JP2000309692A - Flame retardant polybutylene terephthalate resin composition and formed article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a non-halogen flame-retardant PBT resin composition and a formed article containing a non-halogen flame retardant, having high resistances to moist heat and mold staining, and excellent in flame retardance, and a formed article using the resin composition. SOLUTION: This flame-retardant resin composition and its formed article are composed of (A) 100 pts.wt. of a polybutylene terephthalate resin, (B) 0.1-50 pts.wt. of red phosphorus and (C) 0.01-30 pts.wt. of a hindered amine compound and/or an aminotriazole compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant polybutylene terephthalate resin composition and a molded product using a non-halogen flame retardant. More specifically, the present invention relates to a flame-retardant polybutylene terephthalate resin composition and a molded article which are excellent in wet heat resistance, mold contamination and flame retardancy, and are suitable for automobile parts, electric / electronic parts, and mechanical parts.

[0002]

2. Description of the Related Art Polybutylene terephthalate resin (PB)
T) is utilized in a wide range of fields such as mechanical mechanism parts, electric / electronic parts, and automobile parts by making use of its excellent properties such as excellent injection moldability and mechanical properties.

[0003] Further, by compounding a fiber reinforced material with PBT, it is widely used as a material having further excellent mechanical properties and heat resistance. Among the fiber reinforcements, glass fibers are particularly used.

[0004] Because PBT is inherently flammable, it cannot be used for industrial materials such as mechanical and mechanical parts, electric and electronic parts, and automobile parts in addition to the general balance of chemical and physical properties. In many cases, fire safety, that is, flame retardancy is required.

[0005] As a method for imparting flame retardancy to PBT,
In general, a method of compounding a resin with a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant aid is used. However, this method tends to generate a large amount of smoke during combustion.

Therefore, in recent years, it has been strongly desired to use a flame retardant containing no halogen at all.

Heretofore, as a method of making a thermoplastic resin flame-retardant without using a halogen-based flame retardant, it has been widely known to add a hydrated metal compound such as aluminum hydroxide or magnesium hydroxide. In order to obtain sufficient flame retardancy, it is necessary to add a large amount of the above-mentioned hydrated metal compound, which has a disadvantage that the inherent properties of the resin are lost.

On the other hand, as a method for making a thermoplastic resin flame-retardant without using such a hydrated metal compound, the addition of red phosphorus is disclosed in JP-A-51-150553 and JP-A-5-150553.
JP-A-8-108248, JP-A-59-81351, JP-A-5-78560, JP-A-5-2871
No. 19, JP-A-5-295164, JP-A-5-295164
It is disclosed in Japanese Patent Application Laid-Open No. 320486 and Japanese Patent Application Laid-Open No. 5-339417. In addition, since a high level of flame retardancy cannot be obtained with a composition containing only red phosphorus, Japanese Patent Application Laid-Open No.
No. 7 discloses the combined use of a novolak type phenol resin, and JP-A-10-46034 discloses the combined use of a triazine compound.

However, any of the resin compositions is a useful flame-retardant resin material that does not use a halogen-based flame retardant. However, if injection molding is performed for a long time, dirt is generated on the mold surface and the appearance of the molded product is impaired. In addition, it was necessary to interrupt the injection molding operation and repeatedly clean the mold. Alternatively, when treated in a high temperature and high humidity state, there is a problem in that the humid heat resistance is deteriorated such that a bleed-out phenomenon in which a white precipitate is generated on the surface of the molded article is observed.

[0010]

That is, the present invention is to provide a non-halogen flame retardant, which suppresses bleed-out when treated in a high-temperature and high-humidity state. It is an object to obtain an excellent flame-retardant PBT resin composition and a molded product.

[0011]

Means for Solving the Problems In view of the above situation, the present inventors have made intensive studies, and as a result, blended a specific amount of red phosphorus and a hindered amine compound and / or an aminotriazole compound with polybutylene terephthalate resin. As a result, the present inventors have found that a resin material having specifically improved wet heat resistance and contact contamination can be obtained while maintaining highly excellent flame retardancy, and have reached the present invention.

That is, according to the present invention, (B) 0.1 to 50 parts by weight of red phosphorus and (C) a hindered amine compound and / or an aminotriazole compound are added to 100 parts by weight of a polybutylene terephthalate resin. .
Flame-retardant polybutylene terephthalate resin composition and molded article containing from 01 to 30 parts by weight, molded article in which a metal comprising the flame-retardant polybutylene terephthalate resin composition is inserted, and flame-retardant polybutylene terephthalate resin composition It is intended to provide a mechanical mechanism part, an electric / electronic part or an automobile part made of a product. .

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant polybutylene terephthalate resin composition and molded article of the present invention will be specifically described below.

