer grade 1 manufactured by Kanto Chemical Co., Ltd.) is used as the flame retardant. It was.

(3) Preparation of UL94 vertical combustion test piece Using the above pellet structure (C4) as the pellet (A4) and the fiber structure formed inside the mold, electric injection molding is performed in the same manner as in Example 1. The strip test piece for UL94 vertical combustion test was produced using the machine.

(4) UL94 Vertical Combustion Test and Determination Method The UL94 vertical combustion test was performed in the same manner as in Example 1 to determine the combustibility.
(5) Preparation of Izod Impact Test Specimen and Izod Impact Test Using the above pellet (A4) and the fiber structure (C4) in the mold, the same structure as in Example 1 was used. A test piece for an Izod impact test was prepared using an electric injection molding machine, and an Izod impact test in accordance with JIS K 7110 was performed.

Example 5
(1) Production of thermoplastic resin fiber A mesh-like fiber structure was produced in the same manner as in Example 1 using a melting prevention apparatus.

(2) Preparation of flame retardant resin composition 0.1 part by weight of the flame retardant and additive with respect to 100 parts by weight of 80 parts by weight of the thermoplastic polyester resin and 20 parts by weight of the fiber structure (C1) After adding 1 part by weight and dry blending, the mixture was melt-kneaded at a kneading temperature of 180 ° C. using a twin-screw kneading extruder to produce a molding pellet of about 3 mm square. The produced pellet was designated as “pellet (A5)”.
Here, polylactic acid resin (Lacia H-100J manufactured by Mitsui Chemicals, Inc.) is used as the thermoplastic polyester resin, camphorsulfonic acid (C10H16O4S, reagent grade 1 manufactured by Kanto Chemical Co., Ltd.) is used as the flame retardant, and added. Melamine polyphosphate ((C3H6N6) n · Hn + 2PnO3n + 1 (n = 1 or more), MPP-B manufactured by Sanwa Chemical Co., Ltd.)) was used as the agent.

(3) Production of UL94 vertical combustion test piece Electric injection molding machine in the same manner as in Example 1 using the pellet (A5) and the fiber structure (C1) as the fiber structure formed inside the mold Was used to prepare strip test pieces for UL94 vertical combustion test.

(4) UL94 Vertical Combustion Test and Determination Method The UL94 vertical combustion test was performed in the same manner as in Example 1 to determine the combustibility.

(5) Preparation of Izod Impact Test Specimen and Izod Impact Test Using the fiber structure (C1) for the pellet (A5) and the fiber structure formed inside the mold, the same method as in Example 1 was used. A test piece for an Izod impact test was prepared using an electric injection molding machine, and an Izod impact test in accordance with JIS K 7110 was performed.

Example 6
(1) Production of thermoplastic resin fiber Polyethylene terephthalate fiber was used as the thermoplastic polyester resin fiber. The polyethylene terephthalate resin pellets were dried at 50 ° C. for 12 hours using a shelf type hot air dryer, and then 0.1 part by weight of flame retardant and 1 part by weight of additive with respect to 100 parts by weight of the polyethylene terephthalate resin pellets. Dry blending was performed at a ratio of parts. This was drawn and spun into a φ200 μm polyethylene terephthalate filament using a high-temperature melt spinning apparatus. A fiber structure (woven fabric) in which the interval between the spun fibers was 300 μm and was woven in a mesh shape was produced. The produced fiber structure was designated as “fiber structure (C6)”.
As a flame retardant, sodium dodecylbenzenesulfonate (C12H25C6H4SO3Na, reagent deer grade 1 manufactured by Kanto Chemical Co., Ltd.) is used, and Mitsui Chemicals, Inc., PETJ120 manufactured by Mitsui Chemicals Co., Ltd. is used as the polyethylene terephthalate resin constituting the thermoplastic polyester resin fiber. As the additive, melamine polyphosphate ((C3H6N6) n.Hn + 2PnO3n + 1 (n = 1 or more), MPP-B manufactured by Sanwa Chemical Co., Ltd.)) was used.

