JP5059706B2 - Flame retardant thermoplastic resin composition - Google Patents

Description

The present invention relates to a flame retardant thermoplastic polyester resin composition that exhibits excellent flame retardancy without containing a halogen flame retardant. More specifically, the present invention relates to a flame retardant thermoplastic polyester resin composition that is excellent in flame retardancy and also excellent in mechanical properties and electrical properties (tracking resistance).

Thermoplastic polyester resins are widely used in electrical and electronic equipment parts, automobile parts and the like because of their excellent characteristics. In particular, in the electrical and electronic equipment field, a flame retardant is often used in combination to ensure safety against fire. As the flame retardant, a halogen flame retardant or an antimony compound is generally used. However, halogen-based flame retardants may generate dioxins when used resin products are incinerated, which is not preferable in terms of environmental problems.

Therefore, a method for flame-retarding a thermoplastic polyester resin without using a halogen-based flame retardant has been studied, and several methods have been proposed. For example, Patent Document 1 proposes that a calcium salt or aluminum salt of phosphinic acid is blended as a flame retardant. However, the method of Patent Document 1 requires a large amount of addition to give good flame retardancy, and has a problem that moldability and mechanical properties are deteriorated.

Patent Document 2 proposes that a salt of a phosphinic acid and a salt of an amino group-containing triazine compound such as melamine cyanurate are used in combination. Although the flame retardancy is considerably improved by this compound, it is still difficult to stably develop the flame retardancy of V-0 rank when the molded product has a thickness of 1 mm or less.

Patent Document 3 proposes that a triazine compound and a boron compound are mixed and added to the phosphinic acid salt. According to this method, it is shown that flame retardancy is considerably improved and tracking resistance is also improved. However, the flame retardancy in the case of a molded product having a thickness of 0.6 mm or less is insufficient, and further improvement of the flame retardance is demanded.

Patent Document 4 discloses a flame retardant resin composition in which an organic phosphorus compound is used as a flame retardant, and a flame retardant aid is further blended therein. Flame retardant aids include inorganic phosphorus compounds, orthophosphoric acid esters or condensates thereof, phosphoric acid ester amides, phosphonitrile compounds, phosphites having phosphonyl groups or phosphinico groups or metal salts thereof, phosphonyl groups or phosphinico groups Examples include organic phosphinic acid compounds or metal salts thereof, aromatic resins, non-phosphorus nitrogen-containing cyclic compounds or salts thereof, inorganic metal compounds, sulfur-containing compounds, and silicon-containing compounds. Some of these flame retardant aids are themselves flame retardants, and it is not considered that all of these flame retardant aids have the same effect.

JP-A-8-73720 Japanese Patent Laid-Open No. 11-60924 JP 2006-117722 A WO2004 / 061008

The object of the present invention is to make a molded product with a thin wall thickness of 0.6 mm, which is highly flame-retardant without a halogen-based flame retardant and is highly flame-retardant with a relatively small amount of flame retardant, and has a high tracking resistance. An object of the present invention is to provide a flame retardant thermoplastic polyester resin composition capable of exhibiting flame retardancy of V-0 rank.

According to the study by the present inventors, it has been found that it is extremely effective to add a specific phosphinate, a triazine compound, and a specific flame retardant aid in combination with the thermoplastic polyester resin. It came to complete.

That is, the gist of the present invention is as follows.
(A) For 100 parts by weight of the thermoplastic polyester resin,
(B) 5-40 parts by weight of a phosphinic acid salt in which the anion moiety is represented by formula (1) or (2) and the cation moiety is aluminum or calcium,
(C) 1 to 35 parts by weight of an amino group-containing triazine salt,
(D) 0.1 to 35 parts by weight of inorganic flame retardant aid and (E) 0 to 150 parts by weight of reinforcing filler, and (D) inorganic flame retardant aid other than silica and talc The present invention resides in a flame retardant thermoplastic polyester resin composition characterized by being selected from the group consisting of silicate, kaolin, zeolite, metal sulfate and metal carbonate.

(In the formula, R ¹ and R ² each independently represents an alkyl group or an optionally substituted aryl group having 1 to 6 carbon atoms, R ¹ each other may be the same or different, R ³ Represents an alkylene group having 1 to 10 carbon atoms, an arylene group which may be substituted, or a mixed group thereof, and n represents an integer of 0 to 4.)