The polybutylene terephthalate resin (A) in the present invention is a polymer obtained by a polycondensation reaction between terephthalic acid or its ester-forming derivative and 1,4-butanediol or its ester-forming derivative. , In addition to the acid component, isophthalic acid,
Naphthalenedicarboxylic acid, adipic acid, sebacic acid, dodecandic acid, oxalic acid, etc., as a glycol component,
As the glycol component, ethylene glycol, propylene glycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, or the like, or a molecular weight of 400 to 6000
A long-chain glycol, namely polyethylene glycol,
Poly-1,3-propylene glycol, polytetramethylene glycol or the like can be used in an amount of 20 mol% or less. Preferred examples of these polymers or copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decane dicarboxylate), and polybutylene. (Terephthalate / naphthalate) and the like, and may be used alone or as a mixture of two or more. Here, "/"
Means copolymerization.

The polybutylene terephthalate resin has an intrinsic viscosity of 0.36-1.60, particularly 0.52-1.60 measured at 25 ° C. using an O-chlorophenol solvent.
Those having a range of 25 are suitable from the viewpoints of impact strength and moldability of the resulting composition. Further, (A) polybutylene terephthalate resins having different intrinsic viscosities may be used in combination, and among them, each is preferably in the range of 0.36 to 1.60.

Further, these polybutylene terephthalate resins have a COOH terminal group amount determined by potentiometric titration of an m-cresol solution with an alkaline solution in the range of 1 to 50 eq / t (terminal group amount per ton of polymer). Can be preferably used in terms of durability and anisotropy suppressing effect.

The red phosphorus (B) used in the present invention is unstable as it is, and has a property of gradually dissolving in water. Can be As a method for treating such red phosphorus, without crushing red phosphorus described in JP-A-5-229806, without forming a crushed surface having high reactivity with water or oxygen on the surface of red phosphorus, A method of finely dividing red phosphorus, a method of catalytically suppressing oxidation of red phosphorus by adding a small amount of aluminum hydroxide or magnesium hydroxide to red phosphorus, coating red phosphorus with paraffin or wax to prevent contact with moisture. A method of suppressing, a method of stabilizing by mixing with ε-caprolactam or trioxane, and a method of stabilizing red phosphorus by coating it with a thermosetting resin such as a phenolic, melamine, epoxy, or unsaturated polyester resin. Red phosphorus is treated with an aqueous solution of a metal salt such as copper, nickel, silver, iron, aluminum and titanium to precipitate a metal phosphorus compound on the red phosphorus surface and to stabilize the red phosphorus. , Method of coating red phosphorus with aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide, etc., stable by electroless plating coating of red phosphorus surface with iron, cobalt, nickel, manganese, tin, etc. And a method in which these are combined. Preferably, a method in which red phosphorus is stabilized by coating with a thermosetting resin such as a phenol-based, melamine-based, epoxy-based, and unsaturated polyester-based resin, or a method in which red phosphorus is used. This is a method in which phosphorus is stabilized by coating it with aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide, or the like. Further, the above stabilization methods may be used in combination. The average particle size of red phosphorus before being blended with the resin is preferably 50 to 0.01 μm, more preferably 45 to 0.1 μm, from the viewpoint of flame retardancy, impact strength and appearance of the molded product. belongs to.

The conductivity of the (B) red phosphorus used in the present invention when extracted in hot water (where the conductivity is determined by adding 100 mL of pure water to 5 g of red phosphorus,
Extraction treatment at 21 ° C. for 100 hours, the filtrate after red phosphorus filtration can be diluted to 250 mL and measured), usually from 0.1 to 1 in view of flame retardancy and mechanical strength of the obtained molded article.
000 μS / cm, preferably 0.1 to 800 μ
S / cm, more preferably 0.1 to 500 μS / cm
It is.

Examples of such commercially available preferred red phosphorus include "NOVA EXCEL 140" and "NOVA EXCEL F5" manufactured by Rin Kagaku Kogyo KK and equivalents of these commercially available products.

The amount of red phosphorus (B) used in the present invention is (A)
0.1 parts by weight based on 100 parts by weight of polybutylene terephthalate.
1 to 50 parts by weight, preferably 0.1 to 40 parts by weight, more preferably 1 to 20 parts by weight, further preferably 1 to 15 parts by weight.
If the amount is too small, the effect of improving the flame retardancy is small. If the amount is too large, the mechanical properties of the excellent polybutylene terephthalate resin are unfavorably deteriorated.