(2) Preparation of flame retardant resin composition 0.1 parts by weight of the flame retardant and 1 part by weight of the additive are added to 100 parts by weight of the thermoplastic polyester resin, dry blended, and then biaxially kneaded. Using an extruder, melt-kneading was performed at a kneading temperature of 180 ° C. to produce a molding pellet of about 3 mm square. The produced pellet was designated as “pellet (A6)”.
Here, polylactic acid resin (Lacia H-100J manufactured by Mitsui Chemicals, Inc.) is used as the thermoplastic polyester resin, and sodium dodecylbenzenesulfonate (C12H25C6H4SO3Na, reagent deer grade 1 manufactured by Kanto Chemical Co., Ltd.) is used as the flame retardant. The melamine polyphosphate ((C3H6N6) n · Hn + 2PnO3n + 1 (n = 1 or more), MPP-B manufactured by Sanwa Chemical Co., Ltd.)) was used as an additive.

(3) Production of UL94 vertical combustion test piece Electric injection molding machine by the same method as in Example 1 using the above pellet (A6) and the fiber structure (C6) as the fiber structure formed inside the mold Was used to prepare strip test pieces for UL94 vertical combustion test.

(4) UL94 Vertical Combustion Test and Determination Method The UL94 vertical combustion test was performed in the same manner as in Example 1 to determine the combustibility.

(5) Preparation of Izod Impact Test Specimen and Izod Impact Test Using the above pellet (A6) and the fiber structure (C6) in the fiber structure formed in the mold, the same method as in Example 1 was used. A test piece for an Izod impact test was prepared using an electric injection molding machine, and an Izod impact test in accordance with JIS K 7110 was performed.

Example 7
(1) Production of thermoplastic resin fiber Polyethylene terephthalate fiber was used as the thermoplastic polyester resin fiber. The polyethylene terephthalate resin pellets were dried at 50 ° C. for 12 hours using a shelf type hot air dryer, and then 0.1 part by weight of flame retardant and 1 part by weight of additive with respect to 100 parts by weight of the polyethylene terephthalate resin pellets. Dry blending was performed at a ratio of parts. The tip die was changed using a high-temperature melt spinning apparatus, and drawn and spun into a φ200 μm polyethylene terephthalate filament. A fiber structure (woven fabric) in which the interval between the spun fibers was 550 μm and woven in a mesh shape was produced. The produced fiber structure was designated as “fiber structure (C7)”.

  As a flame retardant, sodium dodecylbenzenesulfonate (C12H25C6H4SO3Na, reagent deer grade 1 manufactured by Kanto Chemical Co., Ltd.) is used, and Mitsui Chemicals, Inc., PETJ120 manufactured by Mitsui Chemicals Co., Ltd. is used as the polyethylene terephthalate resin constituting the thermoplastic polyester resin fiber. As the additive, melamine polyphosphate ((C3H6N6) n.Hn + 2PnO3n + 1 (n = 1 or more), MPP-B manufactured by Sanwa Chemical Co., Ltd.)) was used.

(2) Preparation of flame retardant resin composition 0.1 parts by weight of the flame retardant and 1 part by weight of the additive are added to 100 parts by weight of the thermoplastic polyester resin, dry blended, and then biaxially kneaded. Using an extruder, melt-kneading was performed at a kneading temperature of 180 ° C. to produce a molding pellet of about 3 mm square. The produced pellet was designated as “pellet (A7)”.
Here, polylactic acid resin (Lacia H-100J manufactured by Mitsui Chemicals, Inc.) is used as the thermoplastic polyester resin, and sodium dodecylbenzenesulfonate (C12H25C6H4SO3Na, reagent deer grade 1 manufactured by Kanto Chemical Co., Ltd.) is used as the flame retardant. As the additive, melamine polyphosphate ((C3H6N6) n.Hn + 2PnO3n + 1 (n = 1 or more), MPP-B manufactured by Sanwa Chemical Co., Ltd.)) was used.

