JP2000159990A - Flame retarded resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame retarded resin composition excellent in mechanical properties, flame retardancy and electric characteristics, also suppressing a bleed out caused by a moist heat treatment and causing small deterioration in electrical characteristics by the moist heat treatment. SOLUTION: This flame retarded resin composition is obtained by blending (A) 100 pts.wt. thermoplastic polyester resin, (B) 0.1-50 pts.wt. layered silicate of which exchangeable cation existing between layers is exchanged by an organic onium ion and (C) 0.1-30 pts.wt. red phosphorus having 1-1,000 μS/cm conductivity (provided that the above conductivity is that of an extract water obtained by adding 100 mL pure water to 5 g red phosphorus, extracting at 121 deg.C for 100 hr, filtering the red phosphorus and then diluting the filtrate to 250 mL.).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for producing a resin composition, which is excellent in mechanical properties, flame retardancy, and electrical properties, suppresses bleed-out due to wet heat treatment, and reduces electrical properties due to wet heat treatment.
The present invention relates to a flame-retardant resin composition suitable for electric / electronic parts and automobile parts.

[0002]

2. Description of the Related Art Polyester resins typified by polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexane dimethylene terephthalate, etc., take advantage of their excellent characteristics and are used as injection molding materials for mechanical and mechanical parts, electric and electronic parts, and automobiles. It is being used in a wide range of fields such as parts. On the other hand, since these thermoplastic resins are inherently flammable, in order to be used as industrial materials, in addition to the general balance of chemical and physical properties, fire safety, that is, flame retardancy is required. Often.

[0003] Further, in order to impart flame retardancy, it is generally applied to blend a halogen-based flame retardant, but there is a problem that a large amount of smoke is generated during combustion.

[0004] However, the method of blending a halogen-based organic compound has a problem that the amount of smoke generated during combustion is large. 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, addition of red phosphorus is disclosed in JP-A-51-150553 and JP-A-58-1983.
-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. However, although any resin composition is a useful flame-retardant resin material that does not use a halogen-based flame retardant, the excellent mechanical properties of the thermoplastic resin are impaired, or these molded products are treated at high temperature and high humidity. When you do
There has been a problem that the bleeding material is deposited on the surface or the electrical properties are deteriorated by the wet heat treatment, resulting in dielectric breakdown.

In recent years, mechanical and mechanical parts, electric and electronic parts, and automobile parts have tended to be miniaturized and integrated, and high rigidity, high heat resistance and light weight are required. To meet these demands, it has been applied as a general method to blend an inorganic filler such as glass fiber into a thermoplastic resin. However, in order to obtain sufficient rigidity, it is necessary to mix a considerable amount of an inorganic filler, and not only the problem that the obtained resin composition has a high specific gravity, but also the flame retardancy due to the addition of an inorganic filler such as glass fiber. Has a problem of remarkably lowering, and a problem of lowering of electrical characteristics.

As a method for improving the flame retardancy, rigidity and specific gravity, Japanese Patent Application Laid-Open No. 10-60160 discloses a method in which a phosphorus-based flame retardant is used as a thermoplastic resin, and an interlayer containing a layered silicate as a host and an organic onium ion as a guest. A method using a compound and a compatibilizer such as lactones, lactams and polymers thereof is disclosed.

However, although the flame-retardant resin composition obtained by this method is improved in rigidity, it has a problem in that the toughness is reduced and the effect of imparting flame retardancy is not sufficient.

[0010]

That is, the present invention uses a non-halogen flame retardant, and has excellent flame retardancy, excellent mechanical properties, and is processed in a high temperature and high humidity state in a thin molded article. It is an object of the present invention to obtain a flame-retardant resin composition having less bleed-out at the time and having excellent electric characteristics.

[0011]

Means for Solving the Problems In view of the above situation, the present inventors have made intensive studies and as a result, have obtained a layered silicate in which an organic onium ion is inserted between layers in a thermoplastic polyester resin and a specific conductivity. The present inventors have found that the problem can be solved by blending red phosphorus, and have reached the present invention.

That is, the present invention provides (A) 100 parts by weight of a thermoplastic polyester resin, (B) 0.1 to 50 parts by weight of a layered silicate in which exchangeable cations existing between layers have been exchanged with organic onium ions, and (C) conductivity of 0.1 to 1
A flame-retardant resin composition containing 0.1 to 30 parts by weight of red phosphorus having a conductivity of 5,000 μS / cm.
To 100 g of pure water, 100 ml of pure water is added, and the mixture is extracted at 121 ° C. for 100 hours. The flame-retardant resin composition, wherein the red phosphorus (C) is unground red phosphorus and is a red phosphorus coated with a thermosetting resin, (D) a phosphate ester 0 represented by the following general formula (1): The flame-retardant resin composition further comprising 1 to 30 parts by weight,

[0013]

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(In the above formula, R ^{1 to} R ⁸ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.)
Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ represent the same or different phenyl groups or phenyl groups substituted with halogen-free organic residues. Y is a direct bond, O,
Represents S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CHPh;
h represents a phenyl group. N is an integer of 0 or more.
K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less. (A) The thermoplastic polyester resin is one or more selected from polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexane dimethylene terephthalate, and poly (ethylene terephthalate / cyclohexane dimethylene terephthalate). The flame-retardant resin composition, (B) a layered silicate in which exchangeable cations present between layers have been exchanged with organic onium ions, and a layered silicate further treated with a coupling agent having a reactive functional group; (E) an organic compound having at least one functional group reactive with a thermoplastic polyester in a molecule with respect to 100 parts by weight of the thermoplastic polyester resin (A). The above further comprising 10 parts by weight The flame-retardant resin composition, (E) that the functional group of the organic compound having at least one functional group reactive with the thermoplastic polyester resin in the molecule is a carboxylic anhydride group and / or an epoxy group. The flame-retardant resin composition described above, wherein (E) the organic compound having at least one functional group reactive with the thermoplastic polyester resin in the molecule is an olefin compound having a carboxylic anhydride group in the molecule or The flame-retardant resin composition as a polymer of the olefin compound, (A) a thermoplastic polyester resin 10
The flame-retardant resin composition obtained by further mixing 0.01 to 10 parts by weight of a fluorine resin with respect to 0 parts by weight, and a triazine compound and cyanuric acid with respect to 100 parts by weight of the thermoplastic polyester resin (A). Or the flame-retardant resin composition further comprising 0.01 to 20 parts by weight of a salt comprising isocyanuric acid, (A) a thermoplastic polyester resin 1
0.1 to 1 part by weight of polycarbonate resin
(A) a thermoplastic polyester resin, (B) a layered silicate in which exchangeable cations existing between layers have been exchanged with organic onium ions, (C) ) Conductivity of 0.1 to 1000 μS /
cm of red phosphorus in an extruder to produce the flame-retardant resin composition, wherein (A) a part of the thermoplastic polyester resin and ( C) Red phosphorus having a conductivity of 0.1 to 1000 μS / cm is once melt-kneaded to produce a resin composition (F) having a high red phosphorus concentration, and the remaining thermoplastic polyester resin (A) is present between the layers. Producing the above flame-retardant resin composition by melt-kneading a layered silicate (B) in which exchangeable cations have been exchanged with organic onium ions and a resin composition (F) having a high red phosphorus concentration in an extruder; A method for producing a flame-retardant resin composition, and the present invention is a molded article comprising the flame-retardant resin composition, wherein the molded article is a mechanical mechanism part, an electric / electronic part or an automobile part. The molded article, the flame-retardant resin composition A molded article formed from,
The molded article is the above-mentioned molded article, which is a connector, a coil bobbin, a relay or a switch.