The red phosphorus (B) of the present invention can be further improved in stability, strength, heat resistance and the like during extrusion and molding by adding a metal oxide as a stabilizer for red phosphorus. Specific examples of such a metal oxide include:
Cadmium oxide, zinc oxide, cuprous oxide, cupric oxide,
Ferrous oxide, ferric oxide, cobalt oxide, manganese oxide, molybdenum oxide, tin oxide and titanium oxide, among which cadmium oxide, cuprous oxide,
Cupric oxide and titanium oxide are preferred, and cuprous oxide, cupric oxide, and titanium oxide are more preferred, and titanium oxide is particularly preferred.

In particular, titanium oxide is effective not only as a stabilizer for red phosphorus, but also for improving the non-coloring property and the dispersibility of red phosphorus of the obtained molded article.

The addition amount of the metal oxide is preferably from 0.01 to 10 parts by weight, particularly preferably from 0.1 to 5 parts by weight, per 100 parts by weight of the polybutylene terephthalate (A) from the viewpoint of mechanical properties.

As the hindered amine compound (C) of the present invention, a hindered amine represented by the following general formula is used in the molecule.
(Where R1 to R5,
Each _{R7~11 -H, -CH 3, -CH 2} - is a group selected from, may R6 which also being the same or different _{-H, -CH 3, -CH 2 -} , - A group selected from N =, wherein R12 and 13 are each -H, -C
A group selected from H ₃ , —CH ₂ —, —N =, and —COO—, which may be the same or different. ).

[0025]

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[0026]

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Among them, dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-
Tetramethylpiperidine polycondensate, poly [｛6- (1,
(1,3,3-tetramethylbutyl) imino-1,3,
5-triazine-2,4-diyl} (2,2,6
6, -tetramethyl-4-piperidyl) imino {hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], 2- (3,5-di-t-butyl-
4-hydroxybenzyl) -2-n-butylmalonic acid bis (1,2,2,6,6-pentamethyl-4-piperidyl), N, N′-bis (3-aminopropyl) ethylenediamine and 2,4 -Bis [N-butyl-N- (1,
2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine, bis (2,2,6,6-tetramethyl-4-piperidyl) Sebacate is preferred, especially dimethyl succinate-
1- (2-hydroxyethyl) -4-hydroxy-2,
The 2,6,6-tetramethylpiperidine polycondensate is preferred.

The molecular weight of the hindered amine compound used is preferably in the range of 100 to 5,000 in terms of flame retardancy, but as long as the above hindered amine compound is used,
It is not limited to that.

As another aminotriazole compound of the component (C) of the present invention, a compound having one or more aminotriazoles of the following general formula in the molecule can be mentioned (where R is a phenyl group, carbon number A group selected from an aryl group having 6 to 15 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 16 carbon atoms, and a cycloalkyl group having 4 to 15 carbon atoms; A methyl group, an ethyl group, an n-propyl group, an isopropyl group, n
-Butyl group, sec-butyl group, tert-butyl group,
A hydroxymethyl group, a methoxymethyl group, a hydroxyl group, an amino group and the like may be bonded. ). As a specific example, 3- (N-salicyloyl) amino-1.2.4-
Triazole is preferably used.

[0030]

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The aminotriazole compound used may be any of various plastic processing aids (specific examples include, but are not limited to, dispersants, metal soaps, waxes, heat-resistant agents, mold release agents, clays and calcium carbonates, etc.). Granular fillers and inorganic layered compounds such as talc and mica).

The amount of the hindered amine compound and / or aminotriazole compound of the present invention is 0.0 to 100 parts by weight of the thermoplastic resin (A).
It is 1 to 30 parts by weight, preferably 0.05 to 25 parts by weight, more preferably 0.1 to 20 parts by weight.

The (D) polyester resin in the present invention is a polyester resin other than the component (A), and specific examples thereof include a polyethylene terephthalate resin, a polyester elastomer, a polyarylate resin, and a wholly aromatic liquid crystal polyester. Particularly preferred are polyethylene terephthalate resins and polyester elastomers. These are used alone or in combination of two or more.

The amount of the polyester resin (D) to be added is from 1 to 150 parts by weight based on 100 parts by weight of the polybutylene terephthalate resin (A) in view of the effect of improving the flame retardancy and the crystal characteristics of the obtained composition. It is preferably from 2 to 130 parts by weight, more preferably from 3 to 100 parts by weight.

The (D) polyethylene terephthalate resin preferably used in the polyester resin is:
Terephthalic acid is used as the acid component, and ethylene glycol is used as the glycol component.This refers to a high-molecular-weight thermoplastic polyester resin having an ester bond in the main chain.Other acid components include isophthalic acid, adipic acid, and oxalic acid. As a glycol component, propylene glycol,
1,4-butanediol, neopentyl glycol,
1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, etc., or a molecular weight of 4
00-6000 long chain glycols, ie, polyethylene glycol, poly-1,3-propylene glycol,
Polytetramethylene glycol or the like can be used in an amount of 20 mol% or less. Further, the polyethylene terephthalate resin has an intrinsic viscosity of 0.36 to 1.60, particularly 0.45 to 5, measured at 25 ° C. using an O-chlorophenol solvent.
A composition in the range of 1.15 is suitable from the viewpoint of impact strength and moldability of the resulting composition.