(3) Preparation of UL94 vertical combustion test piece The pellet (A7) was dried at 50 ° C. for 12 hours using a shelf-type hot air dryer, and using a 50-ton clamping force electric injection molding machine. A strip test piece for UL94 vertical combustion test was prepared at a mold temperature of 40 ° C., a cylinder temperature of 180 ° C., an injection speed of 20 mm / sec, an injection pressure of 100 MPa, and a cooling time of 60 sec. When the two fiber structures (C7) are cut into a test piece having a length of 125 mm or more and a width of 13 mm or more, and the whole test piece is 100 parts by weight, the thermoplastic polyester fiber is 14 parts by weight. A test piece was prepared by forming the inside of a mold and performing injection molding under the above conditions. The size of the prepared strip test piece was 13 mm in width, 125 mm in length, and 1.6 mm in thickness.

(4) UL94 Vertical Combustion Test and Determination Method The UL94 vertical combustion test was performed in the same manner as in Example 1 to determine the combustibility.
(5) Preparation of Izod Impact Test Specimen After the pellet (A7) was dried at 50 ° C. for 12 hours using a shelf-type hot air dryer, an electric injection molding machine with a clamping force of 50 tons was prepared. A test piece for Izod impact test was prepared using a mold temperature of 40 ° C., a cylinder temperature of 180 ° C., an injection speed of 20 mm / sec, an injection pressure of 100 MPa, and a cooling time of 60 sec. When the produced fiber structure (C7) is cut into a test piece size of 64 mm or more in length and 12.7 mm or more in width, and the entire test piece is taken as 100 parts by weight, the component thermoplastic polyester fiber is A test piece was prepared by configuring the inside of the mold so as to be 14 parts by weight and performing injection molding under the above conditions. The size of the manufactured test piece was No. 2 A test piece having a length of 64 mm, a width of 12.7 mm, a thickness of 12.7 mm, and an A notch.

(6) Izod impact test Using the Izod impact test specimen prepared as described above, an Izod impact test in accordance with JIS K 7110 was performed in the same manner as in Example 1.

Example 8
(1) Production of thermoplastic resin fiber Polyethylene terephthalate fiber was used as the thermoplastic polyester resin fiber. The polyethylene terephthalate resin pellets were dried at 50 ° C. for 12 hours using a shelf type hot air dryer, and then 0.1 part by weight of flame retardant and 1 part by weight of additive with respect to 100 parts by weight of the polyethylene terephthalate resin pellets. Dry blending was performed at a ratio of parts. The tip die was changed using a high-temperature melt spinning apparatus, and drawn and spun into a φ50 μm polyethylene terephthalate filament. A fiber structure (woven fabric) in which the interval between the spun fibers was 70 μm and was woven in a mesh shape was produced. The produced fiber structure was designated as “fiber structure (C8)”.

  As a flame retardant, sodium dodecylbenzenesulfonate (C12H25C6H4SO3Na, reagent deer grade 1 manufactured by Kanto Chemical Co., Ltd.) is used, and Mitsui Chemicals, Inc., PETJ120 manufactured by Mitsui Chemicals Co., Ltd. is used as the polyethylene terephthalate resin constituting the thermoplastic polyester resin fiber. As the additive, melamine polyphosphate ((C3H6N6) n.Hn + 2PnO3n + 1 (n = 1 or more), MPP-B manufactured by Sanwa Chemical Co., Ltd.)) was used.

(2) Preparation of flame retardant resin composition 0.1 parts by weight of the flame retardant and 1 part by weight of the additive are added to 100 parts by weight of the thermoplastic polyester resin, dry blended, and then biaxially kneaded. Using an extruder, melt-kneading was performed at a kneading temperature of 180 ° C. to produce a molding pellet of about 3 mm square. The produced pellet was designated as “pellet (A8)”.
Here, polylactic acid resin (Lacia H-100J manufactured by Mitsui Chemicals, Inc.) is used as the thermoplastic polyester resin, and sodium dodecylbenzenesulfonate (C12H25C6H4SO3Na, reagent deer grade 1 manufactured by Kanto Chemical Co., Ltd.) is used as the flame retardant. As the additive, melamine polyphosphate ((C3H6N6) n.Hn + 2PnO3n + 1 (n = 1 or more), MPP-B manufactured by Sanwa Chemical Co., Ltd.)) was used.

