JP2001002943A - Thermoplastic resin composition - Google Patents

Abstract

(57) [Abstract] (Modified) [Problem] To dramatically suppress the generation of irritating gas, corrosive gas, and black smoke during combustion, and to provide excellent mechanical properties and fluidity inherent to thermoplastic resin. A flame-retardant thermoplastic resin composition capable of exhibiting moldability. SOLUTION: (A) 100 parts by weight of a thermoplastic resin (B) red phosphorus 0.1 to
30 parts by weight (C) filler having a porous structure 0.01 to
50 parts by weight (D) reinforced filler 0-1
50 parts by weight The thermoplastic resin (A) is preferably an aromatic thermoplastic resin, more preferably a condensation type thermoplastic resin, and still more preferably a thermoplastic polyester resin (A1) and an aromatic polycarbonate resin (A2 ) Or a composition with the polyphenylene ether resin (A3), or a polyamide resin (A4) and a composition with the polyphenylene ether resin (A3).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant thermoplastic resin composition using a non-halogen flame retardant. More specifically, the present invention relates to a flame-retardant thermoplastic resin composition and molded article suitable for thin and small electric / electronic device parts such as connectors, relays, transformer members, case members, and coil bobbins, automobile parts, and machine parts.

[0002]

2. Description of the Related Art Among thermoplastic resins, polyester resins are suitably used for electric and electronic parts, automobile parts and the like by using their excellent electric characteristics. In this field, the flame retardancy specified by the UL standard is often required, and it has been known for a long time that flame retardancy is generally imparted by a flame retardant represented by a halogen / antimony flame retardant or the like. . Although imparting flame retardancy by adding various halogen / antimony compounds has been somewhat successful, decomposition products of the halogen flame retardants may corrode metals used in electrical products. In addition, since the effect of some halogen-based flame retardants on the environment has become a problem, non-halogen-based flame-retardant resins have been demanded.

[0003] As non-halogen flame retardants, hydrated inorganic compounds such as aluminum hydroxide and magnesium hydroxide are generally known. However, these water-containing inorganic compounds have a poor flame-retarding effect on halogen-based flame retardants, and need to be added in a relatively large amount, and therefore have the drawback of significantly impairing mechanical strength and moldability. .

Further, a method of using a phosphoric acid ester as a phosphorus compound is disclosed in JP-A-03-281652 and JP-A-05-281652.
It is known from, for example, Japanese Patent No. -70671. However, even in the method using a phosphoric ester, a relatively large amount of addition is required because the flame retardant effect is small as compared with the halogen-based flame retardant, and as a result, a decrease in mechanical strength and a decrease in hydrolysis resistance are caused. There is a disadvantage that. On the other hand, red phosphorus has a relatively high flame-retardant effect, and although the hydrolysis resistance is hardly reduced by appropriate surface treatment itself, it is highly flame-retardant in polybutylene terephthalate, which is flammable. To obtain the property, a large amount of addition is required, and as a result, problems such as a decrease in mechanical strength and mold corrosivity occur, which is not practical. Further, there is a problem that corrosive gas is generated at the time of molding processing or when used for a relay part and the like, and irritating gas, corrosive gas, black smoke is generated at the time of combustion. Further, a method using a nitrogen compound having a triazine ring is disclosed in JP-B-58-5939 and JP-B-60-33.
It is known from the '850 publication. However, nitrogen compounds have problems such as not only having a low flame-retardant effect but also significantly reducing mechanical strength.

[0005] In the case of polyamide resin, a composition containing red phosphorus and an inorganic filler is used as a non-halogen flame-retardant resin having excellent flame retardancy, tracking resistance and mechanical strength. However, when the electric component has a metal contact, there is a problem that the metal is corroded by corrosive gas generated from red phosphorus and the conductivity is reduced. As a means for preventing the metal corrosion, a method of adding a specific metal compound, preferably cupric oxide, to a polyamide composition (US Pat. No. 3,883,475);
A method of adding cadmium oxide (French Patent 2367)
100 specification), a method of adding a zinc compound, preferably zinc oxide, zinc borate or zinc sulfide (JP-A-6-14).
Although these methods are known, the effect of preventing metal corrosion is insufficient.