[0015]

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

As the thermoplastic polyester resin (A), a thermoplastic polyester having an aromatic ring in a chain unit of a polymer can be mentioned. Usually, an aromatic dicarboxylic acid (or an ester-forming derivative thereof) and a diol (or an ester-forming derivative thereof) are used. Ester-forming derivatives) and / or polymers or copolymers obtained by a condensation reaction using hydroxycarboxylic acid as a main raw material. These may be liquid crystalline or non-liquid crystalline.

Specific examples of preferred polyesters in the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate,
Polyalkylene terephthalate such as polycyclohexane dimethylene terephthalate and polyhexylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, polybutylene-2,6-naphthalenedicarboxylate, polyethylene-1,2-bis (phenoxy) ethane- In addition to 4,4′-dicarboxylate, polyethylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polybutylene terephthalate / decane dicarboxylate, polyethylene-4,4′-dicarboxylate / terephthalate,
Non-liquid crystalline polyesters such as poly (ethylene terephthalate / cyclohexane dimethylene terephthalate).

The liquid crystalline polyester forms an anisotropic molten phase composed of structural units selected from aromatic oxycarbonyl units, aromatic dioxy units, aromatic dicarbonyl units, ethylenedioxy units and the like. Polyester can be mentioned.

Examples of the aromatic oxycarbonyl unit include, for example, p-hydroxybenzoic acid and 6-hydroxy-2-
Structural units generated from naphthoic acid, aromatic dioxy units include, for example, 4,4′-dihydroxybiphenyl, hydroquinone, structural units generated from t-butylhydroquinone, and aromatic dicarbonyl units include, for example, terephthalic acid, Examples of the structural unit generated from isophthalic acid and 2,6-naphthalenedicarboxylic acid and the aromatic iminooxy unit include a structural unit generated from 4-aminophenol. Specific examples include liquid crystalline polyesters such as p-oxybenzoic acid / polyethylene terephthalate and p-oxybenzoic acid / 6-oxy-2-naphthoic acid.

Particularly preferred are polybutylene terephthalate, polypropylene terephthalate,
Examples include polyethylene terephthalate, polyethylene naphthalate, polycyclohexane dimethylene terephthalate, and poly (ethylene terephthalate / cyclohexane dimethylene terephthalate). These polyester resins are required for properties such as flame retardancy, moldability, heat resistance, toughness, and surface properties. It is also practically suitable to use as a mixture according to the above, and in particular, one or two selected from polybutylene terephthalate and polyethylene terephthalate are preferred.

The degree of polymerization of these thermoplastic polyesters is not limited, but the intrinsic viscosity measured at 25 ° C. in a 0.5% o-chlorophenol solution is in the range of 0.80 to 1.9, especially 1 Those having a range of 0.0 to 1.5 are preferred.

In the present invention, the term (B) a layered silicate in which exchangeable cations present between layers have been exchanged with organic onium ions refers to (B-1) a layered silicate having exchangeable cations between layers. It is a layered silicate obtained by exchanging an acidic cation with (B-2) an organic onium ion.

(B-1) The layered silicate having exchangeable cations between layers has a width of 0.05 to 0.5 μm and a thickness of 6 to 1 μm.
It has a structure in which 5-angstrom plate-like materials are stacked, and has exchangeable cations between layers of the plate-like materials. The cation exchange capacity is 0.2 to 3 meq / g, and preferably the cation exchange capacity is 0.8 to 1.5 m
eq / g.

Specific examples of the layered silicate include various clay minerals such as smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and sauconite, vermiculite, halloysite, kanemite, keniyaite, zirconium phosphate, titanium phosphate and the like. And swelling mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, Li-type tetrasilicon fluorine mica, etc., and may be natural or synthesized. . Among these, smectite clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Na-type tetrasilicon fluorine mica and Li-type fluorine teniolite are preferred.

(B-2) Examples of the organic onium ion include an ammonium ion, a phosphonium ion, and a sulfonium ion. Among these, ammonium ions and phosphonium ions are preferable, and ammonium ions are particularly preferably used. The ammonium ion may be any of primary ammonium, secondary ammonium, tertiary ammonium and quaternary ammonium.

The primary ammonium ion includes decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, benzyl ammonium and the like.

The secondary ammonium ion includes methyl dodecyl ammonium, methyl octadecyl ammonium and the like.

Examples of the tertiary ammonium ion include dimethyldodecylammonium and dimethyloctadecylammonium.

Examples of the quaternary ammonium ion include benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium and benzyldimethyloctadecylammonium; trioctylmethylammonium; trimethyloctylammonium; , Alkyltrimethylammonium ions such as trimethyloctadecylammonium, dimethyldioctylammonium, dimethyldidodecylammonium,
And dimethyldialkylammonium ions such as dimethyldioctadecylammonium.

In addition, aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine,
-Aminocaproic acid, 11-aminoundecanoic acid, 12
-Ammonium ions derived from aminododecanoic acid and the like.

Among these ammonium ions, preferred are ammonium ions derived from trioctylmethylammonium, trimethyloctadecyl ammonium, benzyldimethyloctadecyl ammonium, 12-aminododecanoic acid, and the like.

In the present invention, (B) a layered silicate in which exchangeable cations present between layers have been exchanged with organic onium ions is (B-1) a layered silicate having exchangeable cations between layers. 2) It can be produced by reacting an organic onium ion by a known method. Specific examples include a method based on an ion exchange reaction in a polar solvent such as water, methanol and ethanol, and a method based on directly reacting a liquid or molten ammonium salt with a layered silicate.

In the present invention, the amount of the organic onium ion with respect to the layered silicate is determined by considering the dispersibility of the layered silicate, the thermal stability during melting, the gas during molding, and the suppression of generation of odor. Typically 0.4 for cation exchange capacity
The range is from 2.0 to 2.0 equivalents, but preferably from 0.8 to 1.2 equivalents.

It is preferable to use these layered silicates by pre-treating them with a coupling agent having a reactive functional group in addition to the above-mentioned organic onium salts in order to obtain more excellent mechanical strength. Examples of such a coupling agent include an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound.

Particularly preferred are organic silane compounds, and specific examples thereof are γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxy). Epoxy group-containing alkoxysilane compounds such as cyclohexyl) ethyltrimethoxysilane, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane,
ureido group-containing alkoxysilane compounds such as γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ- Isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyl Isocyanato group-containing alkoxysilane compounds such as trichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ Amino group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane, .gamma.-hydroxypropyl trimethoxysilane, .gamma.
Hydroxyl-containing alkoxysilane compounds such as hydroxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, N
And carbon-carbon unsaturated group-containing alkoxysilane compounds such as -β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride.
In particular, a carbon-carbon unsaturated group-containing alkoxysilane compound is preferably used. The treatment of the layered silicate with these silane coupling agents can be carried out by adsorbing the silane coupling agent to the layered silicate in a polar solvent such as water, methanol, or ethanol, or a mixed solvent thereof, or by using a Henschel mixer or the like. A method in which a layered silicate is added to a high-speed stirring mixer, and the mixture is dropped and adsorbed in the form of an aqueous solution containing a silane coupling agent or an organic solvent while stirring, and the silane coupling agent is directly added to the layered silicate. Then, any method of mixing and adsorbing in a mortar or the like may be used. When the layered silicate is treated with a silane coupling agent, it is preferable to simultaneously mix water, acidic water, alkaline water and the like in order to promote the hydrolysis of the alkoxy group of the silane coupling agent. Further, in order to enhance the reaction efficiency of the silane coupling agent, water such as methanol or ethanol and an organic solvent that dissolves both the silane coupling agent may be mixed in addition to water. The reaction can be further promoted by heat-treating the layered silicate treated with such a silane coupling agent. When the layered silicate and the thermoplastic polyester are melt-kneaded without using a layered silicate with a coupling agent in advance, a so-called integral blending method of adding these coupling agents may be used.

