JP2008074879A - Flame-retardant resin composition, flame-retardant resin molded product and flame retardant composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic flame-retardant polyester-based resin composition having excellent flame retardance and mechanical properties of a simple composition without adversely affecting environments, to provide a molded product obtained by processing the resin composition and to provide a flame retardant composition imparting flame retardance without deteriorating the mechanical properties thereof by compounding the flame retardant composition with a polyester-based resin. <P>SOLUTION: The flame-retardant polyester-based resin composition is characterized by comprising a polybutylene adipate-terephthalate copolymer which may be treated with a polyisocyanate and a melamine-based flame retardant in the polyester-based resin. The molded product is produced from the composition. The flame retardant composition for the polyester-based resin is composed of the polybutylene adipate-terephthalate copolymer and the melamine-based flame retardant. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a flame retardant resin composition, in particular, a thermoplastic flame retardant polyester resin composition and a molded product obtained by processing the same, and is added to a polyester resin to impair its mechanical properties. The present invention relates to a flame retardant composition that can impart flame retardancy without any problem.

  Thermoplastic polyester resins such as polyethylene terephthalate (hereinafter also referred to as PET) and polybutylene terephthalate (hereinafter also referred to as PBT) have excellent dimensional stability, toughness, electrical insulation, chemical resistance, etc. Widely used as molded products in applications such as the electrical / electronic field, machine component field, automobile field, etc. However, in these applications, flame retardant properties are often required, and in the past, mainly halogen-containing Resins imparted with flame retardancy using a compound and an antimony compound as a flame retardant and a flame retardant auxiliary have been provided.

  However, the halogen-based flame retardant has a high flame-retardant effect, but generates a toxic gas at the time of a fire and waste has an adverse effect on the environment. Therefore, it is desired to use a non-halogen-based flame retardant. Typical non-halogen flame retardants include phosphorus flame retardants, nitrogen flame retardants, and inorganic flame retardants. In these non-halogen flame retardants, the hydrolysis of polyester resins is difficult in the case of phosphorus flame retardants. Accelerates, liquid or softening point is low, there are problems such as bleeding at the time of compounding, heat resistance decreases, and in the case of inorganic flame retardants such as boron-based flame retardant, sufficient flame retardant effect if not blended in large quantities There are problems such as inability to obtain.

  Melamine flame retardants such as melamine cyanurate are known as nitrogen flame retardants. These suppress the density of smoke generated during incomplete combustion in a fire, and the toxicity of the released gas is low, the corrosiveness to molding machines and molds is low, and the resin used is colored because it is a white crystal. Although it has features such as ease, it has poor affinity with polyester resins, resulting in poor dispersion, and if added in a large amount to exhibit a sufficient flame retardant effect, the mechanical properties of the resin will decrease. There was a problem such as.

  Therefore, Patent Document 1 discloses a polyester resin composition in which a polyester resin is blended with an appropriate amount of a boric acid-modified phenol resin obtained by melt-mixing boric acid with a novolac-type phenol resin and melamine cyanurate as a non-halogen flame retardant. It is said that the working environment at the time of resin kneading is good and has high flame retardancy without causing deterioration of mechanical properties.

  Patent Document 2 discloses a flame retardant resin composition in which an aromatic polyester contains an organic phosphorus compound, a nitrogen-containing compound, an inorganic salt, a flame retardant improving resin, and a filler. It has excellent flame resistance and has a balance of industrially useful heat resistance, mechanical properties, etc., and is also said to have good hydrolysis resistance.

  Patent Document 3 discloses a flame retardant thermoplastic polyester resin composition in which a thermoplastic polyester resin contains a phosphinate, a salt of a triazine compound and cyanuric acid or isocyanuric acid, and a boric acid metal salt. The addition of a small amount of a flame retardant is said to have high flame retardancy without degrading properties such as moldability and mechanical properties.

  However, the polyester resin composition of Patent Document 1 cannot avoid the release of formaldehyde due to the structure of the novolac type phenol resin. In addition, the flame retardant resin composition of Patent Document 2 uses a special organic phosphorus compound and has a complicated composition such as addition of a nitrogen-containing compound, an inorganic salt, a flame retardant improving resin, and a filler. Therefore, in order to carry out, there is a problem in obtaining a special organophosphorus compound, and in order to satisfy the required mechanical properties, etc., a great deal of labor is required to study the composition ratio. There is a problem such as. The flame-retardant thermoplastic polyester resin composition of Patent Document 3 also has a complicated composition, and the problem derived from the phosphorus-based flame retardant is not solved.

JP 2002-47398 A JP 2004-189822 A JP 2006-117722 A

  The present invention has been made in view of solving the above-mentioned problems, and is a thermoplastic flame-retardant polyester resin composition that has a simple composition and is excellent in flame retardancy and mechanical properties and does not adversely affect the environment. It is an object of the present invention to provide a flame retardant composition that can be blended with a molded product obtained by processing it and a polyester resin and impart flame retardancy without impairing its mechanical properties.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.