[0006]

Under such circumstances, the present invention has been made to solve the above-mentioned disadvantages of the prior art. That is, the present invention has been a problem when using a flame retardant containing no bromine or chlorine atoms, suppresses the generation of corrosive gas and toxic gas during molding and when used in relay parts and the like, Flame-retardant thermoplastic resin composition that dramatically reduces the generation of irritating gas, corrosive gas, and black smoke during combustion, and can exhibit the excellent mechanical properties, fluidity, and moldability inherent to thermoplastic resins. The purpose is to provide things.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems. The gist of the present invention is that the following components (B) and 100 parts by weight of the thermoplastic resin (A) are used.
The present invention resides in a thermoplastic resin composition containing (C) and (D) in such proportions as to be in the following ranges. (B) red phosphorus 0.1 to 30 parts by weight (C) filler having a porous structure 0.01 to 50 parts by weight (D) reinforcing filler 0 to 150 parts by weight

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic resin (A) is preferably an aromatic thermoplastic resin, and more preferably a condensation type thermoplastic resin. Specifically, the thermoplastic resin (A) is preferably a thermoplastic polyester resin (A1) or a polyamide resin (A4). As the thermoplastic polyester resin (A1) in the present invention, a known aromatic polyester resin can be used. Here, the aromatic polyester resin is a polyester having an aromatic ring in a chain unit of a polymer, and is an aromatic dicarboxylic acid and a diol (and an ester-forming derivative thereof).
And a polymer or copolymer obtained by a polycondensation reaction containing as a main component.

As the aromatic dicarboxylic acid, phthalic acid,
Terephthalic acid, isophthalic acid, orthophthalic acid, 1,5
-Naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid Diphenylether-4,4'-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, diphenylisopropylidene-4,4'-dicarboxylic acid, anthracene-2,
Examples thereof include 5-dicarboxylic acid, anthracene-2,6-dicarboxylic acid, p-terphenylene-4,4′-dicarboxylic acid, and pyridine-2,5-dicarboxylic acid. Of these, terephthalic acid can be preferably used.

These aromatic dicarboxylic acids may be used as a mixture of two or more kinds. If the amount is small, one or more alicyclic dicarboxylic acids such as adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic acid, sebacic acid and dimer acid are used together with these aromatic dicarboxylic acids. be able to.

The diol component includes ethylene glycol, trimethylene glycol, propylene glycol,
Aliphatic glycols having about 2 to 12 carbon atoms, such as 1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexanediol, octanediol, decanediol, and the like, preferably having 2 to 10 carbon atoms
Degree of aliphatic glycol, polyoxyalkylene glycol (alkylene group having about 2 to 4 carbon atoms, glycol having a plurality of oxyalkylene units, for example,
Diethylene glycol, dipropylene glycol, ditetramethylene glycol, triethylene glycol, tripropylene glycol, tritetramethylene glycol, etc.), alicyclic diols (eg, 1,4-cyclohexanediol, 1,4-cyclohexane dimethylol, hydrogenation) Bisphenol A etc.), aromatic diols (e.g. 2,2-bis- (4- (2-hydroxyethoxy) phenyl) propane, xylene glycol etc.)
And the like. As the diol component, halogenated diols such as tetrabromobisphenol A and alkylene oxide (e.g., ethylene oxide and propylene oxide) adducts of tetrabromobisphenol A can also be used. These diol components may be used alone or in combination of two or more. If the amount is small, the molecular weight is 400 to 6,000.
Or a long-chain diol such as polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol or the like.

Preferred thermoplastic polyester resin (A
1) As polyethylene terephthalate (PE)
T), polypropylene terephthalate, polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), poly (cyclohexane-1,4-dimethylene-terephthalate) and the like. Ethylene glycol / isophthalate / terephthalate copolymers;
Copolymerized polyesters such as -butanediol / isophthalic acid / terephthalic acid copolymer and 1,4-butanediol / isophthalic acid / decanedicarboxylic acid copolymer can also be used. Further, a polyester elastomer composed of polybutylene terephthalate and polyoxytetramethylene glycol is also preferably used. In particular, at least one selected from polybutylene terephthalate, a polyester elastomer composed of polybutylene terephthalate and polyoxytetramethylene glycol, or polyethylene terephthalate is preferably used. Preferably, it is a seed, more preferably polybutylene terephthalate.

The thermoplastic polyester resin (A1) can be used alone or in combination of two or more. In addition, the thermoplastic polyester resin (A1) may have not only a linear structure but also a branched chain structure, or may be crosslinked, as long as the melt moldability and the like are not impaired.

The number average molecular weight of the thermoplastic polyester resin (A1) is not particularly limited, and may be, for example, 1 × 10 ⁴ to 10
It can be selected from the range of about 0 × 10 ⁴ , preferably about 3 × 10 ⁴ to 70 × 10 ⁴ , and more preferably about 5 × 10 ⁴ to 50 × 10 ⁴ . The intrinsic viscosity of the polyester resin (A1) is
0.5 to 2 dl / g, preferably 0.6 to 1.5 dl / g
g, more preferably 0.6 dl / g to 1.2 dl / g
It is about. In addition, the intrinsic viscosity is 1,1,1,
It is a value obtained by dissolving a sample in a mixed solvent of 2,2-tetrachloroethane at a weight ratio of 1: 1 and measuring the temperature at 30 ° C. using an Ubbelohde viscometer.