In the present invention, the compounding amount of the layered silicate (B) in which the exchangeable cation existing between the layers is exchanged with the organic onium ion is 1 to 50 parts by weight with respect to (A) 100 parts by weight of the thermoplastic polyester resin. Parts, preferably 2 to 40% by weight, particularly preferably 3 to 30% by weight. If the amount is too small, the effect of improving physical properties and the effect of improving electrical properties during wet heat treatment are small, while if too large, the flame retardancy is reduced and the specific gravity is undesirably increased.

The red phosphorus (C) used in the present invention is unstable as it is, and has the property of gradually dissolving in water or reacting with water gradually. What has been applied is preferably used. As a method for treating such red phosphorus, the method of pulverizing red phosphorus described in JP-A-5-229806 is not performed, and a red crushed surface having high reactivity with water and oxygen is not formed on the surface of red phosphorus. A method of finely dividing phosphorus, a method of catalytically suppressing oxidation of red phosphorus by adding a small amount of aluminum hydroxide or magnesium hydroxide to red phosphorus,
A method of coating red phosphorus with paraffin or wax to suppress contact with moisture, a method of stabilizing by mixing with ε-caprolactam or trioxane, a method of mixing red phosphorus with phenolic, melamine, epoxy, or unsaturated polyester A method of stabilizing by coating with a thermosetting resin such as, red phosphorus is treated with an aqueous solution of a metal salt such as copper, nickel, silver, iron, aluminum and titanium to deposit a metal phosphorus compound on the red phosphorus surface Method of coating and stabilizing red phosphorus, method of coating red phosphorus with aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide, etc., Electroless plating coating of red phosphorus surface with iron, cobalt, nickel, manganese, tin, etc. And a method in which these are combined, but preferably, the surface of the red phosphorus is pulverized without pulverizing the red phosphorus. A method of forming red phosphorus into fine particles without forming a crushed surface, a method of stabilizing red phosphorus by coating it with a thermosetting resin such as a phenolic, melamine, epoxy, or unsaturated polyester type. A method of coating with aluminum oxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide and the like and a method in which these are combined, and particularly preferably, without pulverizing red phosphorus,
Red phosphorus is finely divided without forming a crushed surface on the surface, and coated with aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide, etc., and phenolic, melamine, epoxy, unsaturated polyester For example, a method of stabilizing by coating with a thermosetting resin such as is preferred.

Among the thermosetting resins, a phenol-based thermosetting resin and an epoxy-based thermosetting resin can be preferably used, and a phenol-based thermosetting resin is particularly preferred.

Incidentally, unground red phosphorus, which is a preferable red phosphorus as the red phosphorus used in the present invention, refers to red phosphorus produced without forming a crushed surface.

The average particle size of red phosphorus before being mixed with the resin is 35 from the viewpoints of flame retardancy, mechanical properties, wet heat resistance, and chemical and physical deterioration of red phosphorus due to pulverization during recycling. The thickness is preferably from 0.01 to 0.01 μm, and more preferably from 30 to 0.1 μm.

The average particle size of red phosphorus can be measured by a general laser diffraction type particle size distribution analyzer. There are two types of particle size distribution analyzers: wet method and dry method.
Either one may be used. In the case of the wet method, water can be used as a dispersion solvent for red phosphorus. At this time, red phosphorus surface treatment may be performed with an alcohol or a neutral detergent. It is also possible to use phosphates such as sodium hexametaphosphate and sodium pyrophosphate as the dispersant. It is also possible to use an ultrasonic bath as a dispersing device.

The average particle size of red phosphorus used in the present invention is as described above. However, red phosphorus having a large particle size contained in red phosphorus, that is, red phosphorus having a particle size of 75 μm or more is difficult. In order to significantly reduce the flammability, mechanical properties, wet heat resistance, and recyclability, red phosphorus having a particle size of 75 μm or more is preferably removed by classification or the like. The content of red phosphorus having a particle size of 75 μm or more is preferably 10% by weight or less, more preferably 8% by weight or less, particularly preferably 5% by weight or less from the viewpoints of flame retardancy, mechanical properties, wet heat resistance and recyclability. It is. The lower limit is not particularly limited, but is preferably as close to 0 as possible.

Here, the content of red phosphorus having a particle diameter of 75 μm or more contained in red phosphorus can be measured by classifying the particles with a mesh of 75 μm. That is, 100 g of red phosphorus
From the residual amount A (g) when classifying with a 5 μm mesh,
The content of red phosphorus having a particle size of 75 μm or more is (A / 100) × 10
It can be calculated from 0 (%).

The conductivity of the red phosphorus (C) used in the present invention when extracted in hot water (where the conductivity is red phosphorus 5
g, add 100 mL of pure water, extract in an autoclave at 121 ° C. for 100 hours, dilute the filtrate after red phosphorus filtration to 250 mL, and measure the conductivity of the extracted water.)
Is the moisture resistance, mechanical strength, electrical properties,
0.1 to 1000 μS from the viewpoint of recyclability
/ Cm, preferably 0.1-800 μS / cm,
More preferably, it is 0.1 to 500 μS / cm.

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

The electric conductivity according to the present invention is 0.1 to 1000.
The addition amount of red phosphorus (C) at 0.1 μS / cm is 0.1 to 30 parts by weight, preferably 0.1 to 25 parts by weight, more preferably 1 to 20 parts by weight, per 100 parts by weight of the thermoplastic polyester resin.
Parts by weight, more preferably 2 to 20 parts by weight. Particularly, 4 to 15 parts by weight is particularly preferable.

It is preferable that the flame retardant resin composition of the present invention further contains (D) a phosphoric acid ester, because the flowability, moldability and flame retardancy of the flame retardant resin composition are improved.

The (D) phosphate used in the present invention is represented by the following formula (1).

[0049]

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First, the structure of the flame retardant represented by the above formula (1) will be described. In the formula (1), n is an integer of 0 or more, preferably 0 to 10, particularly preferably 0 to 5
It is. The upper limit is preferably 40 or less from the viewpoint of flame retardancy.

K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less. Preferably, k and m are each an integer of 0 or more and 1 or less;
Particularly preferably, k and m are each 1.