The flame-retardant thermoplastic polyester resin composition provided in the present invention has the following effects.
1) It has excellent flame retardancy even as a molded product having a thickness of 0.6 mm or less.
2) Since it is not necessary to use a halogen-based flame retardant, the generation of harmful substances can be suppressed even if the resin molding after use is incinerated, and the load on the surrounding environment can be expected.
3) Since a resin molded body excellent in tracking resistance and mechanical strength can be provided, it can be applied to a wide range of applications in the electric and electronic fields.
4) Due to the characteristics of the flame retardant, the occurrence of bleeding out of the flame retardant and the like on the surface of the molded product can be suppressed even when the molded product is exposed to a high temperature, and hence the appearance of the molded product surface and the surface electrical resistance can be suppressed.

(A) Thermoplastic polyester resin (A) The thermoplastic polyester resin used in the present invention is a polycondensation of dicarboxylic acid and dihydroxy compound, polycondensation of hydroxycarboxylic acid or polycondensation of these three kinds of bifunctional compounds. It is obtained and may be either homopolyester or copolyester. Dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylethanedicarboxylic acid and other aromatic dicarboxylic acids, cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids, adipic acid and sebacic acid And aliphatic dicarboxylic acids such as The dicarboxylic acid can be used in the polycondensation reaction either as a free acid or as an ester-forming derivative such as dimethyl ester.

Dihydroxy compounds include aliphatic diols such as ethylene glycol, propylene glycol, butanediol, and neopentyl glycol, and aromatic diols such as hydroquinone, resorcin, dihydroxynaphthalene, dihydroxydiphenyl ether, and 2,2-bis (4-hydroxyphenyl) propane. , Cyclohexanediol, polyoxyalkylene glycol and the like.

Examples of the hydroxycarboxylic acid include hydroxycarboxylic acids such as hydroxybenzoic acid, hydroxynaphthoic acid and diphenylhydroxycarboxylic acid, and ester-forming derivatives thereof. In addition to these bifunctional compounds that form the main part of the polyester resin, trifunctional compounds such as trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, and trimethylolpropane for introducing a branched structure The polycondensation reaction may be carried out using a small amount of a monofunctional compound as a molecular weight regulator.

In the present invention, as the polyester resin, a polyester resin in which 70 mol% or more, particularly 95 mol% or more of the acid component is an aromatic dicarboxylic acid, and 70 wt% or more, particularly 95 wt% or more of the alcohol component is an aliphatic diol. It is preferable to use it. Of these, polyethylene terephthalate and polybutylene terephthalate, which are polyesters of terephthalic acid and ethylene glycol or 1,4-butanediol, are preferred. These polyesters preferably have a copolymer component content of 5% by weight or less, particularly 3% by weight or less, or close to that.

As the polyester resin, one having an intrinsic viscosity of 0.5 to 2.0 dl / g is usually used. From the viewpoint of moldability and mechanical properties of the obtained resin composition, it is preferable to use those having an intrinsic viscosity of 0.6 to 1.5 dl / g. When a material having an intrinsic viscosity lower than 0.5 dl / g is used, generally only a resin composition having a low mechanical strength can be obtained. Moreover, when a thing with an intrinsic viscosity higher than 2.0 dl / g is used, the fluidity | liquidity of the resin composition obtained will fall and a moldability may fall.

(B) Phosphinic acid salt (B) As the phosphinic acid salt, one in which the anion moiety is represented by formula (1) or (2) and the cation moiety is aluminum or calcium is used.

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms or an optionally substituted aryl group, and R ¹ may be the same or different, and R ^{1 3} represents an alkylene group having 1 to 10 carbon atoms, an arylene group which may be substituted, or a mixed group thereof, and n represents an integer of 0 to 4.)

Examples of the alkyl group represented by R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an i-butyl group, and an n-hexyl group. Examples of the aryl group which may have a substituent include a phenyl group, a naphthyl group, and those obtained by substituting 1 to 2 alkyl groups or alkoxy groups having 1 to 3 carbon atoms. In addition, when having several R < ¹ > in the same molecule, this R < ¹ > may be same or different.