As the polyamide resin (A4), 3
A lactam having at least a member ring, a polymerizable ω-amino acid, or a polyamide obtained by polycondensation of a dibasic acid and a diamine can be used. Specifically, ε-caprolactam, aminocaproic acid, enantholactam,
7-aminoheptanoic acid, 11-aminoundecanoic acid, 9
Polymers such as -aminononanoic acid, α-pyrrolidone, α-piperidone, diamines such as hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, metaxylylenediamine, and terephthalic acid, isophthalic acid, adipic acid, and sebacic acid ,
Polymers obtained by polycondensation with dicarboxylic acids such as dodecane dibasic acid and glutaric acid, and copolymers thereof, for example, nylon 4, 6, 7, 8, 11,
12, 6.6, 6.9, 6.10, 6.11, 6.1
2,6T, 6 / 6.6,6 / 12,6 / 6T, 6I / 6
T, MXD6 and the like. As the polyamide resin (A4) in the present invention, more preferably, nylon 6, nylon 66, copolymer nylon 6/66, MXD6
Nylon and the like. In addition, a plurality of the above polyamide resins can be used in combination. The polyamide (A4) in the present invention preferably has a degree of polymerization within a certain range, that is, a viscosity. The preferred relative viscosity is JI
According to SK 6810, it is a value measured at a concentration of 1% in 98% sulfuric acid and a temperature of 25 ° C, and is selected from the range of 2.0 to 5.5, particularly preferably 2.2 to 4.5. If the relative viscosity is low, the mechanical properties decrease. Conversely, if it is too high, the moldability is impaired, which is not preferable.

In the present invention, the thermoplastic resin (A) is a thermoplastic polyester resin (A1) and an aromatic polycarbonate resin (A2) in a ratio of 95: 5 to 30:70 (weight ratio), preferably 95: 5 to 30:70. A resin composition blended in a ratio of 50:50 (weight ratio), a thermoplastic polyester resin (A1) and a polyphenylene ether resin (A3) in 9 parts
5: 5 to 30:70 (weight ratio), preferably 95: 5
50:50 (weight ratio), a resin composition, a polyamide resin (A4) and a polyphenylene ether resin (A
3) is also preferably used in a ratio of 95: 5 to 30:70 (weight ratio), preferably 95: 5 to 50:50 (weight ratio). The mixing ratio of these resins can be selected in a wide range according to the purpose, and is not limited to the above range.

The aromatic polycarbonate resin (A2) to be combined with the thermoplastic polyester resin (A1) can be obtained by reacting an aromatic hydroxy compound or a small amount thereof with a phosgene or carbonic acid diester. And a polycarbonate polymer or copolymer which may be branched. These polycarbonate polymers or copolymers may be used as a mixture of two or more kinds. Examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, and bis (4-hydroxyphenyl) -p
-Diisopropylidenebenzene, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl and the like, and preferably bisphenol A. Two or more of these dihydroxy compounds may be used in combination.

In order to obtain a branched aromatic polycarbonate, phloroglucin, 4,6-dimethyl-2,4,6-
Tri (4-hydroxyphenyl) heptene-2,4,6
-Dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3,1,3,5
-Tri (4-hydroxyphenyl) benzol, 1,
1,1-tri (4-hydroxyphenyl) ethane, 2,
6-bis (2-hydroxy-5-methylbenzyl) -4
Polyhydroxy compounds represented by -methylphenol, α, α ', α "-tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, or 3,3-bis (4-hydroxyphenyl) oxy Indole (= isatin bisphenol), 5-chlorisatin bisphenol, 5,7-dichlorisatin bisphenol, 5-bromoisatin bisphenol and the like may be used as a part of the aromatic dihydroxy compound,
The amount used is 0.01 to 10 mol%, preferably 0.1 to 2 mol%.

The viscosity average molecular weight of the aromatic polycarbonate (A2) used in the present invention is a value calculated from a solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, and is preferably 12,000 to 100, 00
0, more preferably 16,000 to 30,000
And most preferably from 18,000 to 23,000.

In order to control the molecular weight of the aromatic polycarbonate (A2), a monovalent aromatic hydroxy compound may be used, and m- and p-methylphenol, m- and p-propylphenol, p-tert-butylphenol and p-long-chain alkyl-substituted phenols and the like.
The aromatic polycarbonate resin (A2) used in the present invention is preferably a polycarbonate resin using bisphenol A as an aromatic dihydroxy compound, or an aromatic polycarbonate copolymer derived from bisphenol A and another aromatic dihydroxy compound. Is mentioned.