  That is, the invention according to claim 1 is characterized in that the polyester resin comprises a polybutylene adipate / terephthalate copolymer which may be treated with polyisocyanate and a melamine flame retardant. It is a composition.

  The invention according to claim 2 is the flame retardant resin composition according to claim 1, wherein the polyester resin is polyethylene terephthalate or polybutylene terephthalate.

  The invention according to claim 3 is characterized in that the polybutylene adipate-terephthalate copolymer is treated with 0.1 to 10% by mass of the polyisocyanate of the copolymer. It is a flame retardant resin composition.

  The invention according to claim 4 is characterized in that the polyester resin comprises 50 to 80% by mass of polybutylene adipate / terephthalate copolymer 10 to 30% by mass and melamine flame retardant 10 to 30% by mass. It is a flame retardant resin composition in any one of 1-3.

  The invention according to claim 5 is characterized in that the melamine flame retardant is at least one selected from the group consisting of melamine phosphate, melamine polyphosphate, melam polyphosphate, melem polyphosphate and melamine cyanurate. Item 5. A flame retardant resin composition according to any one of Items 1 to 4.

  The invention according to claim 6 is a flame-retardant resin molded article produced from the flame-retardant resin composition according to any one of claims 1 to 5.

  The invention according to claim 7 is a flame retardant composition for a polyester resin comprising the polybutylene adipate / terephthalate copolymer and the melamine flame retardant.

  According to the present invention, a flame-retardant polyester resin having good moldability and excellent mechanical properties without using a halogen-based flame retardant that generates toxic gas in a fire and may adversely affect the environment. A flame retardant composition for a flame retardant resin molded article and a polyester resin produced from the composition, the composition can be provided.

  The flame retardant polyester resin composition according to the present embodiment, the flame retardant resin molded product produced from the composition, and the flame retardant composition for polyester resin will be described. In addition, this embodiment is only one form for implementing this invention, and this invention is not limited by this embodiment.

  The polyester resin used in the resin composition of the present invention is not particularly limited, and aromatic dicarboxylic acids such as terephthalic acid and 2,6-naphthalenedicarboxylic acid, ethylene glycol, 1,4-butanediol, Examples include polycondensates with diols such as oxytetramethylene glycol and 1,4-cyclohexanedimethanol, and copolyester resins obtained by polycondensation of three or more of these are also included. Particularly preferred are PET and PBT. Can be used for Also, a resin compatible with a polyester resin such as polycarbonate may be used.

  Examples of the melamine flame retardant used in the resin composition and flame retardant composition of the present invention include melamine phosphate, melamine polyphosphate, melam polyphosphate, melem polyphosphate, and melamine cyanurate. All of these have little impact on the environment and rarely generate toxic gases in the event of a fire, but melamine cyanurate can be suitably used because there are few combustion residues when incinerated. The average particle diameter of these flame retardants is preferably 0.1 to 50 μm, more preferably 1 to 30 μm. The smaller the particle size of the flame retardant, the higher the flame retardant effect. However, when the particle size is less than 0.1 μm, the flame retardant aggregates and cannot be uniformly dispersed. The content of the flame retardant is 10 to 30% by mass of the resin composition. If it is less than 10% by mass, sufficient flame retardancy is not exhibited, and if it exceeds 30% by mass, mechanical properties are deteriorated. The particle size of the flame retardant can be measured using a laser type particle size distribution measuring machine, for example, Microtrack manufactured by Nikkiso Co., Ltd.

  The polybutylene adipate-terephthalate copolymer used in the resin composition and flame retardant composition of the present invention may be made high molecular weight with 0.01 to 10% by mass of polyisocyanate based on the copolymer, Those having a weight average molecular weight of 5,000 to 500,000 are used. Examples of the polyisocyanate include hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, isophorone diisocyanate and the like, and blocked isocyanates thereof. The content of the polybutylene adipate / terephthalate copolymer is preferably 10% by mass or more of the resin composition. If it is less than 10% by mass, sufficient flame retardancy cannot be exhibited.

  The resin composition of the present invention includes an antioxidant, a weather resistance improver, an ultraviolet absorber, a colorant, a pigment, a filler, a slip agent, an antiblocking agent, and an antistatic agent as long as the properties are not affected. Additives such as a crosslinking agent, a flame retardant, a rust inhibitor, an antibacterial agent, a fragrance, a plasticizer, and a processing aid may be added.

  The resin composition of the present invention is obtained by mixing the polyester resin with the polybutylene adipate / terephthalate copolymer, the melamine flame retardant, and the additives as necessary, and a twin screw extruder, a Banbury mixer, or a pressurization. It can be produced by kneading and granulating with a kneader or other kneader, but it is necessary to disperse the flame retardant uniformly and finely in order to achieve a sufficient flame retardant effect, so the polybutylene adipate-terephthalate copolymer It is preferable to knead the coalescence and the melamine flame retardant to produce a flame retardant composition, and knead and granulate it together with the polyester resin. It is also possible to produce a master batch in which a polyester resin and a polybutylene adipate / terephthalate copolymer contain a melamine flame retardant at a high concentration and knead and granulate this with a polyester resin.