Examples of the alkylene group represented by R ³ include a methylene group, an ethylene group, a propylene group, a butylene group, and a 2-ethylhexylene group. The arylene group which may have a substituent includes a phenylene group and a naphthylene group. And those substituted with 1 to 2 alkyl groups or alkoxy groups having 1 to 3 carbon atoms. Examples of the mixed group of an alkylene group and an arylene group include those in which a methylene group, an ethylene group, and a phenylene group are bonded. R1 and R2 are preferably a methyl group, an ethyl group, a propyl group or a phenyl group, and R3 is preferably a methylene group, an ethylene group or a phenylene group.

The phosphinic acid salt is blended in an amount of 5 to 40 parts by weight per 100 parts by weight of the (A) thermoplastic polyester resin. If it is less than 5 parts by weight, the flame retardancy of the resin composition obtained is insufficient. If it exceeds 40 parts by weight, the mechanical properties of the resin composition obtained will deteriorate. From the viewpoint of achieving both flame retardancy and mechanical properties, the amount of the phosphinate is preferably 7 to 35 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin.

Examples of phosphinic acid metal salts include calcium dimethylphosphinate, aluminum dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, methyl-n-propylphosphinate, methyl- n-propylphosphinate aluminum, methanebis (methylphosphinic acid) calcium, methanebis (methylphosphinic acid) aluminum, benzene-1,4-bis (methylphosphinic acid) calcium, benzene-1,4-bis (methylphosphinic acid) aluminum , Calcium methylphenylphosphinate, aluminum methylphenylphosphinate, calcium diphenylphosphinate, aluminum diphenylphosphinate Bromide and the like. Several of these phosphinic acid salts may be used in combination. From the viewpoints of flame retardancy and electrical characteristics of the obtained resin composition, it is preferable to use aluminum diethylphosphinate or calcium diethylphosphinate.

In terms of mechanical strength and appearance of the molded product obtained by molding the resin composition of the present invention, the phosphinic acid salt has 90% by weight or more so that the particle size is 100 μm or less, preferably 50 μm or less. It is preferable to use a pulverized powder. Among these, by using a powder having 90% by weight or more in the particle size range of 0.5 to 40 μm, not only high flame retardancy is exhibited but also the toughness of the molded product is remarkably increased. The particle size is measured by a laser diffraction method.

(C) Salts of amino group-containing triazines As amino group-containing triazines (triazines having amino groups), amino group-containing 1,3,5-triazines are usually used. For example, melamine, substituted melamine (2-methylmelamine, guanylmelamine, etc.), melamine condensate (melam, melem, melon, etc.), melamine co-condensation resin (melamine-formaldehyde resin, etc.), cyanuric acid amides (ammelin, ammelide, etc.) Etc.), guanamine or derivatives thereof (guanamine, methylguanamine, acetoguanamine, benzoguanamine, succinoguanamine, adipoguanamine, phthalogamine, CTU-guanamine, etc.).

As an acid which forms a salt with this, either an inorganic acid or an organic acid may be used. Inorganic acids include nitric acid, chloric acids (chloric acid, hypochlorous acid, etc.), phosphoric acids (phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, etc.), sulfuric acids (non-condensation such as sulfuric acid and sulfurous acid) Sulfuric acid, condensed sulfuric acid such as peroxodisulfuric acid and pyrosulfuric acid), boric acid, chromic acid, antimonic acid, molybdic acid, and tungstic acid. Of these, phosphoric acid or sulfuric acid is preferred. Organic acids include organic sulfonic acids (aliphatic sulfonic acids such as methanesulfonic acid, aromatic sulfonic acids such as toluenesulfonic acid and benzenesulfonic acid), cyclic ureas (uric acid, barbituric acid, cyanuric acid, acetylene urea, etc. ) And the like. Among these, arylenesulfonic acid having 6 to 12 carbon atoms which may be substituted with an alkyl group having 1 to 3 carbon atoms such as alkanesulfonic acid having 1 to 4 carbon atoms such as methanesulfonic acid or toluenesulfonic acid, cyanuric Acid is preferred.

Examples of salts of amino group-containing triazines include melamine cyanurate, melam, melem double salt, melamine phosphate (melamine polyphosphate, melamine polyphosphate, melam, melem double salt, etc.), melamine sulfate (melamine sulfate, Dimelamine sulfate, dimram pyrosulfate), melamine sulfonates (melamine methanesulfonate, melam methanesulfonate, melem methanesulfonate, melamine methanesulfonate, melam, melem double salt, melamine toluene sulfonate, melam toluene sulfonate, Melamine, melam, melem double salt, etc.). These salts of amino group-containing triazines can be used alone or in combination of two or more.