The polyester elastomer (D) preferably used among polyester resins includes polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), and polybutylene (terephthalate). / Decanedicarboxylate), polybutylene (terephthalate /
Naphthalate), one selected from polybutylene adipate and polyethylene terephthalate as a hard segment, polytetramethylene glycol, polypropylene glycol, an ethylene oxide adduct of polypropylene glycol, and a copolymer having a soft segment of polyethylene glycol and polylactone, These can be used alone or as a mixture.

As the (E) polycarbonate resin used in the present invention, an aromatic dihydric phenol compound, phosgene, carbonic acid diester, carbon monoxide or N, N'-
Those obtained by reacting with carbonyldiimidazole and the like can be mentioned. Further, a copolycarbonate obtained by copolymerizing the above polycarbonate with tere (iso) phthalic acid dichloride or polydimethylsiloxane may be used. The aromatic homo or copolycarbonate resin usually has a viscosity average molecular weight of 10,000 to 100,000.
0 and a viscosity average molecular weight of 10,000 to
If it is in the range of 1,000,000, polycarbonate resins having different viscosity average molecular weights may be used in combination. Here, as the dihydric phenol compound, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4
-Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-3,5-diphenyl) butane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,
2-bis (4-hydroxy-3,5-diethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1-bis (4
-Hydroxyphenyl) ethane and the like can be used, and these can be used alone or as a mixture.

The amount of the polycarbonate resin (E) is usually selected from (A) the polybutylene terephthalate resin 10 in view of the effect of improving the flame retardancy and the crystallinity of the obtained composition.
1 to 150 parts by weight, preferably 2-1 to 0 parts by weight
It is 30 parts by weight, more preferably 3 to 100 parts by weight.

As the fibrous reinforcing material (F) of the present invention, glass fiber, aramid fiber, carbon fiber and the like can be mentioned.
The above-mentioned glass fiber is a chopped strand type or roving type glass fiber used for an ordinary PBT reinforcing material, and is a silane coupling agent such as an aminosilane compound or an epoxysilane compound and / or bisphenol A diglycidyl ether or novolak. Glass fibers treated with a sizing agent containing one or more epoxy compounds such as a series epoxy compound are preferably used. The compounding amount of the (F) fibrous reinforcing material is preferably from 1 to 200 parts by weight, particularly preferably from 2 to 100 parts by weight of (A) the polybutylene terephthalate resin, from the viewpoint of flame retardancy and fluidity during molding. 190 parts by weight.

(G) Ethylene (co) used in the present invention
Examples of the polymer include an ethylene polymer and / or an ethylene copolymer such as high-density polyethylene, low-density polyethylene, and ultra-low-density polyethylene, and the ethylene copolymer is ethylene and a monomer copolymerizable therewith. Are obtained by copolymerizing As copolymerizable monomers, propylene, butene-1, vinyl acetate,
Monocarboxylic acids such as isoprene, butadiene, acrylic acid, and methacrylic acid, and ester acids thereof, and dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid are included. The ethylene copolymer can be usually produced by a known method. Specific examples of the ethylene copolymer include ethylene / propylene, ethylene / butene 1, ethylene / vinyl acetate, ethylene / ethyl acrylate, ethylene / methyl acrylate, and ethylene / ethyl methacrylate. Further, a copolymer obtained by grafting or copolymerizing the above ethylene (co) polymer with an acid anhydride or glycidyl methacrylate is also preferably used. Such ethylene (co) polymers are used alone or in combination of two or more. One or more of the above ethylene (co) polymers is mixed with a copolymer obtained by grafting or copolymerizing the above-mentioned acid anhydride or glycidyl methacrylate. May be used. Also,
(G) Among ethylene (co) polymers, a copolymer obtained by grafting or copolymerizing polyethylene with an acid anhydride or glycidyl methacrylate is preferably used because of its good compatibility with PBT. The amount of the ethylene (co) polymer (G) to be added is preferably 1 to 100 parts by weight, particularly preferably 100 parts by weight, based on 100 parts by weight of the polybutylene terephthalate resin in view of the effect of improving impact strength and flame retardancy. Is 1
９０90 parts by weight or less.