The polyphenylene ether (A3) which can be used in combination with the thermoplastic polyester resin (A1) or the polyamide resin (A4) in the present invention is, specifically, poly (2,6-dimethyl-1,4- Phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-
Phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-
Examples thereof include 6-propyl-1,4-phenylene) ether, and particularly, poly (2,6-dimethyl-1,4-phenylene) ether and 2,6-dimethylphenol /
A 2,3,6-trimethylphenol copolymer and a graft copolymer obtained by graft-polymerizing styrene onto these are preferred. In the present invention, a modified polyphenylene ether obtained by reacting the polyphenylene ether with an unsaturated aliphatic carboxylic acid or an acid anhydride thereof can also be used. When the acid anhydride of the unsaturated aliphatic carboxylic acid is used, a modified polyphenylene ether is obtained by reacting the acid anhydride of the unsaturated aliphatic carboxylic acid and polyphenylene ether in a melt-mixed state without using a catalyst. Can be.
In this case, the method of melt mixing is not particularly limited, such as a kneader, a Banbury mixer, and an extruder. However, in consideration of operability and the like, it is preferable to use an extruder. Examples of the unsaturated carboxylic anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride and the like, and among them, maleic anhydride is preferable. The proportion of the unsaturated carboxylic acid or anhydride required for modifying the polyphenylene ether is based on 100 parts by weight of the polyphenylene ether.
0.01 to 10 parts by weight, preferably 0.1 to 3 parts by weight,
Particularly preferably, it is 0.1 to 1 part by weight. When the amount is 0.01 part by weight or less, the effect of the combined use with the thermoplastic polyester resin (A1) and the polyamide resin (A4) is small, and
Exceeding the weight part is not preferred because the acid anhydride is thermally decomposed, resulting in practical inconveniences such as a decrease in heat resistance and poor appearance. When an unsaturated aliphatic carboxylic acid is used for modifying polyphenylene ether, a radical generator such as benzoyl peroxide, dicumyl peroxide, and cumene hydroperoxide can be used as a catalyst, if necessary.

The red phosphorus (B) used in the present invention can be blended without any treatment.
Since there is a risk of ignition or hydrolysis during storage, those treated to prevent this are preferably used. As a method of such a treatment, a method described in a known document is used.For example, a red phosphorus is added to red phosphorus by adding a small amount of aluminum hydroxide, magnesium hydroxide, zinc hydroxide and a hydroxide of titanium. There is a method of catalytically suppressing the oxidation of phosphorus. In addition, a method of coating with paraffin or wax, a method of coating with a thermosetting resin such as a phenolic, melamine, epoxy, or unsaturated polyester type, or an aqueous solution of red phosphorus with a metal salt such as copper, nickel, or silver And a method of precipitating and stabilizing a metal phosphorus compound on the surface of red phosphorus by treating with the above method. Also,
The average particle size of red phosphorus before being blended with the resin is not particularly limited, but is preferably 10% from the viewpoint of suppressing a decrease in mechanical strength.
μm or less, more preferably 1 μm or less.

The amount of the red phosphorus (B) is 1 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 2 to 15 parts by weight, based on 100 parts by weight of the thermoplastic resin (A). . If the amount of red phosphorus (B) is less than 1 part by weight, the flame-retardant effect is not sufficient, and if it exceeds 30 parts by weight, the mechanical properties are significantly reduced, which is not preferable.

In the present invention, it is an essential requirement that an additive (C) having a porous structure is further used in combination. It is considered that this can suppress the adsorption of corrosive gas and irritating gas generated during molding or the like, which has been a problem when red phosphorus, which is a non-halogen flame retardant, is used. In the present invention, the additive (C) having the porous structure preferably has a BET specific surface area of 30 m ² / g or more. Specifically, a synthetic adsorbent containing silica gel, (active) alumina, zeolite, activated clay, activated carbon, magnesium oxide, magnesium hydroxide, magnesium silicate, Mg, Al or Si oxide or a combination thereof as a main component ( Specific examples include Kyowa Corporation's trade name (Kyoward) and synthetic adsorbents represented by hydrotalcite. Among them, when using the thermoplastic polyester resin (A1), preferably, silica gel,
(Active) alumina and zeolite are used. When a polyamide resin (A4) is used, magnesium oxide and silica gel are preferably used.

The amount of the additive (C) having a porous structure is 0.0 to 100 parts by weight of the thermoplastic resin (A).
It is 1 to 50 parts by weight, preferably 0.01 to 20 parts by weight. When the amount is less than 0.01 part by weight, the effect of improving the corrosiveness is not sufficient, and when the amount is more than 50 parts by weight, the mechanical properties are lowered and the fluidity is remarkably lowered.