In the formula (1), R ^{1 to} R ⁸ represent the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms. Here, specific examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-isopropyl, neopentyl , Tert-
Pentyl group, 2-isopropyl, neopentyl, ter
t-pentyl group, 3-isopropyl, neopentyl, t
tert-pentyl group, neoisopropyl, neopentyl, tert-pentyl group and the like.
A methyl group and an ethyl group are preferable, and hydrogen is particularly preferable.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different aromatic groups or aromatic groups substituted by halogen-free organic residues. As the aromatic group, an aromatic group having a benzene skeleton, a naphthalene skeleton, an indene skeleton, or an anthracene skeleton is preferable, and an aromatic group having a benzene skeleton or a naphthalene skeleton is preferable. These may be substituted with an organic residue containing no halogen (preferably an organic residue having 1 to 8 carbon atoms), and the number of substituents is not particularly limited, but may be 1 to 3. preferable. Specific examples include a phenyl group,
Examples thereof include aromatic groups such as a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a naphthyl group, an indenyl group, and an anthryl group.A phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a naphthyl group are preferable, and a phenyl group is particularly preferable. , A tolyl group and a xylyl group are preferred.

Y is a direct bond, O, S, SO ₂ , C
(CH ₃ ) ₂ , CH ₂ , and CHPh, and Ph represents a phenyl group.

Examples of such a phosphoric ester include PX-200, TPP, CR-733 and CR-7 manufactured by Daihachi Kagaku.
41 and their equivalents.

Among the above-mentioned phosphoric esters, those having the following structures are particularly preferred.

[0057]

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In the above structural units, n is preferably from 0 to 5,
Particularly, 1 is preferable.

As such a phosphoric ester, PX-200 and TPP manufactured by Daihachi Chemical Co., Ltd. can be used.

In the present invention, a mixture of two or more phosphate esters may be used.

The amount of the above phosphoric ester (D) is usually 1 to 3 with respect to 100 parts by weight of the thermoplastic polyester resin.
0 parts by weight, preferably 2 to 25 parts by weight, more preferably 3 to 20 parts by weight.

If the amount of the phosphoric ester (D) is too small, the effect of improving the fluidity, moldability and flame retardancy is not recognized. If the amount is too large, the mechanical properties and heat resistance of the molded article are impaired. Not preferred.

The (C) organic compound having at least one functional group reactive with the thermoplastic polyester used in the present invention, if necessary, chemically reacts with the terminal group of the thermoplastic polyester. An organic compound having one or more functional groups in a molecule that can be used. The functional group is not particularly limited as long as it is reactive with a carboxyl group or a hydroxyl group which is a terminal group of the thermoplastic polyester. Preferred examples thereof include a carboxylic acid anhydride group, an epoxy group, an isocyanate group, and a carbodiimide group. And an oxazoline group. Examples of the compound having one or more of these functional groups in the molecule include an olefin compound having a carboxylic anhydride group in the molecule, a polymer of these olefin compounds, a monoepoxy compound,
Examples include diepoxy compounds, polyepoxy compounds, isocyanate compounds, diisocyanate compounds, carbodiimide compounds, polycarbodiimide compounds, oxazoline compounds, and bisoxazoline compounds.

Among these compounds, preferred compounds include olefin compounds having a carboxylic anhydride group in the molecule or polymers of these olefin compounds. Specific examples thereof include maleic anhydride, itaconic anhydride,
Examples include glutaconic anhydride, citraconic anhydride, aconitic anhydride, and polymers of these substituted olefin compounds. In the olefin compound polymer, olefins other than the olefin compound having a carboxylic anhydride group in the molecule, such as styrene, isobutylene, methacrylic acid ester, and acrylic acid ester, are copolymerized within a range that does not impair the effects of the present invention. Although it does not matter, it is preferable that the polymer is substantially composed of a polymer of an olefin compound having a carboxylic anhydride group in the molecule. The polymerization degree of the olefin compound polymer is preferably from 2 to 100,
0 is more preferable, and 2 to 20 is most preferable. Among them, maleic anhydride and polymaleic anhydride are most preferably used. As polymaleic anhydride,
For example, J. Macromol. Sci.-Revs. Macromol. Chem., C13
(2), 235 (1975) and the like can be used.

The olefin compound having a carboxylic anhydride group in the molecule or a polymer of these olefin compounds used here may have an anhydride structure substantially when melt-kneaded with the thermoplastic polyester. The olefin compound or the polymer of the olefin compound is hydrolyzed and subjected to melt-kneading in the form of a carboxylic acid or an aqueous solution thereof, and subjected to a dehydration reaction by heating during the melt-kneading,
It may be melt-kneaded with the thermoplastic polyester substantially in the form of an acid anhydride.

Another preferred compound as the component (C) is an epoxy compound. Specific examples thereof include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether,
Monoepoxy compounds such as glycidyl benzoate and glycidyl methacrylate, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol A type epoxy resin, Diglycidyl compounds such as glycidyl phthalate, diglycidyl cyclohexanedicarboxylate, glycidyl ether oxybenzoate, glycerol polyglycidyl ether, trimethylolpropane diglycidyl ether, sorbitol diglycidyl ether, glycidyl methacrylate / ethylene copolymer, etc. And the like.

Among these, polyethylene glycol diglycidyl ether, bisphenol A type epoxy resin, glycidyl oxybenzoate and the like are preferred.

These may be used alone or in combination of two or more.

In the present invention, when the organic compound having one or more functional groups reactive with the thermoplastic polyester (C) in the molecule is added, the amount of the organic compound to be added is 0 to 100 parts by weight of the thermoplastic polyester (A). 0.05 to 10 parts by weight is preferable from the viewpoint of the effect of improving the impact strength and the fluidity of the composition, more preferably 0.1 to 5 parts by weight, and further preferably 0.1 to 3 parts by weight. is there.

In the present invention, there is no particular limitation on the method of blending (A) the thermoplastic polyester and (B) the layered silicate.
It is also possible to mix by the presence of a layered silicate, but (A) thermoplastic polyester and (B)
It is preferable to melt-knead the layered silicate. As a method of melt kneading, any method can be used as long as mechanical shearing can be performed in a molten state of the thermoplastic polyester. The processing method may be either a batch method or a continuous method, but a continuous method capable of continuous production is preferable from the viewpoint of working efficiency. The specific kneading apparatus is not limited, but an extruder, particularly a twin-screw extruder, is preferable in terms of productivity. It is also preferable to provide a vent for the purpose of removing water and low-molecular-weight volatile components generated during melt-kneading. When a twin-screw extruder is used, a layered silicate obtained by exchanging (A) a thermoplastic polyester and an exchangeable cation existing between layers (B) with an organic onium ion is previously mixed in a blender or the like, and then mixed. Feeding from the feed port of the extruder,
(A) the component is supplied from a feed port on the upstream side of the extruder,
There is no particular limitation on the supply method such as the method of supplying the component (B) from the downstream feed port. The screw arrangement of the extruder is not particularly limited, but a kneading zone is preferably provided in order to finely disperse the layered silicate.

Further, if necessary, even if (C) an organic compound having at least one functional group reactive with the thermoplastic polyester in the molecule is blended, there is no particular limitation on the method of addition. After dry blending polyester and (B) layered silicate in advance, melt kneading,
(A) and (B) may be added during melt-kneading.

When the flame-retardant resin composition of the present invention is further added with a fluorine-based resin and / or a silicone-based compound, the drop (drip) of droplets during combustion is suppressed.

Examples of such a fluorine resin include polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, Examples include a tetrafluoroethylene / ethylene copolymer, a (hexafluoropropylene / propylene) copolymer, a polyvinylidene fluoride, and a (vinylidene fluoride / ethylene) copolymer. Among them, polytetrafluoroethylene, (tetra (Fluoroethylene / perfluoroalkylvinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer, and polyvinylidene fluoride Preferred, in particular polytetrafluoroethylene, (tetrafluoroethylene / ethylene) copolymer are preferable.