(3) Preparation of UL94 vertical combustion test piece The pellet (A8) was dried at 50 ° C. for 12 hours using a shelf-type hot air dryer, and using a 50-ton clamping force electric injection molding machine. A strip test piece for a UL94 vertical combustion test was prepared at a mold temperature of 40 ° C., a cylinder temperature of 180 ° C., an injection speed of 20 mm / sec, an injection pressure of 100 MPa, and a cooling time of 60 sec. And 8 pieces of the above-mentioned fiber structure (C8) are cut into a test piece size of 125 mm or more in length and 13 mm or more in width, and when the whole test piece is taken as 100 parts by weight, the thermoplastic polyester fiber is 20 parts by weight. A test piece was prepared by performing the injection molding under the above conditions. And the size of the created strip test piece was 13 mm in width, 125 mm in length, and 1.6 mm in thickness.

(4) UL94 Vertical Combustion Test and Determination Method The UL94 vertical combustion test was performed in the same manner as in Example 1 to determine the combustibility.

(5) Preparation of test piece for Izod impact test After the pellet (A8) was dried at 50 ° C. for 12 hours using a shelf-type hot air dryer, an electric injection molding machine with a clamping force of 50 tons was prepared. A test piece for Izod impact test was prepared using a mold temperature of 40 ° C., a cylinder temperature of 180 ° C., an injection speed of 20 mm / sec, an injection pressure of 100 MPa, and a cooling time of 60 sec. When 30 pieces of the above-mentioned fiber structure (C8) are cut into a test piece having a length of 64 mm or more and a width of 12.7 mm or more, and the total test piece is 100 parts by weight, the thermoplastic polyester fiber is 20 parts by weight. A test piece was prepared by performing the injection molding under the above conditions. The size of the manufactured test piece was No. 2 A test piece having a length of 64 mm, a width of 12.7 mm, a thickness of 12.7 mm, and an A notch.

(6) Izod impact test Using the Izod impact test specimen prepared as described above, an Izod impact test in accordance with JIS K 7110 was performed in the same manner as in Example 1.

Next, a comparative example will be described.
[Comparative Example 1]
(1) Preparation of flame retardant resin composition To 100 parts by weight of polylactic acid used in Example 1, 0.1 part by weight of camphor sulfonic acid, which is an aliphatic sulfonic acid compound used in Example 1, was added as a flame retardant. After dry blending, the mixture was melt-kneaded at a temperature of 180 ° C. with a twin-screw kneading extruder to produce 3 mm square molding pellets.

(2) Production of UL94 vertical combustion test piece Using the above molding pellets, a strip test piece for UL94 vertical combustion test was produced in the same manner as in Example 1 using an electric injection molding machine. .

(3) UL94 vertical combustion test and determination method thereof The UL94 vertical combustion test was performed in the same manner as in Example 1 to determine the combustibility.

(4) Preparation of Izod Impact Test Specimen and Izod Impact Test Using an electric injection molding machine in the same manner as in Example 1 using the resin pellets in Example 1 above, for Izod impact test A test piece was prepared and subjected to an Izod impact test in accordance with JIS K 7110.

[Comparative Example 2]
(1) Preparation of flame retardant resin composition To 100 parts by weight of polylactic acid used in Example 1, 0.1 part by weight of camphor sulfonic acid, which is an aliphatic sulfonic acid compound used in Example 1, was added as a flame retardant. Further, 1 part by weight of melamine polyphosphate used in Example 5 was added as an additive, dry blended, and then melt-kneaded at a temperature of 180 ° C. with a twin-screw kneading extruder to produce a 3 mm square molding pellet. did.

(2) Production of UL94 vertical combustion test piece Using the resin pellets, a strip test piece for UL94 vertical combustion test was produced in the same manner as in Example 1 using an electric injection molding machine.

(3) UL94 vertical combustion test and determination method thereof The UL94 vertical combustion test was performed in the same manner as in Example 1 to determine the combustibility.

(4) Preparation of Izod Impact Test Specimen and Izod Impact Test Using the above resin pellets, an electric injection molding machine was used to prepare an Izod impact test specimen in the same manner as in Example 1. Then, an Izod impact test based on JIS K 7110 was performed.