The reinforcing filler (D) used in the present invention may be an organic filler or an inorganic filler, for example, glass fiber, glass flake, glass beads, carbon, silica, silica / alumina, zirconia, boron, boron nitride, Silicon nitride, potassium titanate, stainless steel, aluminum, titanium, copper, brass, talc, mica, kaolin, wollastonite, calcium carbonate, titanium oxide, zinc oxide, barium sulfate, potassium titanate whisker, aluminum borate whisker, etc. Inorganic fibers, metal fibers and other inorganic fillers, as well as organic fibers (eg, aromatic polyamide fibers, fluororesin fibers, liquid crystalline aromatic polyester fibers, etc.) are included. In the present invention, a preferable reinforcing filler (D) includes inorganic fibers (for example, glass fibers). The glass fiber of the preferable reinforcing filler is not particularly limited as long as it is usually used for a thermoplastic resin, but a chopped strand made of E glass (alkali-free glass) is preferable. The reinforcing filler (D) can be used alone or in combination of two or more.

When the reinforcing filler (D) is an inorganic or organic fiber, its average fiber diameter is not particularly limited.
To 100 μm, preferably 1 to 50 μm, more preferably 3 to 30 μm, still more preferably 1 to 20 μm, and most preferably about 5 to 15 μm, and the average fiber length is not particularly limited. 20mm,
It is preferably about 1 to 10 mm.

The reinforcing filler (D) may be used as a sizing agent or a surface treatment agent (for example, an epoxy compound, an acrylic compound, an isocyanate compound) in order to improve the interfacial adhesion with the thermoplastic resin (A). , A silane compound, a titanate compound or the like). The reinforcing filler (D) may be surface-treated in advance with the sizing agent or the surface treatment agent, or may be surface-treated by adding the sizing agent or the surface treatment agent during preparation of the thermoplastic resin composition. Good. The amount of the reinforcing filler (D) added is 0% based on the entire thermoplastic resin composition.
It is preferably from 60 to 60% by weight, more preferably from 10 to 50% by weight, and even more preferably from 0 to 40% by weight. If the added amount exceeds 60% by weight, the fluidity may be remarkably reduced or the formability or appearance may be impaired. On the other hand, if the added amount is small, the material strength may be reduced, so that it is not preferable.

The thermoplastic resin composition of the present invention may contain a nitrogen-containing compound (E) in order to further increase the flame retardancy in addition to the components (A) to (D). Examples of the nitrogen-containing compound (F) include triazine-based compounds such as melamine and cyanuric acid, and tetrazole compounds. Preferable examples include a salt of melamine and cyanuric acid, or melam and / or melem, which is a dimer and / or trimer of melamine. The addition amount of the nitrogen-containing compound (E) is 1 to 50 parts by weight based on 100 parts by weight of the thermoplastic resin (A). If the amount is less than 1 part by weight, the effect of improving the flame retardancy by adding these compounds is not sufficient. If the amount is more than 50 parts by weight, the mechanical properties are significantly reduced, which is not preferable. When the polyamide resin (A4) is used in the present invention, magnesium hydroxide, zinc borate, polyphosphate, etc. may be used instead of the nitrogen-containing compound (E) as long as the effects of the present invention are not impaired. A phosphorus-based flame retardant other than red phosphorus may be included.

Further, the resin composition of the present invention may contain polytetrafluoroethylene (F). This functions as an anti-dripping agent, for example, polytetrafluoroethylene having fibril-forming ability.
This shows a tendency to easily disperse in the polymer and combine the polymers to form a fibrous material. Polytetrafluoroethylene having fibril-forming ability is AST
Classified into Type 3 by M standard. Examples of the polytetrafluoroethylene having a fibril-forming ability include polyeflon FA-500 (trade name) from Daikin Industries, Ltd., or Teflon 6J (trade name) or Teflon 3 from Mitsui / Dupont Fluorochemicals Co., Ltd.
It is commercially available as 0J (trade name) or the like. Fluorinated polyolefins such as polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, and vinylidene fluoride, and the like are preferable, and polytetrafluoroethylene and tetrafluoroethylene are preferable. An ethylene / hexafluoropropylene copolymer is preferred.

The amount of polytetrafluoroethylene (F) added is based on 100 parts by weight of the thermoplastic resin (A).
It is 0.1 to 5 parts by weight, preferably 0.1 to 3 parts by weight. When the amount of the polytetrafluoroethylene added is 0.
If the amount is less than 1 part by weight, the ability to prevent dripping during combustion is insufficient.
If the amount is more than 5 parts by weight, the fluidity and mechanical properties are notably reduced, which is not preferable.

The thermoplastic resin composition of the present invention may further contain conventional additives, if necessary, depending on the type of the resin. As the additive, an antioxidant,
Stabilizers such as UV absorbers, heat stabilizers, and weather stabilizers,
Impact modifiers such as elastomers, lubricants, release agents, coloring agents such as dyes and pigments such as carbon black, catalyst deactivators, antistatic agents, foaming agents, plasticizers, crystal nucleating agents, crystallization accelerators, etc. Can be

The method for producing the thermoplastic resin composition of the present invention is not limited to a particular method, but is preferably by melt-kneading, and a kneading method generally used for thermoplastic resins can be applied.