Among these amino group-containing triazine salts, an adduct (addition salt) with cyanuric acid or isocyanuric acid is preferable. The composition of this adduct is usually 1 to 1 (molar ratio), optionally 1 to 2 (molar ratio). Examples thereof include melamine cyanurate, benzoguanamine cyanurate, acetoguanamine cyanurate, and melamine cyanurate is preferred. These salts can be produced by a known method. For example, a mixture of a triazine compound and cyanuric acid or isocyanuric acid is made into a water slurry, and mixed well to form both salts in the form of fine particles, and then the slurry is filtered and dried, and thus generally obtained in powder form. .

The salt does not need to be pure, and unreacted triazine compound, cyanuric acid, isocyanuric acid, or the like may remain. Moreover, the average particle diameter of the salt before blending with the resin is 100 to 100 as measured by a laser diffraction method from the viewpoint of flame retardancy, mechanical strength, heat and humidity resistance, residence stability, and surface properties of the molded product. 0.01 μm is preferable, and 80 to 1 μm is more preferable. In addition, when the dispersibility of these salts is poor, a dispersant such as tris (β-hydroxyethyl) isocyanurate or a known surface treatment agent may be used in combination.

(C) The compounding quantity of the salt of amino group containing triazine is 1-35 weight part with respect to 100 weight part of (A) thermoplastic polyester resin, Preferably it is 5-30 weight part. If the blending amount exceeds 35 parts by weight, the mechanical properties of the resulting resin composition tend to be lowered. In addition, it is preferable that the compounding ratio (weight ratio) of the salt of (B) phosphinic acid metal salt and (C) amino group-containing triazine is 0.1 to 2 from the viewpoint of flame retardancy. It is preferable that it is -1.5, especially 0.3-1.0.

In order to improve the dispersibility of the salts of phosphinates and amino group-containing triazines, these may be treated with a dispersant, or a dispersant may be added when preparing the resin composition. As a dispersing agent, the liquid dispersing agent currently disclosed by Unexamined-Japanese-Patent No. 2004-269885 can be used.

For example, diols such as ethylene glycol and butanediol, isocyanates such as TDI and MDI, polyols such as polyethylene glycol, polyether polyol and polyester polyol, bisphenol A diglycidyl ester, phenol-formaldehyde resin and cresol-formaldehyde resin An epoxy compound such as polyglycidyl ester can be used.

Further, when the flame retardant is blended after being granulated, the dispersibility at the time of blending can be improved. For example, a phosphinic acid metal salt granulated with a binder as disclosed in JP-A-2004-99893. It is also preferable to use.

Examples of the binder include alkyl alkoxylates, polyethylene ethylene glycol, waxes (such as carnauba wax, montan wax, polyethylene wax). The melting point of the binder is preferably 50 to 200 ° C. The amount of the binder is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the flame retardant.

(D) Inorganic flame retardant aid (D) As the inorganic flame retardant aid, one selected from the group consisting of silica, silicate, kaolin, zeolite, metal sulfate and carbonate is used. These are fine granular materials, and have an effect of improving flame retardancy by a combination of a phosphinic acid salt which is a flame retardant and a salt of an amino group-containing triazine. However, talc is excluded from silicates. As is well known, unlike other silicates, talc is a flake-like or scaly fine powder that is extremely soft and does not have an effect as a flame retardant aid in the present invention.

Examples of the silicate include salts of metals of groups 2 to 4 of the periodic table of silicic acid, such as calcium silicate and zirconium silicate. As the metal sulfate, alkaline earth metal salts such as barium sulfate and calcium sulfate are preferable, and barium sulfate is particularly preferable. As the metal carbonate, an alkaline earth metal salt is preferable, and calcium carbonate is particularly preferable.

These flame retardant aids may be used after being subjected to surface treatment as necessary. The average particle size of the flame retardant aid is preferably 10 μm or less, more preferably 7 μm or less, and even more preferably 0.1 to 5 μm. The average particle size is a value obtained by adding an appropriate amount of a flame retardant aid to a 3% neutral detergent aqueous solution and stirring to obtain a dispersion, which was measured by LA-700 laser diffraction scattering particle size distribution measurement method manufactured by Horiba, Ltd. It is.