In the present invention, it is possible to further blend (H) an inorganic layered compound. Such an inorganic layered compound is an inorganic layered compound in which unit crystal layers are stacked on each other to have a layered crystal structure and have cleavage properties. Compound. Specific examples of the inorganic layered compound include silicates such as kaolinite, talc, smectite, vermiculite, and mica, and phosphates such as zirconium phosphate and titanium phosphate.These inorganic layered compounds include cups. Ring treatment or organic treatment for ion exchange of inorganic ions with organic ions may be performed for those having an inorganic ion between layers. Further, the addition amount of the inorganic layered compound (H) is preferably 0.1 to 30 parts by weight, particularly preferably 0.1 to 25 parts by weight, per 100 parts by weight of the polybutylene terephthalate (A) from the viewpoint of impact resistance. . Further, the average particle size of the inorganic layered compound is preferably from 0.1 to 4 μm, particularly preferably from 0.3 to 3 μm from the viewpoint of the impact strength of the obtained composition.

In the present invention, it is possible to suppress the drop (drip) of droplets during combustion by further mixing (I) a fluorine-based resin. Examples of such fluororesins include polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, and (tetrafluoroethylene / Ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / ethylene) copolymer and the like. Among them, polytetrafluoroethylene, (tetrafluoroethylene / (Perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer, and polyvinylidene fluoride are preferred. Polytetrafluoroethylene, (tetrafluoroethylene / ethylene) copolymer are preferable. Also,
The addition amount of (I) the fluorine-based resin is usually 0.1 to 10 parts by weight, preferably 0.1 to 8 parts by weight, per 100 parts by weight of the polybutylene terephthalate resin (A) from the viewpoint of impact strength and moldability. Parts, more preferably 0.1 to 6 parts by weight.

In the present invention, it is also possible to further blend (J) a lubricant. Examples of such a lubricant include metal soaps such as calcium stearate and barium stearate, salts of fatty acid esters, and salts of fatty acid esters (partly into salts). Fatty acid amides such as ethylenebisstearamide, polycondensates of ethylenediamine and stearic acid and sebacic acid or fatty acid amides of polycondensates of phenylenediamine and stearic acid and sebacic acid, polyalkylene waxes, Examples thereof include acid anhydride-modified polyalkylene wax, but are not limited thereto.

The lubricant used in blending the polycarbonate resin (E) is a lubricant which is not saponified with calcium, sodium, or the like, or is not bonded thereto, from the viewpoint of contact contamination and flame retardancy. Desirably. When a lubricant which is saponified or bonded with calcium or sodium is used as part or all of the lubricant when blending the polycarbonate resin (E), the following (L) phosphite-based stabilizer is used. And / or 0.1 to 5 parts by weight of (N) a trivalent phosphorus compound per 100 parts by weight of (A) polybutylene terephthalate. The (N) trivalent phosphorus compound includes, but is not limited to, phosphoric acid, triethyl phosphate, trimethyl phosphate, polyphosphoric acid, and phosphate, and particularly phosphoric acid and triethyl phosphate. It is preferably used. The amount of the trivalent phosphorus compound is preferably 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, per 100 parts by weight of the polybutylene terephthalate resin (A) from the viewpoint of impact strength. Parts by weight, more preferably 0.1 to 2 parts by weight.

The addition amount of the lubricant (J) is preferably 0.1 to 30 parts by weight, and more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the polybutylene terephthalate (A) in view of the impact strength of the composition obtained. More preferably, it is 1 to 25 parts by weight.

In the present invention, it is possible to further blend (K) carbon black. The amount of carbon black added is (A) in view of the impact strength of the resulting composition.
0.1 to 30 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the polybutylene terephthalate resin,
More preferably, the amount is 0 to 15 parts by weight.

In the present invention, by blending the (L) hindered phenol-based stabilizer and / or phosphite-based stabilizer, extremely good heat aging resistance can be obtained even when exposed to a high temperature for a long time. Examples of such a hindered phenol-based stabilizer include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4).
-Hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate],
2,2-thio-diethylenebis [3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate
Diethyl ester, 1,3,5-trimethyl-2,4,
6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis or tris (3-t-butyl-6-methyl-4-hydroxyphenyl) propane, N, N′-hexamethylenebis (3,5-di-t-
Butyl-4-hydroxy-hydrocinnamamide), N,
N'-trimethylenebis (3,5-di-t-butyl-4
-Hydroxy-hydrocinnamide) and the like. Examples of the phosphite-based stabilizer include tris (2,4-di-t-butylphenyl) phosphite,
2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, trisnonylphenyl phosphite, alkyl allyl phosphite, trialkyl phosphite, triallyl phosphite, pentaerythritol phosphite compound, etc. Is mentioned.

In the present invention, such a hindered phenol-based stabilizer and / or phosphite-based stabilizer (L) can be added as required, and the amount added at that time can be obtained. In view of the impact strength of the composition, (A) polybutylene terephthalate resin 1
0.1 to 5 parts by weight, preferably 0.1 to 100 parts by weight
To 4 parts by weight, more preferably 0.1 to 3 parts by weight.