[Comparative Example 3]
In Comparative Example 3, a strip test piece for UL94 vertical combustion test and a test piece for Izod impact test were prepared and tested only for the polylactic acid resin used in Example 1 by the same method as in Example 1. The details are as follows.

(1) Production of thermoplastic resin fiber Polyethylene terephthalate fiber was used as the thermoplastic polyester resin fiber. The polyethylene terephthalate resin pellets were dried at 50 ° C. for 12 hours using a shelf-type hot air dryer, and then drawn and spun into φ200 μm polyethylene terephthalate filaments using a high-temperature melt spinning apparatus. A flat fiber structure (woven fabric) having a spacing of the spun fibers of 1100 μm and woven in a mesh shape was produced. The produced fiber structure was designated as “fiber structure (CH4)”.
Note that Mitsui PETJ120 manufactured by Mitsui Chemicals, Inc. was used as the polyethylene terephthalate resin constituting the thermoplastic polyester resin fiber.

(2) Preparation of flame retardant resin composition For 100 parts by weight of 92 parts by weight of thermoplastic polyester resin and 8 parts by weight of fiber structure (CH4), 0.1% by weight of the component flame retardant After the addition and dry blending, melt kneading was performed at a kneading temperature of 180 ° C. using a twin-screw kneading extruder to obtain a molding pellet of about 3 mm square. The produced pellet was designated as “pellet (AH4)”. Here, a polylactic acid resin (Lacia H-100J manufactured by Mitsui Chemicals, Inc.) was used as the thermoplastic polyester resin, and camphorsulfonic acid (C10H16O4S, reagent grade 1 manufactured by Kanto Chemical Co., Ltd.) was used as the flame retardant.

(3) Production of UL94 vertical combustion test piece The pellet (AH4) was dried at 50 ° C. for 12 hours using a shelf-type hot air dryer, and using a 50-ton clamping force electric injection molding machine. A strip test piece for UL94 vertical combustion test was prepared at a mold temperature of 40 ° C., a cylinder temperature of 180 ° C., an injection speed of 20 mm / sec, an injection pressure of 100 MPa, and a cooling time of 60 sec. Then, the two produced fiber structures (CH4) were cut into test pieces having a length of 125 mm or more and a width of 13 mm or more, and when the entire test piece was taken as 100 parts by weight, the thermoplastic polyester fiber was 8 parts by weight. Thus, the size of the strip specimen prepared by performing the injection molding under the above-described conditions was 13 mm in width, 125 mm in length, and 1.6 mm in thickness.

(4) UL94 vertical combustion test and determination method thereof Using the produced combustion test piece, a UL94 vertical combustion test was performed in the same manner as in Example 1 to determine combustibility.

(5) Preparation of test piece for Izod impact test After the produced pellet (AH4) was dried at 50 ° C. for 12 hours using a shelf-type hot air dryer, an electric injection molding machine with a clamping force of 50 tons Were used to prepare Izod impact test specimens at a mold temperature of 40 ° C., a cylinder temperature of 180 ° C., an injection speed of 20 mm / sec, an injection pressure of 100 MPa, and a cooling time of 60 sec. When 8 pieces of the above (CH4) fiber structure are cut into a test piece having a length of 64 mm or more and a width of 12.7 mm or more, and the total test piece is 100 parts by weight, the component thermoplastic polyester fiber is 8 wt. A test piece was prepared by performing injection molding under the above conditions. The size of the test piece was a No. 2 A test piece having a length of 64 mm, a width of 12.7 mm, a thickness of 12.7 mm, and an A notch.

(6) Izod impact test An Izod impact test based on JIS K 7110 was performed in the same manner as in Example 1 using the above-mentioned Izod impact test specimen.

[Comparative Example 5]
(1) Production of thermoplastic resin fiber Polyethylene terephthalate fiber was used as the thermoplastic polyester resin fiber. Polyethylene terephthalate resin pellets were dried at 50 ° C. for 12 hours using a shelf-type hot air dryer, then drawn and spun into φ50 μm polyethylene terephthalate filaments using a high-temperature melt spinning apparatus, and the spacing between the spinning fibers was 30 μm. Then, a flat fiber structure (woven fabric) was produced by weaving in a mesh shape. The produced fiber structure was designated as “fiber structure (CH5)”.
Note that Mitsui PETJ120 manufactured by Mitsui Chemicals, Inc. was used as the polyethylene terephthalate resin constituting the thermoplastic polyester resin fiber.