The silicone compound of the present invention is a silicone resin and / or silicone oil.

The silicone resin used in the present invention is:
Chemically bonded siloxane units selected from units represented by the following general formulas (2) to (5) and mixtures thereof (where R is a saturated or unsaturated monovalent hydrocarbon group, a hydrogen atom, A polyorganosiloxane comprising a group selected from a hydroxyl group, an alkoxyl group, an aryl group, a vinyl or an allyl group, and preferably a methyl group and / or a phenyl group. Although a resin having a viscosity of centipoise is preferable, the viscosity is not limited to the above silicone resin.

[0076]

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The silicone oil used in the present invention is represented by the following general formula (6) (where,
R represents an alkyl group or a phenyl group, particularly preferably a methyl group and / or a phenyl group.
n is an integer of 1 or more. ). The silicone oil used preferably has a viscosity of 0.65 to 100,000 centistokes, but is not limited to the above silicone oil.

[0078]

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In the present invention, a silicone resin and / or a silicone oil can be used as the silicone compound. However, flame retardancy, heat resistance, bleed-out resistance, contact contamination resistance, and deterioration of electrical properties after wet heat treatment. In view of the above, a silicone resin is preferable.

The amount of the fluorine-based resin and / or silicone-based compound of the present invention is usually 0.01 to 10 parts by weight based on 100 parts by weight of the polybutylene terephthalate resin (A) from the viewpoint of mechanical properties and moldability. , Preferably 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight.

The above-mentioned fluororesin and silicone compound can be added in combination. In this case, the total amount of the fluororesin and silicone resin is as follows:
The amount is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and still more preferably 0.1 to 10 parts by weight based on 100 parts by weight of the polybutylene terephthalate resin (A).
2-3 parts by weight.

The flame-retardant resin composition of the present invention is preferably further blended with a triazine compound and a salt of cyanuric acid or isocyanuric acid, because the flame retardancy and tracking resistance are improved.

Such a triazine compound and a salt of cyanuric acid or isocyanuric acid are adducts of cyanuric acid or isocyanuric acid with a triazine compound, and are usually 1: 1 (molar ratio). And a salt of cyanuric acid or isocyanuric acid are adducts of cyanuric acid or isocyanuric acid with a triazine-based compound, and usually have a composition of 1: 1 (molar ratio), sometimes 1: 2 (molar ratio). Is an adduct having Of the triazine compounds, those that do not form a salt with cyanuric acid or isocyanuric acid are excluded.

Examples of the triazine-based compound include compounds represented by the following general formula (2).

[0085]

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In the general formula (1), R ⁹ , R ¹⁰ , R
¹¹ and R ¹² are the same or different hydrogen, aryl group, alkyl group, aralkyl group, cycloalkyl group, or -C
ONH ₂ . Here, the aryl group has 6 to 6 carbon atoms.
Preferred are those having 15 carbon atoms, those having 1 to 10 carbon atoms as alkyl groups, those having 7 to 16 carbon atoms as aralkyl groups, and those having 4 to 15 carbon atoms as cycloalkyl groups. R is -NR ⁹ R ¹⁰ or -NR ¹¹ R in the above formula.
^The same group as ¹² , or independently of these, hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group,
NH ₂ or —CONH ₂ , wherein the aryl group has 6 to 15 carbon atoms, the alkyl group has 1 to 10 carbon atoms, and the aralkyl group has 7 to 16 carbon atoms. And cycloalkyl groups having 4 to 15 carbon atoms are preferred.

Specific examples of R ⁹ , R ¹⁰ , R ¹¹ and R ¹² include hydrogen, phenyl, p-toluyl, α-naphthyl, β-naphthyl, methyl, ethyl and n-propyl. Group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, hydroxymethyl group, methoxymethyl group, benzyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 2-methyl-1-pentyl group, Examples thereof include a 4-methyl-1-cyclohexyl group and an amide group, and among them, hydrogen, a phenyl group, a methyl group, a hydroxymethyl group, a methoxymethyl group, a benzyl group, and an amide group are preferable.

Specific examples of R ¹³ include an amino group, an amide group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a mono (hydroxymethyl) amino group and a di (hydroxymethyl) amino group. , Mono (methoxymethyl) amino group, di (methoxymethyl)
Amino group, phenylamino group, diphenylamino group, hydrogen, phenyl group, p-toluyl group, α-naphthyl group, β
-Naphthyl group, methyl group, ethyl group, n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
tert-butyl group, benzyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 2-methyl-1-
Examples thereof include a pentyl group and a 4-methyl-1-cyclohexyl group, among which hydrogen, an amino group, an amide group, a methyl group, a mono (hydroxymethyl) amino group, a di (hydroxymethyl) amino group, and a mono (methoxymethyl) group An amino group, a di (methoxymethyl) amino group, a phenyl group, and a benzyl group are preferred.

Among the salts of the compound represented by formula (7) with cyanuric acid or isocyanuric acid, melamine, benzoguanamine, acetoguanamine, 2-
Amide-4,6-diamino-1,3,5-triazine,
Mono (hydroxymethyl) melamine, di (hydroxymethyl) melamine and tri (hydroxymethyl) melamine salts are preferred, especially melamine, benzoguanamine,
Acetoguanamine salts are preferred.

The salt of the triazine compound and the cyanuric acid or isocyanuric acid was prepared by mixing a mixture of the triazine compound and the cyanuric acid or isocyanuric acid with a water slurry and mixing them well to form fine particles of both salts. Thereafter, this slurry is a powder obtained by filtering and drying, and is different from a mere mixture. The salt does not need to be completely pure, and a somewhat unreacted triazine-based compound or cyanuric acid or isocyanuric acid may remain.

The average particle size of the salt before being mixed with the resin is determined by considering the flame retardancy, mechanical strength and surface properties of the molded product.
It is preferably from 0 to 0.01 μm, more preferably from 80 to 0.01 μm.
10 μm. The average particle size of the salt can be measured in the same manner as the average particle size of the red phosphorus. If the salt has poor dispersibility, a dispersant such as tris (β-hydroxyethyl) isocyanurate may be used in combination.

The amount of the salt used is usually 0.01 to 50 parts by weight, preferably 0.1 to 40 parts by weight, more preferably 0.5 to 30 parts by weight, per 100 parts by weight of the thermoplastic polyester resin (A). Parts by weight.

The flame-retardant resin composition of the present invention is preferably further blended with a polycarbonate resin because it can impart not only flame retardancy but also effects of improving mechanical properties, lowering specific gravity, lowering warpage, and increasing toughness.

Examples of such a polycarbonate resin (B) include aromatic homo- or copolycarbonates obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester. The aromatic homo or copolycarbonate resin preferably has a viscosity average molecular weight in the range of 10,000 to 1,000,000. 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.

In the present invention, the amount of the polycarbonate resin (B) to be added depends on the amount of the thermoplastic polyester resin (A) 1
0.1 to 100 parts by weight, preferably 0.5 to 80 parts by weight, more preferably 1 to 60 parts by weight,
Particularly preferably, it is 5 to 50 parts by weight.

The flame-retardant resin composition of the present invention can further improve the 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 has an effect not only as a stabilizer for red phosphorus, but also for improving the non-coloring property of the resulting resin composition and the dispersibility of red phosphorus.

The amount of the metal oxide to be added is preferably 0.01 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight, per 100 parts by weight of the thermoplastic polyester resin (A) from the viewpoint of mechanical properties and moldability. Department.