As the kneading method, for example, if necessary, each component is uniformly mixed with a substance as an additional component using a Henschel mixer, a ribbon blender, a V-type blender or the like, and then a single-screw or multi-screw extruder is used. ,roll,
It can be kneaded with a Banbury mixer, Labo Plastomill (Bradender) or the like.

Each component, including additional components (additives),
It is performed at any stage from resin polymerization to molding,
It is preferable to perform melt kneading using an extruder. These may be fed to the kneader at once or sequentially. Further, a mixture of two or more components selected from each component including an additional component may be used in advance. The molding method of the thermoplastic resin composition of the present invention is not particularly limited, and a molding method generally used for thermoplastic resins, that is, injection molding, hollow molding, extrusion molding,
A molding method such as press molding can be applied.

[0036]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, unless the present invention exceeds the gist thereof,
The present invention is not limited to the following embodiments. The evaluation of the physical properties and the like of the resin composition was performed by the following tests. The abbreviations and contents of the components used in the present examples and comparative examples are as follows. (1) Polybutylene terephthalate: a product of Mitsubishi Engineering-Plastics Co., Ltd., trade name Novadur (registered trademark) 5008AS (hereinafter, referred to as “PBT”). (2) Aromatic polycarbonate: a product of Mitsubishi Engineering-Plastics Corporation. Brand name NOVAREX (registered trademark) 7022PJ, viscosity average molecular weight 22,000.
(Hereinafter, referred to as “PC”) (3) Polyamide 6 resin: a product of Mitsubishi Engineering-Plastics Corporation, trade name Novamid (registered trademark) 1
010 J, relative viscosity 2.5. (4) Red phosphorus master pellets: Red phosphorus (product name: Nova Excel 140, manufactured by Rin Kagaku Kogyo Co., Ltd.) surface-coated with phenol resin and aluminum hydroxide by PBT
What was made into a master pellet in. The mixing ratio is PBT70
30 parts by weight of Nova Excel 140 based on parts by weight (5) Red phosphorus: Nippon Chemical Industrial Co., Ltd., trade name: Hishigard TP-10 (coated with titanium oxide) (6) GF1: Glass fiber (Nippon Electric Glass) Products, Inc.
(Trade name: T-123, GF diameter: 13 μm) (7) GF2: glass fiber (manufactured by NEC Corporation,
Product name T-283, GF diameter 13 μm. (8) Nitrogen-containing compound: melamine cyanurate (Mitsubishi Chemical
(9) Polytetrafluoroethylene: PTFE (manufactured by Daikin Industries, Ltd., trade name: Polyflon FA-500).
(Hereinafter also referred to as “PTFE”) (10) Silica gel: (Fuji Silysia Chemical Ltd. product,
Trade name Cycilia 330 (BET value 300 m ² / g).
(Hereinafter, referred to as “silica gel”) (11) Activated alumina: (product name: BK112 (BET value: 300 m ² / g) manufactured by Sumitomo Chemical Co., Ltd.) (hereinafter, referred to as “activated alumina”) (12) Magnesium oxide: (product of Kyowa Chemical Co., Ltd., trade name Micromag 3-150 (BET value 150 m ² /
g). (Hereinafter, referred to as “MgO”)

The evaluation test was conducted by the following method.
Was. (A) Tensile strength: according to ASTM standard D-638
ASTM D-6 using the tensile test piece prepared
Thirty-eight tensile tests were performed. The tensile strength is kg
/ Cm^Two Display in units of. (B) Flexural modulus: according to ASTM standard D-790
Using the prepared bending test piece, ASTM D-790
A bending test was performed. Flexural modulus is kg / cm ^TwoSimply
Display in place.

(C) Flammability 1: UL of Underwriter's Laboratories Inc.
Using a 1/32 "thick test piece prepared according to Standard 94, a 20 mm vertical combustion test of UL Standard 94 was performed. From the highest flame retardancy level, V-0>V-1> V-
2> HB. (D) Flammability 2: Glow wire ignitability test (IEC-6)
(E) Corrosion: 50 g of pretreated pellets are placed in a 120 cc glass jar. Further, a Cu plate to be corroded is placed in a petri dish placed above the pellet so as not to be in contact with the pellet, and sealed. Then 150 ° C
And the degree of corrosion was observed. The pretreatment of the pellets was carried out at 120 ° C. for 6 hours, and then at 23 ° C.-5
Conditioning was performed at 0% RH for 48 hours. (F) Metal corrosion: A silver plate was placed on a tensile test piece (ASTM No. 1 dumbbell), wrapped strictly in aluminum foil, taken out after heat treatment at 140 ° C. for 300 hours in a hot air oven, and the state of corrosion of the silver plate was visually observed. .