Further, as long as the object of the present invention is not impaired with respect to the flame-retardant polybutylene terephthalate resin composition of the present invention, plate-like inorganic fillers such as glass flake, talc, kaolin and mica, silica, talc, Granular inorganic fillers such as glass beads, antioxidants and heat stabilizers, UV absorbers, mold release agents, plasticizers, UV inhibitors, flame retardants other than the present invention and ordinary coloring agents including dyes and pigments A material in which one or more additives are blended can also be used.

The flame-retardant polybutylene terephthalate resin composition and molded article of the present invention are produced by a generally known method. For example, (A) polybutylene terephthalate resin,
(B) red phosphorus, (C) hindered amine compound and / or aminotriazole compound, and other necessary (D) polyester resin, (E) polycarbonate resin, (F) fiber reinforcing material, (G) ethylene A) a polymer, (H) an inorganic layered compound, (I) a fluororesin,
The additives such as (J) a lubricant, (K) carbon black and (L) a hindered phenol-based stabilizer and / or a phosphite-based stabilizer are premixed or supplied to an extruder or the like without or with sufficient mixing. The resin composition is prepared by melt-kneading. However, from the viewpoint of handleability and productivity, (A) a part of polybutylene terephthalate resin and / or (D) polyester resin or (E) is preferable.
A part of the polycarbonate resin and (B) red phosphorus are once melt-kneaded to produce a resin composition having a high red phosphorus concentration, and the remaining (A) polybutylene terephthalate resin and / or the remaining (D) polyester resin or (E) It is prepared by melt-kneading the above-mentioned resin composition having a high red phosphorus concentration and other optional additives into a polycarbonate resin. Such red phosphorus having a high red phosphorus concentration is preferably used in the form of a so-called master pellet, but is not limited thereto, and is not limited to a so-called chip-like form.
It may be in the form of a powder or a mixture thereof. The (A) polybutylene terephthalate resin, the (D) polyester resin and the (E) polycarbonate resin to be blended during the production of the master pellets are preferably in the form of pellets, but are not limited thereto. A mixture of a chip and a powder may be used. Furthermore, blend with master pellet (A)
It is preferable that the shapes, sizes, and shapes of the polybutylene terephthalate resin, the (D) polyester resin, and the (E) polycarbonate resin are substantially the same or similar to each other because they can be uniformly mixed. Further, when adjusting the resin composition having a high red phosphorus concentration, a part or all of other necessary additives may be adjusted together.

As an example of the pre-mixing of the composition of the present invention, the effect of the present invention can be exhibited only by dry blending, but mixing using a mechanical mixing device such as a Henschel mixer can be mentioned. Further, (F) a method may be used in which the fiber reinforcing material is added by installing a side feeder in the middle of the base portion and the vent portion of a multi-screw extruder such as a twin-screw extruder.

In producing the flame-retardant polybutylene terephthalate resin composition, for example, but not limited to, a single-screw extruder or a twin-screw extruder equipped with a “Unimelt” or “Dalmage” type screw And a three-screw extruder and a kneader-type kneader.

The flame-retardant polybutylene terephthalate resin composition thus obtained can be molded by a generally known method. For example, injection molding, extrusion molding, compression molding, sheet molding, film molding, etc. In particular, injection molding is preferable, and a molded product obtained by an injection molding method by insert molding in which a part of a metal component is directly integrated with the molded product may be used.

In addition, molded articles made of the flame-retardant polybutylene terephthalate resin composition of the present invention can be used to produce molded articles that are required to be safe against flames and molded articles that have excellent mold contamination and excellent surface appearance. Since the resulting material and the inside of the device become hot and humid and are useful as molded products that require wet heat characteristics, they are used in general home appliances, OA devices, and coil bobbins and connectors incorporated in the above products and devices. It is a molded article suitable for electric parts such as relays and transformers, mechanical mechanism parts, and automobile parts.

[0055]

The effects of the present invention will be described in more detail with reference to the following examples. Here, all parts are parts by weight. The measuring method of each characteristic is as follows.

Reference Example 1 (A) Polybutylene terephthalate <A-1> Polybutylene terephthalate (PBT) resin, Toray PBT1100S (manufactured by Toray Industries, Inc.) was used.

Reference Example 2 (B) Red phosphorus <B-1>"NOVA EXCEL 140" (manufactured by Rin Kagaku Kogyo KK) was used.

Reference Example 3 (C) Hindered amine compound and / or aminotriazole compound <C-1> Dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6 is used as the hindered amine compound. , 6-tetramethylpiperidine polycondensate ("TINUVIN" 622LD (manufactured by Ciba-Geigy)) was used. <C-2> As an aminotriazole-based compound,
(N-salicyloyl) amino-1,2,4-triazole ("MARK" CDA-1 (made by Asahi Denka Co., Ltd.)) was used.