The flame retardant aid has an oil absorption of 5 ml / 100 g or more, particularly preferably 10 ml / g or more, as measured by the JIS K-5101 method. When the oil absorption is small, the effect as a flame retardant aid tends to be small. Moreover, when a flame retardant aid having an excessively large oil absorption amount is used, the fluidity of the resulting resin composition tends to deteriorate.

Examples of flame retardant aids that satisfy preferred conditions such as particle size and oil absorption, have little influence on the thermoplastic polyester resin, and are easily available include zeolite, silica, and calcined kaolin.

The blending amount of the flame retardant aid is 0.1 to 35 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. When the amount is less than 0.1 part by weight, the effect of improving flame retardancy is not exhibited. If it exceeds 35 parts by weight, the mechanical strength of the resulting resin composition will be adversely affected. The blending amount of the flame retardant aid is preferably 0.25 to 30 parts by weight, and more preferably 0.5 to 20 parts by weight.

(E) Reinforcing filler It is preferable to further add (E) reinforcing filler to the resin composition of the present invention. The reinforcing filler has an effect of improving its mechanical properties by being blended into a resin composition as is well known, and preferably has a glass fiber, carbon fiber, basalt fiber, potassium titanate fiber, etc. A fibrous material is used. In view of mechanical strength, rigidity and heat resistance, it is preferable to use glass fiber.

(E) The compounding quantity of a reinforcement filler is 0-150 weight part with respect to 100 weight part of (A) thermoplastic polyester resin, Preferably it is 5-120 weight part. If the blending amount is small, a desired reinforcing effect cannot be obtained, and if it is more than 150 parts by weight, the fluidity of the resin composition is lowered and the mechanical properties (particularly toughness) are also lowered.

Furthermore, a known auxiliary agent that is generally added to a thermoplastic resin or the like can be added to the resin composition of the present invention in accordance with desired properties. Specifically, for example, crystallization accelerators, antioxidants, ultraviolet absorbers, stabilizers such as light stabilizers, antistatic agents, lubricants, mold release agents, colorants such as dyes and pigments, plasticizers, water resistance Degradability improvers (epoxy compounds, carbodiimide compounds, etc.) and the like can be blended. In particular, the addition of an antioxidant and a release agent for improving the heat resistance is effective. Of course, these additions must be made within a range not to impair the object of the present invention.

Further, it is preferable to add a phosphorus-based stabilizer to suppress the mold deposit of the flame retardant. As the phosphorus stabilizer, an organic phosphite compound or a metal phosphate is preferable, and bis (2,6-di-t-4methylphenyl) pentaerythritol diphosphite, bis (2,4-di-). t-butylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene phosphite, monocalcium phosphate, monohydrate of monobasic sodium phosphate, etc. Can be mentioned.

Of these, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite or tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene phosphite is preferably used.
The compounding quantity of a phosphorus stabilizer is 0.001-3 weight part with respect to 100 weight part of (A) thermoplastic polyester resins, Preferably it is 0.02-1 weight part. If it is less than 0.01 part by weight, the improvement effect by addition is low, and if it exceeds 3 parts by weight, deterioration of the appearance due to seepage from the molded product and hydrolysis of the resin may be promoted, which is not preferable.

Moreover, you may add the compound which suppresses dripping of the molten grain at the time of combustion. As such a compound, for example, polytetrafluoroethylene produced by emulsion polymerization can be used.

Moreover, in addition to the said component, another thermoplastic resin can also be used together with the flame-retardant polyester resin composition of this invention further auxiliaryly according to the objective. Other thermoplastic resins used here are not particularly limited as long as they are stable at high temperatures. For example, polyamide, polyphenylene oxide, polystyrene resin, polyphenylene sulfide ethylene, polysulfone, polyethersulfone, polyetherimide, Examples thereof include polyether ketone and fluororesin. These thermoplastic resins can be used in combination of two or more. Furthermore, elastomers which are impact resistance improvers can be blended.

The flame-retardant thermoplastic polyester resin composition of the present invention can be easily prepared by equipment and methods generally used as a conventional resin composition preparation method. For example, 1) A method in which each component is mixed and then melt-kneaded with a single-screw or twin-screw extruder to form pellets. 2) A pellet having a different composition is once prepared, and a predetermined amount of the pellet is mixed to form. And 3) a method of directly charging each component into a molding machine. It is also a preferable method to mix a part of the polyester resin with other components in advance as a fine powder.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In addition, the measuring method of the characteristic evaluation shown below is as follows.