[Examples 1 to 5] The components shown in Table 1 were sufficiently mixed and stirred at the mixing ratios shown in Table 1, and then the mixture was extruded into a twin-screw extruded product of Nippon Steel Corporation with a vent port. (Trade name: TEX30C), the pressure is reduced to 600 Torr from the vent port installed downstream of the first hopper, and the set temperature 2
Under a kneading condition of 55 ° C. and a screw rotation speed of 200 rpm, the mixture was melt-kneaded to obtain a composition, which was then pelletized to obtain a thermoplastic resin composition. The production rate was 20 kg / hr. The obtained pellets were dried at 120 ° C. for 6 hours in advance, injection-molded to obtain various test pieces, and evaluated. Table 1 shows the evaluation results.

[0040]

[Table 1]

[Comparative Examples 1 to 5] The components shown in Table 2 were mixed at the mixing ratios shown in Table 2 in the same manner as in Examples 1 to 5 to obtain pellets. The obtained pellets are
After drying at 6 ° C. for 6 hours, injection molding was performed to obtain various test pieces, which were evaluated. Table 2 shows the evaluation results.

[0042]

[Table 2]

From the above results, it is clear that all the examples maintain high strength, are excellent in flame retardancy, and show excellent corrosion resistance. Comparative Example 1 shows that sufficient flame retardancy cannot be obtained without red phosphorus (B), and Comparative Examples 2 and 3 show that flame retardancy is reduced by using red phosphorus (B). Although sufficient, it shows that it is inferior in corrosiveness, and Comparative Examples 4 and 5 show that even if there is red phosphorus (B), sufficient flame retardancy cannot be obtained without an aromatic polycarbonate resin. ing.

[Examples 6 and 7 and Comparative Examples 6 and 7] The polyamide resin, red phosphorus, porous filler, and reinforcing inorganic filler were blended with the components shown in Table 3 in the amounts shown in Table 3. Using a TEX30HCT type twin screw extruder manufactured by Nippon Steel Corporation, the mixture was melt-mixed at a set temperature of 280 ° C. to obtain pellets of a polyamide resin composition. The pellets were injection-molded according to each molded product, and the mechanical properties, flammability, and metal corrosivity were evaluated. Table 3 shows the evaluation results.

[0045]

[Table 3]

Example 8 and Comparative Example 8 The following Example 8
The components used in Comparative Example 8 are as follows. (1) Modified polyphenylene ether (modified PPE): 50 g of maleic anhydride was added to 5 kg of a product of Mitsubishi Engineering-Plastics Corporation, trade name Iupiace (registered trademark) CPX, and mixed with a super mixer for 3 minutes. The mixture was kneaded with a twin-screw extruder at 300 ° C. while being heated and melted to obtain maleic anhydride-modified PPE. (2) Polyamide MXD6 (a crystalline thermoplastic resin obtained from meta-xylylenediamine and adipic acid): a product of Mitsubishi Engineering-Plastics Corporation, trade name Lenny (registered trademark) 6000). (3) Polyamide 66: product of Toray Industries, grade name 3
001N. (4) GF3: glass fiber (manufactured by NEC Corporation,
Trade name: T-296A (GF diameter: 10 μm) The components shown in Table 4 were added in the amounts shown in Table 4 in modified PPE,
After blending the polyamide resin, red phosphorus, the porous filler, and the reinforcing inorganic filler, the mixture is melt-mixed at a set temperature of 285 ° C. using a single screw extruder manufactured by Nakatani Corporation to obtain pellets of the polyamide resin composition. Was. The pellets were injection-molded according to the respective molded articles, and the mechanical properties, flammability, and metal corrosivity were evaluated. Table 4 shows the evaluation results.

[0047]

[Table 4]

[0048]