Reference Example 4 (D) Polyester resin <D-1> A polyethylene terephthalate (PET) resin having an intrinsic viscosity of 0.65 (a mixed solvent of phenol / tetrachloroethane of 1: 1 at 25 ° C.) was used.

Reference Example 5 (E) Polycarbonate (P
C) Resin <E-1> Iupilon S3000 (manufactured by Mitsubishi Engineering-Plastics Corporation) was used.

Reference Example 6 (F) Glass Fiber <F-1> A chopped strand glass fiber of "CS3J948" manufactured by Nitto Boseki Co., Ltd. was used.

Reference Example 7 (G) Ethylene (co) polymer <G-1> Ethylene / acrylic acid methacrylate copolymer (“Font First-E” manufactured by Sumitomo Chemical) <G-2> Ethylene / Phthene-1 / anhydrous A maleic acid copolymer ("MH5020" manufactured by Mitsui Tufon Polychemical) was used.

Reference Example 8 (H) Inorganic Layered Compound <H-1> Talc "HE-5" manufactured by Takehara Chemical Co., Ltd. was used.

Reference Example 9 (I) Fluorine-based resin <I-1> Polytetrafluoroethylene (“Teflon 6J” manufactured by Du Pont-Mitsui Fluorochemicals) was used.

Reference Example 10 (J) Lubricant <J-1> Lubricant in which a part of fatty acid ester was converted into calcium salt ("Hoechst Wax OP" manufactured by Hoechst Japan) <J-2> Composed of ethylenediamine, stearic acid and sebacic acid Polycondensate (Kyoeisha Chemical "Light Amide WH-255") <J-3> Acid anhydride modified polyalkylene wax (Mitsui Petrochemical Industries "Mitsui High Wax 1105A") Reference Example 11 (K) Carbon black <K -1> Mitsubishi Chemical # 3050 was used.

Reference Example 12 (L) Hindered phenol-based stabilizer and / or phosphite-based stabilizer <L-1> Hindered phenol-based stabilizer, pentaerythryl-tetrakis [3- (3,5-di- t-Butyl-4-human peroxyphenyl) fluoropionate] (manufactured by Chiba Kaiki Co., Ltd.! R-1010 ") <L-2> Phosphite stabilizer, pentaerythritol phosphite compound (“ PEP-24G ”manufactured by Asahi Denka) It was used.

REFERENCE EXAMPLE 14 (M) Trivalent phosphorus compound <M-1> A primary triethyl phosphate reagent was used.

Examples 1 to 25, Comparative Examples 1 to 4 Using a twin screw extruder (TEX-30α, manufactured by Nippon Steel Works) having a screw diameter of 30 mm and L / D35 with a co-rotating vent, (A) polybutylene was used. Terephthalate resin (PB)
T), (B) red phosphorus, (C) a hindered amine-based compound and / or an aminotriazole-based compound, and other additives were mixed in the composition shown in Tables 1 and 2, and added from the main filling portion. Further, a side feeder was set in the middle of the filling portion and the vent portion, and the glass fiber (F) was added in the same amount as shown in Tables 1 and 2 as described above. In addition,
The mixture was melt-mixed under a kneading temperature of 270 ° C. and an extrusion condition of a screw rotation of 150 rpm, discharged in a strand form, passed through a cooling path, and pelletized by a strand cutter.

After the obtained pellets were dried, each test piece was molded by an injection molding machine, and the physical properties were measured under the following conditions.

(1) Flame Retardancy Flame retardancy evaluation test pieces injection molded using a Toshiba Machine's IS55EPN injection molding machine at a molding temperature of 270 ° C. and a mold temperature of 80 ° C. are specified in UL94. The flame retardancy was evaluated according to the evaluation criteria. Flame retardant level is V-0
>V-1>V-2> HB. The thickness of the test piece is 1/16 "and 1/32", and the smaller the thickness, the more severe the flame retardancy.

(2) Moisture and heat resistance Bleed-out A 3 mm-thick 80 mm thick film was obtained at a molding temperature of 270 ° C. and a mold temperature of 80 ° C. using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd.
× 80 square plate was injection molded, and the obtained square plate
After treating at 1 ° C. and a humidity of 100% RH for 100 hours, the surface of the test piece was observed with an optical microscope.

Judgment of bleed-out ：: Not observed Δ: Somewhat observed ×: Decreases in order of observable amount.

(3) Mold Contamination Using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd., the mold was removed at a molding temperature of 270 ° C., a mold temperature of 80 ° C., an injection time of 15 seconds and a cooling time of 15 seconds. × 15
80mm x 80m of 3mm thickness with core of square mm
Injection molding of the m square plate was performed 2000 times. After injection molding, remove the 20 × 15mm square core and inspect the appearance,
Evaluation of mold contamination was performed by the following judgment.