  The flame-retardant resin molded article of the present invention can be produced by molding by a method generally used in molding a thermoplastic resin such as extrusion molding or injection molding.

  The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Table 1 shows the names of the materials used in the present invention and the manufacturing company.

Example 1
A flame retardant composition obtained by kneading and extruding 30 parts by mass of polybutylene adipate / terephthalate copolymer (Ecoflex FBX7011 manufactured by BASF Japan Ltd.) and 20 parts by mass of melamine cyanurate (MC600 manufactured by Nissan Chemical Co., Ltd.). Pellets were obtained.
50 parts by mass of PET (Mitsui Chemicals, Ltd., Mitsui PET J005) was added to 50 parts by mass of the flame retardant composition, and the mixture was kneaded and extruded by a twin screw extruder to obtain a flame retardant resin composition pellet. The results of the flame retardancy test and mechanical strength test are shown in Table 3.

Example 2
50 parts by mass of PET (Mitsui Chemicals, Ltd., Mitsui PET J005), 30 parts by mass of polybutylene adipate-terephthalate copolymer (BASF Japan Co., Ltd., Ecoflex FBX7011) and melamine phosphate (Nissan Chemical Co., Ltd. Hosmel 200) 20 The mass part was kneaded and extruded by a twin screw extruder to obtain a flame retardant resin composition pellet. The results of the flame retardancy test and mechanical strength test are shown in Table 3.

Examples 3-6
The mixture shown in Table 2 was kneaded and extruded in the same manner as in Example 2 to obtain flame retardant resin composition pellets. The results of those flame retardancy tests and mechanical strength tests are listed in Table 3.

Comparative Examples 1-6
The composition shown in Table 2 was kneaded and extruded in the same manner as in Example 2 to obtain resin composition pellets. The results of those flame retardancy tests and mechanical strength tests are listed in Table 3.

<Preparation of test piece for resin composition>
1) The resin composition pellets obtained in Examples and Comparative Examples were formed into a sheet by hot pressing, and test pieces for vertical combustion test and oxygen index measurement were prepared from the sheet.
2) The resin composition pellets obtained in Examples and Comparative Examples were injection-molded to prepare test pieces for measuring Izod impact strength and flexural modulus.

<Flame retardance 1: Vertical combustion test>
A test piece having a length of 125 ± 5 mm, a width of 13 ± 0.5 mm, and a thickness of 1 ± 0.25 mm was prepared, and a vertical combustion test in accordance with UL-94 was performed using a UL combustion test chamber HVUL2 manufactured by Toyo Seiki Co., Ltd. V-2 suitability was judged, and the case where it conformed was marked with ◯, and the non-conformity was marked with ×.

<Flame retardance 2: Oxygen index>
A test piece having a width of 6.5 ± 0.5 mm and a thickness of 1 ± 0.25 mm was prepared and measured according to JIS K7201-2 using an oxygen index measuring device D manufactured by Toyo Seiki Co., Ltd., 28.0 Above, it was set as the flame retardance pass in the test.

<Izod impact strength>
A No. 2 type test piece was used and measured using an Izod impact tester manufactured by Intesco in accordance with JIS K7110.

<Bending elastic modulus>
A test piece having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm was prepared and measured using a universal material testing machine 210XL manufactured by Intesco under a test speed of 3 mm / min in accordance with JIS K7171.

  As is apparent from Table 3, all the examples have flame retardancy that conforms to V-2, exceeds the oxygen index 28, and has the same mechanical properties as the original resin (Comparative Examples 7 and 8). Is maintained. On the other hand, in a comparative example, it turns out that a flame retardance is inadequate or mechanical strength is inadequate even if a flame retardance is a pass.

Claims (7)

  A flame retardant resin composition comprising a polyester resin and a polybutylene adipate / terephthalate copolymer which may be treated with polyisocyanate and a melamine flame retardant.   The flame-retardant resin composition according to claim 1, wherein the polyester resin is polyethylene terephthalate or polybutylene terephthalate.   The flame-retardant resin composition according to claim 1 or 2, wherein the polybutylene adipate / terephthalate copolymer is treated with 0.01 to 10% by mass of a polyisocyanate. .   The polyester resin (50 to 80% by mass) comprises 10 to 30% by mass of a polybutylene adipate / terephthalate copolymer and 10 to 30% by mass of a melamine flame retardant. The flame-retardant resin composition as described.   The melamine-based flame retardant is at least one selected from the group consisting of melamine phosphate, melamine polyphosphate, melam polyphosphate, melem polyphosphate, and melamine cyanurate. The flame-retardant resin composition as described.   A flame-retardant resin molded article produced from the flame-retardant resin composition according to any one of claims 1 to 5.   A flame retardant composition for a polyester resin comprising the polybutylene adipate / terephthalate copolymer and the melamine flame retardant.