(2) Preparation of flame retardant resin composition
To 100 parts by weight of 92 parts by weight of the thermoplastic polyester resin and 8 parts by weight of the fiber structure (CH5), 0.1 part by weight of a flame retardant is added and dry blended. The resulting mixture was melt kneaded at a kneading temperature of 180 ° C. to produce a molding pellet of about 3 mm square. The produced pellet was designated as “pellet (AH5)”.
Here, a polylactic acid resin (Lacia H-100J manufactured by Mitsui Chemicals, Inc.) was used as the thermoplastic polyester resin, and camphorsulfonic acid (C10H16O4S, reagent grade 1 manufactured by Kanto Chemical Co., Ltd.) was used as the flame retardant.

(3) Production of UL94 vertical combustion test piece The above pellet (AH5) was dried at 50 ° C. for 12 hours using a shelf-type hot air dryer, and using a 50-ton clamping force electric injection molding machine. A strip test piece for UL94 vertical combustion test was prepared at a mold temperature of 40 ° C., a cylinder temperature of 180 ° C., an injection speed of 20 mm / sec, an injection pressure of 100 MPa, and a cooling time of 60 sec. When two pieces of the above-mentioned fiber structure (CH5) are cut into a test piece having a length of 125 mm or more and a width of 13 mm or more and the whole test piece is taken as 100 parts by weight, the thermoplastic polyester fiber becomes 8 parts by weight. Thus, the test piece was prepared by injection molding under the above conditions. And the size of the strip test piece was 13 mm in width, 125 mm in length, and 1.6 mm in thickness.

(4) UL94 vertical combustion test and determination method thereof Using a combustion test piece as described above, a UL94 vertical combustion test was performed in the same manner as in Example 1 to determine combustibility.

(5) Preparation of test piece for Izod impact test The pellet (AH5) was dried at 50 ° C for 12 hours using a shelf-type hot air dryer, and then an electric injection molding machine with a clamping force of 50 tons was used. Then, an Izod impact test specimen was prepared at a mold temperature of 40 ° C., a cylinder temperature of 180 ° C., an injection speed of 20 mm / sec, an injection pressure of 100 MPa, and a cooling time of 60 sec. When 8 pieces of the above-mentioned fiber structure (CH5) are cut into a test piece having a length of 64 mm or more and a width of 12.7 mm or more and the whole test piece is taken as 100 parts by weight, the component thermoplastic polyester fiber is 8 parts. A test piece was prepared by forming in the mold so as to be part by weight and injection molding under the above conditions. The size of the strip test piece was No. 2 A test piece having a length of 64 mm, a width of 12.7 mm, a thickness of 12.7 mm, and an A notch.

(6) Izod impact test An Izod impact test in accordance with JIS K 7110 was performed in the same manner as in Example 1 using the above-mentioned Izod impact test specimen.

Next, test results of Examples and Comparative Examples will be described.
〔Test results〕
Regarding Examples 1 to 8 and Comparative Examples 1 to 5, the formability evaluation results at the time of UL94 vertical combustion test, Izod impact test, and test piece molding are as shown in Tables 1 and 2 below.

From the test results for Examples 1 to 8 in Tables 1 and 2, it can be seen that the flame retardancy is secured by V-2 or more and the Izod impact strength is improved.
In particular, Examples 5 and 6 are improved in flame retardancy and impact resistance over the other examples.
Further, in the comparative example, there is a combination in which the flame retardancy achieves V-1, but the Izod impact strength is as low as 1.6 kJ / m ^2, and none has both flame retardancy and impact resistance. .