(1) Tensile strength The tensile strength was measured based on ISO527-1,2.

(2) Flammability test (UL-94)
In accordance with the method of Subject 94 (UL94) of Underwriters Laboratories, flame retardancy was tested using five test pieces (thickness: 0.4 mm and 0.8 mm). Flame retardancy was classified into V-0, V-1, V-2, and HB according to the evaluation method described in UL94. V-0 has the highest flame retardancy.

(3) Comparative tracking index test (abbreviation: CTI test)
For the test piece (a flat plate having a thickness of 3 mm), the CTI was determined by the test method defined in the international standard IEC60112. CTI shows the resistance to tracking at a voltage of 25 V in increments of 100 V to 600 V when wet-contaminated with an electric field applied to the surface of a solid electrical insulating material. The higher the value, the better. Is 600V or higher.

Materials used in Examples and Comparative Examples (A) Thermoplastic polyester resin: polybutylene terephthalate resin Novaduran (registered trademark) 5008 manufactured by Mitsubishi Engineering Plastics

(B) Phosphinic acid salt (B-1) 1,2 Aluminum salt of diethylphosphinic acid: Prepared according to the examples of JP-A-11-060924.

(B-2) Calcium salt of 1,3 ethane-1,2-bismethylphosphinic acid: Prepared according to the examples of JP-A-11-060924. In addition, 90% by weight or more of both the phosphinic acid salts of (B-1) and (B-2) had a diameter of 40 μm.

(C) Salt of amino group-containing triazine (C-1) Melamine polyphosphate: melapure (trade name) manufactured by Ciba Specialty Chemicals 200/20

(C-2) Melamine cyanurate: MX44 manufactured by Mitsubishi Chemical Corporation

(D) Flame retardant aid (D-1) Zeolite: Mizusawa Chemical Co., Ltd., Shilton (trade name) AMT-50, average particle size 2.5 μm, oil absorption 26 ml / 100 g according to JIS K-5101 method

(D-2) Silica: Silicia (trade name) 310 manufactured by Fuji Silysia, average particle diameter of 2.5 μm

(D-3) Surface-treated calcined kaolin: TRANSLINK (trade name) 555 manufactured by Hayashi Kasei Co., Ltd. Average particle size 0.8 μm, oil absorption 80 ml / 100 g according to JIS K-5101 method

(D-4) Zirconium silicate: A-PAX average particle diameter of 1.0 μm manufactured by Kinsei Matec Co., Ltd.

(D-5) Barium sulfate: Sakai Chemical Co., Ltd. B-54 average particle size 1.2 μm, oil absorption 13 ml / 100 g according to JIS K-5101 method

(D-6) Calcium carbonate: Softon (trade name) 2200 manufactured by Shiraishi Calcium Co., Ltd. Average particle size 1.0 μm, oil absorption 35 ml / 100 g according to JIS K-5101 method

Flame retardant aids outside the scope of the present invention: (D-7) to (D-10);
(D-7) Zinc borate: Borax Japan Co., Ltd., Fire Break (trade name) 500

(D-8) Talc: MW5000S, Hayashi Kasei Co., Ltd. average particle size 2.8 μm

(D-9) Zinc oxide: Zinc oxide ZnO manufactured by Sakai Chemical Co., Ltd.

(D-10) Zinc stannate: ALCNEX-ZHS manufactured by Mizusawa Chemical Industry Co., Ltd.

(E) Reinforcing filler (E) Glass fiber: Asahi Fiber Glass Co., Ltd. Chopped strand 03JA-FT592

(F) Antioxidant (F-1) Hindered phenolic antioxidant: Irganox (trade name) 1010 manufactured by Ciba Specialty Chemicals

(F-2) Phosphorous antioxidant: PEP-36 manufactured by ADEKA

(G) Release agent: Paraffin wax FT100 manufactured by Nippon Seiwa Co., Ltd.

[Examples 1 to 10 and Comparative Examples 1 to 7]
Components other than glass fibers were mixed together at a blending ratio (weight ratio) shown in Table 1 with a super mixer (SK-350 type, manufactured by Shinei Machinery Co., Ltd.). The mixture is put into a hopper of a twin screw extruder (manufactured by Nippon Steel Works, TEX30XCT) with L / D = 42, and glass fiber is side-fed to a discharge rate of 20 kg / h, a screw rotation speed of 200 rpm, and a barrel temperature of 260. Extrusion was performed under the condition of ° C. to obtain pellets of a polybutylene terephthalate resin composition.