It has been found that when the flame retardant resin composition of the present invention is further used in combination with a hindered phenol-based stabilizer, extremely good hydrolysis resistance can be maintained even when exposed to high temperatures for a long period of time. As such a stabilizer, for example, triethylene glycol-bis [3- (3-t-butyl-
5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3-
(3,5-di-t-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.

In the present invention, such a hindered phenol-based stabilizer can be added as needed, and the amount of the hindered phenol-based stabilizer added at that time is usually the thermoplastic polyester resin (A ) 0.01 to 3 parts by weight, preferably 0.02 to 2 parts by weight, more preferably 0.03 to 0.5 part by weight, per 100 parts by weight.

Further, the polyester resin composition of the present invention may contain various commonly used additives such as inorganic fillers such as glass fiber, carbon fiber and glass flake, and various elastomers within a range not to impair the object of the present invention. Impact modifier, crystal nucleating agent, coloring inhibitor, antioxidant such as hindered amine, release agent such as ethylene bisstearylamide and higher fatty acid ester, plasticizer, heat stabilizer, lubricant, UV inhibitor, coloring agent, Additives other than the present invention, such as flame retardants, can be added.

The flame-retardant resin composition of the present invention is usually produced by a known method. For example, (A) a thermoplastic polyester resin (A), a layered silicate (B) in which exchangeable cations existing between layers have been exchanged with organic onium ions, and red phosphorus (C)
And other necessary additives are preliminarily mixed or supplied to an extruder or the like, and are prepared by sufficiently melting and kneading.However, from the viewpoint of handling properties and productivity, thermoplastic polyester is preferably used. A part of the resin (A) and red phosphorus (C) are once melt-kneaded to produce a resin composition (F) having a higher red phosphorus concentration than the amount of red phosphorus to be actually incorporated into the flame-retardant resin composition. The remaining thermoplastic polyester resin (A), the layered silicate (B) in which exchangeable cations present between layers have been exchanged with organic onium ions, and a resin composition (F) having a high red phosphorus concentration and other optional components It is prepared by melt-kneading additives that can be used for the above.

In the step of producing the resin composition (F) having a higher red phosphorus concentration than the amount of red phosphorus to be actually blended into the flame-retardant resin composition as described above, it can be used arbitrarily. When the additives are blended, it is preferable that these optional additives are mixed with red phosphorus in advance.

Among the additives that can be used arbitrarily, when a metal oxide used as a stabilizer for red phosphorus, particularly titanium oxide, is added, the titanium oxide produces a red phosphorus-rich product (F). It is preferable to mix them in stages, and if red phosphorus and titanium oxide are mixed in advance using a mechanical mixing device such as a Henschel mixer, the stability of red phosphorus, the dispersibility of red phosphorus, and the resulting resin composition The non-coloring property of the product can be improved.

The content of red phosphorus in the high-concentration red-phosphorus product (F) is determined based on the production of the high-concentration red-phosphorus product, the dispersibility of red phosphorus, the flame retardancy of the resin composition finally obtained, From the viewpoint of mechanical properties and moldability, 30 to 30 parts by weight based on 100 parts by weight of the thermoplastic polyester resin (A) blended in the red phosphorus-rich product
The amount is preferably 0 parts by weight, particularly preferably 35 to 200 parts by weight.

The resin composition (F) having a high red phosphorus concentration
Is preferably used in the form of a so-called master pellet, but is not limited thereto, and may be in the form of a chip, a powder, or a mixture thereof. The thermoplastic polyester resin (A) to be blended with the component (F) is preferably in the form of a pellet, but is not limited thereto, and may be in the form of a chip, a powder, or a mixture of a chip and a powder. Good. Further, it is preferable that the form, size, and shape of the component (F) and the thermoplastic polyester resin to be blended with the component (F) are substantially the same, or similar to each other, in that they can be uniformly mixed. In producing the flame-retardant resin composition, for example, a single-screw extruder, a twin-screw, a triple-screw extruder, and a kneader-type kneader equipped with a “unimelt” type screw can be used.

The flame-retardant resin composition and the molded article thus obtained can be molded by a generally known method, and molded articles such as injection molding, extrusion molding, compression molding, and molded articles of all shapes such as sheets and films. It can be.
Among them, it is particularly suitable for use in injection molded products. It is also suitable for molded products with complicated shapes such as molded products with welds and hinges and insert molded products, and thin molded products.
It is suitable for various mechanical mechanism parts, electric and electronic parts or automobile parts.

For example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors,
Variable condenser case, optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, housing, semiconductor, liquid crystal display parts, FDD carriage , FDD chassis, HDD parts, motor brush holders, parabolic antennas, electrical and electronic parts such as computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio parts・ Sound equipment parts such as laser discs and compact discs, lighting parts,
Home, office electrical product parts, office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, oilless bearings, such as refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. , Stern bearings, underwater bearings, and other various bearings, motor parts, mechanical parts such as lighters, typewriters, microscopes, binoculars, cameras,
Optical equipment represented by watches, precision machinery-related parts, alternator terminals, alternator connectors,
IC regulator, potentiometer base for light deer, various valves such as exhaust gas valve, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel pump,
Engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, thermostat for air conditioner Base, Heating hot air flow control valve, Brush holder for radiator motor, Water pump impeller, Turbine vane, Wiper motor related parts, Distributor, Starter switch, Starter relay, Wire harness for transmission,
Window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation board, step motor rotor, lamp socket, lamp reflector,
It is useful for various applications such as lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, etc. Among the above, the features of the present invention, in particular, the flame retardancy, mechanical properties, and electrical properties of thin molded products It can be suitably used for connectors, coil bobbins, relays, and switches as parts that take advantage of moisture and heat resistance.

[0109]