  Moreover, regarding the thermoplastic polyester fiber in the present invention, any thermoplastic resin that satisfies the temperature condition in the means of the invention according to claim 1 with respect to the melting point of the thermoplastic polyester resin to be flame-retarded can be used. Without limitation, for example, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, poly 1,4 cyclohexane dimethacrylate, polyethylene 2,6 naphthalate, polyester resin such as polyglycolic acid, polytetrafluoroethylene, tetrafluoroethylene / hexa Fluoropolymers such as fluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, polychlorotrifluoroethylene (trifluoride) Or the like can be used.

  The thermoplastic polyester resin is desirably an aliphatic polyester resin in which at least a part of the raw material is a biomass material. In addition to the polylactic acid resin, polyhydroxyalkanoic acids that are microorganism-produced resins, such as P (3HB), One type selected from P (3HB-co-3HV), P (3HB-co-3HA), P (3HB-co-3HHx), P (3HB-co-4HB), or a mixture of two or more types Also good. The thermoplastic polyester resin may be an aromatic polyester resin in which at least a part of the raw material is made of a biomass material. Examples of the aromatic polyester resin include polytrimethylene terephthalate obtained by synthesizing 1.3 propanediol, which is a part of a raw material, with a biomass material.

  Aliphatic sulfonic acid is a compound represented by the general formula R-SO3H, where R is a carbon chain, and R includes not only a straight chain structure but also a branched chain structure, a cyclic structure, and a hydroxy group. Includes structure. Monoterpene sulfonic acids including camphorsulfonic acid and its sodium or potassium salts are preferred, but other sulfonic acids such as methanesulfonic acid, propanesulfonic acid, butanesulfonic acid and octanesulfonic acid should also be used. Can do.

  Aromatic sulfonic acid refers to a sulfonic acid containing a benzene ring, and alkylbenzenesulfonic acid other than dodecylbenzenesulfonic acid and its sodium salt or potassium salt can also be used. Also, chlorobenzenesulfonic acid, dichlorobenzenesulfonic acid, trichlorobenzenesulfonic acid, aminobenzenesulfonic acid, diaminobenzenesulfonic acid, nitrobenzenesulfonic acid, dinitrobenzenesulfonic acid, hydrazinobenzenesulfonic acid, hydroxybenzenesulfonic acid, laurylbenzenesulfonic acid Aromatic sulfonic acids such as formylbenzenesulfonic acid and benzenesulfonic acid can also be used.

  The aliphatic carboxylic acid represents a compound represented by the general formula R—COOH, and R is composed of a carbon chain. For example, a saturated fatty acid having only a single carbon chain, and a double bond or triple bond in the carbon chain. Unsaturated fatty acids and their sodium or potassium salts can be used. Further, R includes not only a linear structure but also a branched fatty acid having a branched chain, a cyclic fatty acid having a cyclic structure, a hydroxyl fatty acid containing a hydroxy group, and the like.

  The aromatic carboxylic acid is a carboxylic acid containing a benzene ring. For example, benzoic acid, methylbenzoic acid, dimethylbenzoic acid, trimethylbenzoic acid, isopropylbenzoic acid, phthalic acid, methylisophthalic acid, phenylacetic acid, phenylpropane Aroma such as acid, phenylacrylic acid, salicylic acid, hydroxybenzoic acid, hydroxymethylbenzoic acid, dihydroxybenzoic acid, methoxybenzoic acid, dimethoxybenzoic acid, trihydroxybenzoic acid, dihydroxymethoxybenzoic acid, hydroxydiphenylacetic acid, hydroxyphenylpropanoic acid The group carboxylic acids and their sodium or potassium salts can be used.

If the additive of Claim 4 in this invention is a phosphate, there will be no restriction | limiting in particular. Examples thereof include phosphates containing at least one of melamine phosphate, melamine pyrophosphate, melamine polyphosphate, and ammonium polyphosphate.
In addition, various additives such as compatibilizers, plasticizers, antioxidants, ultraviolet absorbers, processing aids, antistatic agents, colorants, hydrolysis inhibitors, and the like are added to the fiber reinforced flame retardant resin composition. An agent can be appropriately blended.