Using the resin composition pellets, an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., model SH-100) is used and the above conditions (2) and (3) are performed under conditions of a cylinder temperature of 270 ° C. and a mold temperature of 80 ° C. ) Test pieces (a flat plate test piece of 10 cm in length and width and a thickness of 3 mm, and a UL-94 standard combustion test piece of thickness 0.4 mm and 0.8 mm). Moreover, as a test piece of (1), an ISO tensile test piece (ISO 3167) was formed at 265 ° C. using an injection molding machine (model S-75MIII manufactured by Sumitomo Heavy Industries, Ltd.). The evaluation results are shown in Table 1.

The flame retardancy of the composition of Comparative Example 1 containing only the phosphinic acid salt and the triazine-based compound can ensure V-0 at a thickness of 0.8 mm, but decreases to V-1 at a thickness of 0.4 mm. In Comparative Examples 2 and 7 containing zinc borate disclosed in Patent Document 3, the flame retardancy of V-0 could not be ensured at a thickness of 0.4 mm. In Comparative Examples 3 to 5 in which a compound outside the scope of the present invention was further added to the composition of Comparative Example 1, the flame retardancy was not improved.

On the other hand, in Examples 1 to 10 in which the flame retardant aid of the present invention is blended with Comparative Example 1, high flame retardancy of V-0 can be secured even at a thickness of 0.4 mm, and CTI is 600 V, The mechanical strength was also good, and it had excellent flame-retardant polyester resin properties that were more functional than the comparative composition.

Claims (6)

(A) To 100 parts by weight of thermoplastic polyester resin,
(B) 5-40 parts by weight of a phosphinic acid salt in which the anion moiety is represented by formula (1) or (2) and the cation moiety is aluminum or calcium,
(C) 1 to 35 parts by weight of an amino group-containing triazine salt,
(D) 0.1 to 35 parts by weight of an inorganic flame retardant aid and (E) 0 to 150 parts by weight of a reinforcing filler are blended, and the inorganic flame retardant aid is a silicate other than silica and talc. A flame retardant thermoplastic polyester resin composition, which is selected from the group consisting of zeolite, kaolin, metal sulfate, and metal carbonate.

(In the formula, R ¹ and R ² each independently represents an alkyl group or an optionally substituted aryl group having 1 to 6 carbon atoms, R ¹ each other may be the same or different, R ³ Represents an alkylene group having 1 to 10 carbon atoms, an arylene group which may be substituted, or a mixed group thereof, and n represents an integer of 0 to 4.) (D) The flame retardant heat according to claim 1, wherein the inorganic flame retardant aid is selected from the group consisting of silica, zeolite, calcined kaolin, zirconium silicate, barium sulfate and calcium carbonate. A plastic polyester resin composition. (A) A thermoplastic polyester resin is a polybutylene terephthalate resin, The flame-retardant thermoplastic polyester resin composition of Claim 1 or 2 characterized by the above-mentioned. (A) 7 to 35 parts by weight of a phosphinic acid salt in which (B) an anion part is represented by the formula (3) or (4) and a cation part is aluminum or calcium in 100 parts by weight of a polybutylene terephthalate resin (C) amino group Addition salt of containing triazines with cyanuric acid or isocyanuric acid 5-30 parts by weight (D) Inorganic flame retardant aid selected from the group consisting of silica, zeolite, calcined kaolin, barium sulfate and calcium carbonate 0.5- 20 parts by weight and (E) 0 to 150 parts by weight of glass fiber are blended, a flame retardant thermoplastic polyester resin composition.

(In the formula, R ¹ and R ² each independently represents an alkyl group or an optionally substituted aryl group having 1 to 6 carbon atoms, R ¹ each other may be the same or different, R ³ Represents an alkylene group having 1 to 10 carbon atoms, an arylene group which may be substituted, or a mixed group thereof, and n represents an integer of 0 to 4.) The flame-retardant thermoplastic polyester resin composition according to any one of claims 1 to 4, wherein the phosphinate is an aluminum or calcium salt of diethylphosphinic acid. The flame retardant heat according to any one of claims 1 to 5, wherein the weight ratio of the salt of (B) amino group-containing triazine to phosphinate is 0.3 to 1.5. A plastic polyester resin composition.