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. (1) Mechanical properties ASTM for dumbbell specimens obtained by injection molding
The tensile yield strength was measured according to D-638. (2) Impact characteristics A was injection-molded using a Toshiba Machine's IS55EPN injection molding machine at a molding temperature of 280 ° C and a mold temperature of 80 ° C.
Izod impact strength of 1/4 inch (notched) thickness was measured according to STM D-648. (3) Flame retardancy A test piece for evaluating flame retardancy obtained by injection molding obtained by injection molding using an IS55EPN injection molding machine manufactured by Toshiba Machine at a molding temperature of 280 ° C. and a mold temperature of 80 ° C.
The flame retardancy was evaluated according to the evaluation criteria set forth in. The flame retardancy level decreases in the order of V-0>V-1>V-2> HB. The sum of the burning times of the five samples was used as an index of flame retardancy. (4) Bleed-out characteristics A test piece obtained by injection molding was subjected to a temperature of 120 ° C and a humidity of 100.
After performing a wet heat treatment at% RH for 120 hours, the surface of the test piece was observed with an optical microscope. Bleed-out was evaluated by judging that: ○: hardly any precipitate was observed, x: no precipitate was observed. (5) Surface specific resistance After measuring the surface specific resistance of a test piece of 40 mm × 40 mm and a thickness of 3 mm obtained by injection molding using a SM-10E ultra-insulation meter manufactured by Toa Denpa Kogyo Co., Ltd., the temperature was adjusted to 12 ° C.
After heat treatment at 0 ° C and humidity of 100% RH for 120 hours,
The surface resistivity was measured again. Reference Example 1 (B-1) Na-type montmorillonite (Kunimine Industries: Knipia F,
100 g of a cation exchange capacity (120 meq / 100 g) was stirred and dispersed in 10 liters of warm water, and 2 L of warm water in which 51 g of benzyldimethyloctadecyl ammonium chloride (equivalent to the cation exchange capacity) was added.
Stirred for hours. The resulting precipitate was separated by filtration and washed with warm water. This washing and filtration were repeated three times, and the obtained solid was vacuum-dried at 80 ° C. to obtain a dried organic layered silicate. The amount of inorganic ash in the obtained organically modified layered silicate was measured and found to be 66% by weight. In addition, the measurement of the amount of inorganic ash is a value obtained by ashing 0.1 g of the organically modified layered silicate in an electric furnace at 500 ° C. for 3 hours. Reference Example 2 (B-2) Na-type synthetic mica (COPE CHEMICAL: ME-100) 10
0 g was stirred and dispersed in 10 liters of warm water, and 47 g of dimethylbenzyloctadecyl ammonium chloride was added thereto.
(Equivalent to the cation exchange capacity) in 2 L of warm water dissolved therein and stirred for 1 hour. After that, as in Reference Example 1,
After washing and drying, a dried organically modified layered silicate was obtained. The amount of inorganic ash in the organically modified layered silicate measured in the same manner as in Reference Example 1 was 69% by weight. Reference Example 3 (B-3) Organized layered silicate in the same manner as in Reference Example 1, using 100 g of montmorillonite and 30.2 g of 12-aminododecanoic acid hydrochloride (equivalent to the cation exchange capacity) as in Reference Example 1. Was manufactured. The amount of inorganic ash in the organically modified layered silicate measured in the same manner as in Reference Example 1 was 76% by weight. Reference Example 4 Highly Concentrated Red Phosphorus (F-1) Phosphorus ("NOVA EXCEL" 140 manufactured by Rin Kagaku Kogyo Co., Ltd.), 100 g of pure water was added to 5 g of red phosphorus and 100 g of 121 g in an autoclave. After extracting with time, filtering the red phosphorus, diluting the solution to 250 mL, and measuring the conductivity using a conductivity meter (Personal SC meter, manufactured by Yokogawa Electric Corporation) with a conductivity of 200 μm S / cm and a particle size of 75 μm or more. 100 parts by weight of red phosphorus content) and a nitrogen flow, while a screw diameter of 30 mm, L / D = 45.5, coaxial rotary twin screw extruder (Nippon Seiko Co., Ltd., TEX-30)
Was melt-extruded at a resin temperature of 280 ° C. to produce a PET-rich red phosphorus-rich product (D-1).

A polybutylene terephthalate resin (hereinafter referred to as P
BT) and Toray PBT1100S (Toray Industries, Inc.)
Manufactured by Rin Kagaku Kogyo Co., Ltd., “Nova Excel” 140: average particle size 29.7 μm, 5 g of red phosphorus
100 mL of pure water was added to the autoclave at 121 ° C.
For 100 hours, and the back solution obtained by filtering the red phosphorus is used for 25 hours.
Dilute to 0 mL and conductance meter (Personal S manufactured by Yokogawa Electric Corporation)
200 μm S when measured using a C meter)
/ Cm), and while flowing nitrogen, the resin temperature was measured using a coaxially rotating twin-screw extruder (TEX-30, manufactured by Nippon Seiko Co., Ltd.) having a screw diameter of 30 mm and L / D = 45.5. The mixture was melt-extruded at 280 ° C. to produce a red phosphorus-rich PBT resin (D-1). Reference Example 5 Production of high-concentration product of red phosphorus (F-2) Polybutylene terephthalate resin (hereinafter abbreviated as PBT)
100 parts by weight of Toray PBT1100S (manufactured by Toray Industries, Inc.) and "Novared" 120 (manufactured by Rin Kagaku Kogyo KK) as red phosphorus (average particle size 38 μm, conductivity 1200 μS /
cm, a red phosphorus content of 15% or more having a particle size of 75 μm or more) was used in the same manner as in Reference Example 4 except that 100 parts by weight was used.

Hereinafter, the present effect will be described with reference to Examples and Comparative Examples, but the present effect is not limited to these Examples. The compounding agents used in the examples and comparative examples are as follows.・ Polyethylene terephthalate (hereinafter abbreviated as PET) Polyethylene terephthalate having an intrinsic viscosity of 0.65 (a mixed solvent of phenol / tetrachloroethane of 1: 1 at 25 ° C.) ・ Polycarbonate (hereinafter abbreviated as PC) “Iupilon” S3000 (Mitsubishi Engineering Plastics)・ Fluoroplastic polytetrafluoroethylene (“Teflon 6J” manufactured by DuPont-Mitsui Fluorochemicals) ・ Silicone resin “DC4-7105” (manufactured by Dow Corning Toray Silicone Co., Ltd.) ・ Cyanur Melamine cyanurate ("MCA" manufactured by Mitsubishi Chemical Corporation) Bisphenol A type epoxy resin "Epototo" YD115 (manufactured by Toto Kasei Co., Ltd.) Phosphate PX-200 (manufactured by Daihachi Chemical Company) Example 1, Comparative Example 1 Table 1 for 2 PBT In case the ratio, by mixing a layered silicate prepared in Reference Example (B) and red phosphorus-enriched product (F) and other additives, screw diameter 30 mm, L / D45.
5 twin-screw extruder (TEX-3, manufactured by Nippon Steel Corporation)
0: The screw uses two screws of 3.5 mm that engage with each other with two threads, and screw elements consisting of 10 kneading disks inclined at 45 degrees with L / D = 4 are provided in reverse order. And melt extruded at a resin temperature of 280 ° C. using a reverse kneading element having a strong kneading force. After drying the obtained pellets, injection molding was performed (cylinder temperature: 280 ° C., mold temperature: 80 ° C.) to obtain test pieces.

The sample was measured for flame retardancy, tensile strength, impact strength, bleed-out state due to wet heat treatment, and surface resistivity as electrical characteristics before and after wet heat treatment. Table 1 shows the results.

[0113]

[Table 1]

From the evaluation results of Example 1 and Comparative Examples 1 and 2,
It can be seen that the addition of the layered silicate (trioctylammonated montmorillonite) produced in Reference Example 1 to PBT has specifically high flame retardancy and excellent mechanical properties and moisture-heat bleed-out. Further, it can be seen that the surface specific resistance value is high and the electrical characteristics are excellent. Also, it can be seen that the surface specific resistance value due to the moisture resistance heat treatment is high.

On the other hand, it can be seen that Comparative Example 1 in which the layered silicate was not blended was inferior in flame retardancy, mechanical properties and electrical properties.

Comparative Example 2 containing red phosphorus having high conductivity
It can be seen that the surface resistivity is remarkably low. In addition, bleeding is observed by the wet heat treatment, and the surface specific resistance value is significantly reduced by the wet heat treatment. Example 2 and Comparative Example 3 In Example 2 and Comparative Example 3, (C) a bisphenol A type epoxy resin was further compounded as an organic compound having one or more functional groups reactive with the thermoplastic polyester in the molecule. , Example 1 and Comparative Example 2.