As described above, in the present invention, the thermoplastic resin composition using the thermoplastic polyester resin enhances the flame retardancy with a non-halogen flame retardant, and further has a problem in that case. It suppresses the generation of toxic and corrosive gases at the time of molding and burning, and can highly express the excellent mechanical properties, fluidity and moldability inherent to thermoplastic polyester resins. On the other hand, the thermoplastic resin composition using a polyamide resin in the present invention has excellent flame retardancy and mechanical strength, and has low metal contact corrosion, so that it has metal contacts such as breakers, switches, and electromagnetic switches. Suitable for use in electrical components.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/34 C08K 3/34 3/36 3/36 5/3492 5/3492 7/14 7/14 7 / 22 7/22 7/24 7/24 C08L 67/02 C08L 67/02 69/00 69/00 71/12 71/12 77/00 77/00 // (C08L 101/16 27:18) (72 ) Inventor Shigeru Muramatsu 5-6-2 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Inside the Engineering Center of Mitsubishi Engineering-Plastics Co., Ltd. Inside the Technology Center of the Company (72) Inventor Kazuo Oyama 5-6-2 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Inside the Technology Center of Mitsubishi Engineering-Plastics Co., Ltd. (72) Masami Suzuki Higashihachi, Hiratsuka-shi, Kanagawa 5-6-2 Mitsubishi Engineering Plastics Co., Ltd. Technology Center F term (reference) 4J002 BD123 BD154 BD164 BN18X CF04W CF05W CF06W CF07W CF08W CF09W CF10W CF12W CF14W CF16W CF183 CG01X CG03X CH07X CL01W CL02W CL03W CL05WCL06 DA06 DA078 DA088 DA098 DC008 DE077 DE098 DE138 DE147 DE188 DE238 DE287 DG048 DJ007 DJ008 DJ017 DJ018 DJ038 DJ058 DK008 DL008 EU009 EU189 EU199 FA018 FA048 FA068 FA088 FA097 FB076 FB266 FD013 FD017 FD018 FD020 FD100 FD100 FD0000 FD060 FD070 FD060 FD070 FD060 FD060 FD070 FD070 FD070 FD070 FD070 FD060 FD070 FD060

Claims (20)

[Claims] 1. A thermoplastic resin composition comprising the following components (B), (C) and (D) in the following ranges with respect to 100 parts by weight of the thermoplastic resin (A). object. (B) red phosphorus 0.1 to 30 parts by weight (C) filler having a porous structure 0.01 to 50 parts by weight (D) reinforcing filler 0 to 150 parts by weight 2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (A) is an aromatic thermoplastic resin. 3. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (A) is a condensation type thermoplastic resin. 4. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (A) is a thermoplastic polyester resin (A1). 5. The thermoplastic polyester resin (A1) comprises:
5. The thermoplastic resin composition according to claim 4, wherein the thermoplastic resin composition is at least one selected from polybutylene terephthalate, a polyester elastomer composed of polybutylene terephthalate and polyoxytetramethylene glycol, or polyethylene terephthalate. 6. The thermoplastic resin (A) is a thermoplastic polyester resin (A1): an aromatic polycarbonate resin (A).
2) The thermoplastic resin composition according to any one of claims 1 to 5, wherein the resin composition has a weight ratio of 95: 5 to 30:70. 7. A thermoplastic polyester resin (A1): an aromatic polycarbonate resin (A2) = 95: 5 to 50:
The thermoplastic resin composition according to claim 6, wherein the weight ratio is 50 (weight ratio). 8. The thermoplastic resin composition according to claim 6, wherein the filler (C) having a porous structure is at least one selected from alumina, silica gel, activated carbon and zeolite. 9. The thermoplastic resin (A) is a thermoplastic polyester resin (A1): a polyphenylene ether resin (A).
3) = 95: 5 to 50:50 (weight ratio).
6. The thermoplastic resin composition according to any one of items 1 to 5. 10. A thermoplastic polyester resin (A1):
Polyphenylene ether resin (A3) = 95: 5-5
The thermoplastic resin composition according to claim 9, wherein the ratio is 0:50 (weight ratio). 11. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyamide resin (A4). 12. The thermoplastic resin (A) is a polyamide resin (A4): polyphenylene ether resin (A3) = 9.
The thermoplastic resin composition according to any one of claims 1 to 3, and 11, wherein the ratio is 5: 5 to 50:50 (weight ratio). 13. The thermoplastic resin (A) is a polyamide resin (A4): polyphenylene ether resin (A3) = 9.
The thermoplastic resin composition according to claim 12, wherein the ratio is 5: 5 to 50:50 (weight ratio). 14. The thermoplastic resin composition according to claim 1, comprising 1 to 50 parts by weight of the nitrogen-containing compound (E) based on 100 parts by weight of the thermoplastic resin (A). . 15. The thermoplastic resin composition according to claim 14, wherein the nitrogen-containing compound (E) is a triazine-based compound. 16. The thermoplastic resin composition according to claim 15, wherein the triazine compound is melamine and is a salt with cyanuric acid or isocyanuric acid. 17. The thermoplastic resin composition according to claim 16, wherein the triazine-based compound is melam which is a dimer of melamine and / or melem which is a trimer of melamine. 18. Polytetrafluoroethylene (F)
From 0.1 to 100 parts by weight of the thermoplastic resin (A)
The thermoplastic resin composition according to any one of claims 1 to 17, comprising 5 parts by weight. 19. The thermoplastic resin composition according to claim 1, wherein the reinforcing filler (D) is glass fiber. 20. A molded article obtained by molding the thermoplastic resin composition according to any one of claims 1 to 19.