Judgment of mold contamination ：: Almost no change in appearance of core surface △: Part of core surface is brown or black, and contamination is observed X: １ ／ or more of core surface is brown or black And is extremely contaminated.

(4) Impact Strength Using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., an Izod impact test piece having a thickness of 1/8 ″ was injection-molded at a molding temperature of 270 ° C. and a mold temperature of 80 ° C., and subjected to ASTM D2.
According to 56, the impact value was determined.

(5) Appearance of molded article 3 mm-thick 8 mm used in the moisture-heat resistance bleed-out test
The surface appearance of the 0 × 80 square plate was visually observed.

Judgment of appearance of molded article ◎: No defect in appearance and glossy ○: No defect in appearance ×: Irregularities are observed in part of appearance

[0078]

[Table 1]

[0079]

[Table 2]

[0080]

[Table 3]

From the evaluation results of Examples 1 to 8 in Table 1, PB
By blending red phosphorus and a hindered amine compound and / or aminotriazole compound in the T resin, a resin composition having specifically excellent wet heat properties and mold contamination can be obtained while maintaining high flame retardancy. You can see that.

On the other hand, it can be seen that the incorporation of only red phosphorus into the PBT resin causes poor wet heat properties and mold contamination (Comparative Example 1).

When a mixture of PET resin, PC resin or glass fiber is used as the PBT resin, the PBT resin exhibits more excellent flame retardancy as compared with the case of using the PBT resin alone, and also has a specific wet heat property and It can be seen that a resin composition having excellent mold contamination can be obtained.

On the other hand, even when a mixture of PET resin, PC resin or glass fiber was used as the PBT resin, it was found that the incorporation of red phosphorus alone caused poor wet heat characteristics and mold contamination (Comparative Example 2). , 3,4).

From Examples 9 to 25 in Table 2, when the ethylene (co) polymer of the present invention was used in combination, a great effect of improving the impact strength was observed while maintaining the excellent characteristics of the present invention. Further, when any of talc and a lubricant was added to the composition of the present invention or a combination thereof, an effect of improving the appearance of a molded product while maintaining the excellent characteristics of the present invention was recognized. Further, it can be seen that further improved flame retardancy can be obtained by blending any one of or a combination of the fluororesin and the stabilizer with the composition of the present invention.

Further, from Examples 20 to 25 in Table 2, when (E) PC of the present invention was blended with a lubricant in which a part of a fatty acid ester was converted into a calcium salt, trivalent It is clear that a composition having good wet heat resistance can be obtained by combining the phosphorus compound or the phosphite-based stabilizer. Further, the electric component of the present invention is sometimes used as a black colored product, and it is clear that excellent performance is maintained even when the carbon black of the present invention is used in combination.

[0087]

EFFECTS OF THE INVENTION By blending red phosphorus and a hindered amine compound and / or an aminotriazole compound with a PBT resin, bleed-out resistance when treated in a high-temperature and high-humidity state is suppressed, and the heat and moisture resistance and mold contamination are reduced. A flame-retardant PBT resin composition and a molded product using a non-halogen flame retardant having excellent flame retardancy can be obtained, and it can be expected to greatly contribute to market expansion of automobile parts, electric / electronic parts and mechanical parts.

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Claims (7)

[Claims] 1. A polybutylene terephthalate resin (A)
Flame-retardant poly obtained by blending (B) 0.1 to 50 parts by weight of red phosphorus and (C) 0.01 to 30 parts by weight of a hindered amine compound and / or an aminotriazole compound with respect to 00 parts by weight. Butylene terephthalate resin composition. 2. A polybutylene terephthalate resin (A)
(D) 1 to 15 parts by weight of the polyester resin per 100 parts by weight
The flame-retardant polybutylene terephthalate resin composition according to claim 1, further comprising 0 parts by weight. 3. A polybutylene terephthalate resin (A)
(E) Polycarbonate resin 1-1 to 100 parts by weight
3. The flame-retardant polybutylene terephthalate resin composition according to claim 1, further comprising 50 parts by weight. 4. A polybutylene terephthalate resin (A)
The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 3, further comprising (F) 5 to 200 parts by weight of the fibrous reinforcing material with respect to 00 parts by weight. 5. A polybutylene terephthalate resin (A)
(G) Ethylene (co) polymer 1-1 to 100 parts by weight
The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 4, further comprising 00 parts by weight. 6. A molded article in which a metal comprising the flame-retardant polybutylene terephthalate resin composition according to claim 1 is inserted. 7. A mechanical mechanism part, an electric / electronic part or an automobile part comprising the flame-retardant polybutylene terephthalate resin composition according to claim 1.