In Example 2, in which a bisphenol A type epoxy resin was further added, there was a tendency that the mechanical properties were improved and the burning time was shortened. In addition, a tendency that the electric characteristics are slightly improved is recognized. On the other hand, in Comparative Example 3 in which red phosphorus having a high electrical conductivity was blended, the surface resistivity was remarkably low, and bleed-out due to the moisture heat treatment was observed, and the surface resistivity was also reduced. Examples 3 and 4 In Example 3, the same procedures as in Example 2 were carried out except that PET or PC was further added and the amount of the high-concentration red phosphorus product was reduced. It is understood that flame retardancy can be imparted by adding a small amount of red phosphorus by blending PET or PC, and mechanical properties and surface resistivity before and after wet heat treatment are improved. Example 5 Example 4 was repeated except that Teflon was further added.
The same was done. It can be seen that the combustion time is further shortened by adding Teflon. Example 6 In Example 6, benzyl dimethyl octadecyl ammonium-modified synthetic mica was used in place of trioctylammonated montmorillonite as the layered silicate, and melamine cyanurate was blended to reduce the amount of red phosphorus high-concentration product added. Was performed in the same manner as in Example 3.

By incorporating melamine cyanurate, flame retardancy is obtained even with a small amount of red phosphorus, and the mechanical properties are improved.
Further, it is understood that the surface resistivity before and after the wet heat treatment is also improved. Examples 7 and 8 In Examples 7 and 8, 12-aminododecanoic acid hydrochloride montmorillonite was used as a layered silicate, and a phosphate ester,
Example 2 was repeated except that PET, PC, Teflon or silicone resin was blended.

It can be seen that all of the mechanical properties, flame retardancy, and surface resistivity are improved as compared with Example 2.

The flame-retardant resin composition of the present invention has not only high flame retardancy but also excellent mechanical properties (strength, impact), electrical properties, bleed-out properties due to moisture resistance treatment and electrical properties, It is a material that satisfies the required characteristics of mechanical mechanism parts, electric and electronic parts or automobile parts. In particular, because it has a contact surface with metal and is used under severe high temperature and high voltage conditions, parts to which voltage is applied such as connectors, coil bobbins, relays, switch parts, etc. have high flame retardancy, mechanical properties, electrical properties In addition, it is required to maintain electrical characteristics by wet heat treatment. The flame-retardant resin composition of the present invention is extremely suitable for these uses.

[0121]

(1) A layered silicate according to the present invention in which exchangeable cations existing between layers have been exchanged with organic onium ions.
The flame-retardant resin composition containing red phosphorus having a specific electric conductivity has not only high flame retardancy but also excellent mechanical properties compared to other conventionally known red phosphorus-containing flame retardant resin compositions. Strength, impact) and electrical characteristics, and furthermore, bleed-out due to wet heat treatment is suppressed, and electrical characteristics due to moisture resistance treatment are excellent. (2) The flame-retardant resin composition obtained by the present invention is useful for mechanical parts, electric / electronic parts, and automobile parts utilizing these characteristics, and is particularly suitable for connectors, coil bobbins, relays, and switch parts.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C08L 69:00) (C08K 13/06 3:02 5: 523 3:34 9:04 5: 3492)

Claims (15)

[Claims] (A) 100 parts by weight of a thermoplastic polyester resin, (B) 0.1 to 50 parts by weight of a layered silicate in which exchangeable cations existing between layers have been exchanged with organic onium ions, and (C) Conductivity of 0.1 to 1000 μS / cm
A flame-retardant resin composition comprising 0.1 to 30 parts by weight of red phosphorus. (However, the conductivity is 5 g of red phosphorus and 100 m of pure water.
L, extract at 121 ° C. for 100 hours, filter the red phosphorus, and dilute the solution to 250 mL to obtain the conductivity of extracted water. ) 2. The flame-retardant resin composition according to claim 1, wherein the red phosphorus (C) is unground red phosphorus and is red phosphorus coated with a thermosetting resin. 3. A flame-retardant resin composition further comprising (D) 0.1 to 30 parts by weight of a phosphoric ester represented by the following general formula (1). Embedded image (In the formula, R ¹ to R ⁸ represent identical or different hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The Ar ^1,
Ar ² , Ar ³ , and Ar ⁴ represent the same or different phenyl groups or phenyl groups substituted with halogen-free organic residues. Y is a direct bond, O, S, S
O ₂ , C (CH ₃ ) ₂ , CH ₂ , and CHPh, and Ph represents a phenyl group. N is an integer of 0 or more. K and m are each an integer of 0 or more and 2 or less, and k +
m is an integer of 0 or more and 2 or less. ) 4. The thermoplastic polyester resin (A) is selected from the group consisting of polybutylene terephthalate, polypropylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polycyclohexane dimethylene terephthalate, and poly (ethylene terephthalate / cyclohexane dimethylene terephthalate). The flame-retardant resin composition according to any one of claims 1 to 3, which is at least one kind. 5. The layered silicate wherein the exchangeable cation present between the layers (B) has been exchanged with an organic onium ion is a layered silicate further treated with a coupling agent having a reactive functional group. The flame-retardant resin composition according to any one of claims 1 to 4. 6. An organic compound having (E) one or more functional groups reactive with the thermoplastic polyester per molecule based on 100 parts by weight of the thermoplastic polyester resin (A).
The flame-retardant resin composition according to any one of claims 1 to 5, further comprising 0.05 to 10 parts by weight. 7. The method according to claim 6, wherein the functional group of the organic compound having at least one functional group reactive with the thermoplastic polyester resin in the molecule is a carboxylic anhydride group and / or an epoxy group. Flame-retardant resin composition. 8. An organic compound having (E) at least one functional group reactive with a thermoplastic polyester resin in the molecule, wherein the olefin compound has a carboxylic anhydride group in the molecule or a polymer of the olefin compound. Claim 6
Or the flame-retardant resin composition according to 7. 9. The flame-retardant resin composition according to claim 1, further comprising (A) 0.01 to 10 parts by weight of a fluororesin based on 100 parts by weight of the thermoplastic polyester resin. . 10. A thermoplastic polyester resin (A) 100.
The flame-retardant resin composition according to any one of claims 1 to 9, further comprising 0.01 to 20 parts by weight of a salt composed of a triazine compound and cyanuric acid or isocyanuric acid with respect to parts by weight. 11. (A) Thermoplastic polyester resin 100
0.1 to 100 parts by weight of polycarbonate resin
The flame-retardant resin composition according to any one of claims 1 to 10, further comprising parts by weight. (A) a thermoplastic polyester resin,
(B) a layered silicate in which exchangeable cations present between layers have been exchanged with organic onium ions, (C) a conductivity of 0.1 to
A method for producing a flame-retardant resin composition, comprising producing the flame-retardant resin composition according to any one of claims 1 to 11 by melt-kneading 1000 μS / cm of red phosphorus with an extruder. 13. A resin composition (F) having a high red phosphorus concentration by melt-kneading (A) a part of the thermoplastic polyester resin and (C) red phosphorus having a conductivity of 0.1 to 1000 μS / cm.
And extruding the remaining thermoplastic polyester resin (A), the layered silicate (B) in which exchangeable cations existing between layers have been exchanged with organic onium ions, and the resin composition (F) having a high red phosphorus concentration. Claim 1 by melting and kneading with a machine
13. A method for producing a flame-retardant resin composition, comprising producing the flame-retardant resin composition according to any one of items 12 to 12. 14. A molded article comprising the flame-retardant resin composition according to claim 1, wherein the molded article is a mechanical mechanism part, an electric / electronic part or an automobile part. 15. A molded article comprising the flame-retardant resin composition according to any one of claims 1 to 13, wherein the molded article is used for a connector, a coil bobbin, a relay or a switch.