FIG. 3 is a plan view of a mesh fiber structure in an example Is a cross-sectional view showing the setting state of the molding die in the embodiment FIG. 4 is a cross-sectional view showing the mold opening state of the molding die in the embodiment

Explanation of symbols

1: Fiber structure 2: Molded body 3: Mold slide 4: Mold

Claims (9)

At least, a molded body composed of a thermoplastic polyester resin, a flame retardant, and a fiber reinforced flame retardant resin composition containing thermoplastic polyester fibers,
The thermoplastic polyester resin contains at least a part of an aliphatic polyester resin containing a biomass material, an aromatic polyester resin, or a plurality of types, and the aliphatic polyester resin is a polylactic acid resin, Or a microorganism-produced resin, polybutylene succinate, polyethylene succinate, or any one or more of polytrimethylene terephthalate,
And, at least one of an aliphatic sulfonic acid compound, an aromatic sulfonic acid compound, an aliphatic carboxylic acid compound, an aromatic carboxylic acid compound, and a metal salt thereof is used as the flame retardant,
The melting point of the thermoplastic polyester fiber is higher than the melting point of the thermoplastic polyester resin in a range of 40 ° C. to 160 ° C. and lower than the decomposition point of the thermoplastic polyester resin,
The thermoplastic polyester fiber has a structure woven in a mesh shape inside the molded body, and is a fiber-reinforced flame-retardant resin molded body.   The fiber-reinforced flame-retardant resin molded article according to claim 1, wherein the thermoplastic polyester fiber has a cross-sectional diameter in the range of 50 µm to 200 µm.   The fiber-reinforced flame-retardant resin molded article according to claim 1 or 2, wherein an interval at which the thermoplastic polyester fiber is woven is in a range of 1 to 3 times the diameter of the thermoplastic polyester fiber.   In combination with the flame retardant, a phosphate containing at least one of melamine phosphate, melamine pyrophosphate, melamine polyphosphate, and ammonium polyphosphate is used as an additive. 3. The fiber-reinforced flame-retardant resin molded product according to any one of 3 above.   5. The flame retardant is 0.001 to 1 part by weight when the weight of the thermoplastic polyester resin and the thermoplastic polyester fiber is 100 parts by weight. One of the fiber-reinforced flame-retardant resin moldings.   6. The additive according to claim 1, wherein the additive is 0.1 to 5 parts by weight when the weight of the thermoplastic polyester resin and the thermoplastic polyester fiber is 100 parts by weight. One of the fiber-reinforced flame-retardant resin moldings.   A method for producing the fiber-reinforced flame-retardant resin composition, comprising a resin composition containing 0.001 to 1 part by weight of a flame retardant in advance with respect to 100 parts by weight of a thermoplastic polyester resin constituting a thermoplastic polyester fiber A step of producing a flame retardant resin fiber, and 100 weight parts containing 0.001 to 1 part by weight of a flame retardant with respect to 100 parts by weight of a thermoplastic polyester resin and combining the thermoplastic polyester resin and the thermoplastic polyester fiber The method for producing a fiber-reinforced flame-retardant resin composition according to any one of claims 1 to 6, further comprising a step of containing 0.1 to 5 parts by weight of an additive with respect to parts.   It is a manufacturing method of the said fiber reinforced flame retardant resin composition, Comprising: 0.001-1 weight part of flame retardants and additives 0.1-5 with respect to 100 weight part of thermoplastic polyester resins which comprise a thermoplastic polyester fiber A step of producing a flame-retardant resin fiber from a resin composition preliminarily containing parts by weight, and 0.001 to 1 part by weight of a flame retardant and 0.1 to 5 additives for 100 parts by weight of a thermoplastic polyester resin It has the process of containing a weight part, The manufacturing method of the fiber reinforced flame-retardant resin composition in any one of Claims 1-6 characterized by the above-mentioned.   A method for molding a fiber-reinforced flame-retardant resin molded body, wherein the flame-retardant resin composition containing the thermoplastic polyester resin and a flame retardant is preliminarily formed inside a mold when being injected using an injection molding machine. 9. The flame retardant resin composition is filled with a fiber structure woven from the thermoplastic polyester fibers in a state where tension is simultaneously applied in at least two or more directions. A method for molding a fiber-reinforced flame-retardant resin molded article according to any one of the above.

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