JPH06888B2 - Flame-retardant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to a flame-retardant resin composition having excellent mechanical properties.

<Prior Art> Polyether ester amides having a polyamide repeating unit, a polyether repeating unit and an ester bond in the polymer main chain are known. (US Patent No. 304498
(Specification No. 7) Polyether ester amide has been attracting attention in recent years as a new material in the elastomer field because it has excellent impact resistance and rubber elasticity like polyester amide.

Polyether ester amides are particularly promising for various molding applications because they are excellent in lightness and transparency and hardly cause burrs and sink marks during molding.

<Problems to be Solved by the Invention> However, although the polyether ester amide has the above-mentioned characteristics, it easily burns, so that it is strongly required to have safety against fire such as electric and electronic parts, that is, flame retardancy. Use is restricted in.

The present invention has been made to solve the above problems and to provide a flame-retardant resin composition having excellent mechanical properties.

The present inventors have conducted extensive studies to improve the problem of flame retardation of polyether ester amide, and as a result, by using a halogen-containing bisphenol-type copolymerized polycarbonate oligomer as a flame retardant, it has excellent mechanical properties and flame retardancy. The inventors have found that a flame-retardant resin composition having improved properties is obtained, and have reached the present invention.

<Means for Solving the Problems> That is, the present invention relates to an aminocarboxylic acid or lactam having 6 or more carbon atoms, or a salt (a) of a diamine and dicarboxylic acid having 6 or more carbon atoms and a number average molecular weight of 300 to 6,000.
Represented by the following general formula (I) with respect to 100 parts by weight of a polyetheresteramide (A) composed of the poly (alkylene oxide) glycol (b) and the dicarboxylic acid (c) having 4 to 20 carbon atoms. A flame-retardant resin composition containing 1 to 60 parts by weight of a halogen-containing bisphenol-type copolycarbonate oligomer (B) is provided.

(Wherein R represents an alkylene group in the formula, a carbonyl group, an ether group, -S- or SO 2 _-. The, R 'and R "are the halogenated phenyl group, X represents a bromine atom or a chlorine atom or, m , N is m ≧ 1, n ≧ 0, 2 ≦ m + n
It is an integer satisfying ≦ 20) In the polyether ester amide (A) of the present invention, an aminocarboxylic acid having 6 or more carbon atoms or a lactam or a salt of a diamine having 6 or more carbon atoms and a dicarboxylic acid (a) includes ω -Aminocaproic acid, ω-aminoenanthic acid, ω
-Aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and other aminocarboxylic acids, or lactams such as caprolactam, enantolactam, capryllactam, laurolactam and hexamethylene Diamine-dicarboxylic acid such as diamine-adipate, hexamethylenediamine-sebacate, hexamethylenediamine-isophthalate, undecametalenediamine-adipate, 4,4'-diaminodicyclohexylmethane-dodecanedioate However, 11-aminoundencanic acid and 12-aminododecanoic acid are particularly preferable, and they may be used in combination depending on the purpose and application.

Further, it is acceptable to use another amide-forming component as a copolymerization component for the purpose of lowering the melting point of the polyether ester amide or increasing the adhesiveness, as long as it is in a small amount range.

Polyether ester amide (A) of the present invention has a number average molecular weight of 300 to 6,000 poly (alkylene oxide) glycol (b), polyethylene glycol, poly (1,2- and 1,3-propylene oxide) glycol,
Examples include poly (tetramethylene oxide glycol), poly (hexamethylene oxide) glycol, block or random copolymers of ethylene oxide and propylene oxide, block or random copolymers of ethylene oxide and tetrahydrofuran, and among others, heat resistance and water resistance. Poly (tetramethylene oxide) glycol is preferably used because of its excellent physical properties such as mechanical strength, elastic recovery and the like. The number average molecular weight of poly (alkylene oxide) glycol is 30
It is necessary to be in the range of 0 to 6,000, but a molecular weight range is selected in which coarse phase separation does not occur during polymerization, and low temperature characteristics and mechanical properties are excellent. This optimum molecular weight range depends on the type of poly (alkylene oxide) glycol. For example, polyethylene glycol 300-6,000,
Particularly preferably 1,000 to 4,000, in the case of poly (propylene oxide) glycol 300 to 5,000, particularly preferably 50
In the case of 0 to 3,000, and in the case of poly (tetramethylene oxide) glycol, those having a molecular weight range of 500 to 3,000, particularly preferably 500 to 2,500 are preferably used.

Examples of the dicarboxylic acid (c) having 4 to 20 carbon atoms in the polyetheresteramide (A) of the present invention include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid and diphenyl- 4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, aromatic dicarboxylic acid such as sodium 3-sulfoisophthalate,
Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid, and succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedioic acid (decane Aliphatic dicarboxylic acids such as dicarboxylic acids) can be mentioned. Especially terephthalic acid, isophthalic acid, 1,4
-Dicarboxylic acids such as cyclohexanedicarboxylic acid, adipic acid, sebacic acid and dodecanedioic acid are preferably used in view of polymerizability, color tone and physical properties of polymer.

In order to show the effect of the present invention most noticeably, the polyether ester amide (A) is composed of a polyether ester unit composed of a poly (alkylene oxide) glycol (b) and a dicarboxylic acid (c). The polymerization amount is preferably 5 to 90% by weight. When the amount of copolymerization is less than 5% by weight, flexibility and elastic recovery are lost, and when it is more than 90% by weight, high temperature properties, tensile properties and mechanical properties are insufficient.

The method for polymerizing the polyether ester amide (A) is not particularly limited, and a known method can be used. For example,
Aminocarboxylic acid or lactam or diamine and dicarboxylic acid salt (a) are reacted with dicarboxylic acid (c) to form a polyamide prepolymer having carboxylic acid groups at both ends, and poly (alkylene oxide) glycol (b) is vacuumed on it. Method of reacting under, or by charging the compound of (a), (b), (c) in a reaction tank, by heating reaction at high temperature in the presence or absence of water at a high temperature carboxylic acid-terminated polyamide prepolymer Is known, and then the polymerization is allowed to proceed under normal pressure or reduced pressure. In addition, the above (a),
There is also a method in which the compounds (b) and (c) are simultaneously charged in a reaction tank, melt polymerization is performed, and then the polymerization is advanced under high vacuum all at once.
Rather, this method is preferable because it causes less coloring of the polymer.

The halogen-containing bisphenol-type copolymerized polycarbonate oligomer (B) of the general formula (I) used as the flame retardant in the present invention can be obtained by polymerizing a halogen-containing bisphenol compound, a bisphenol compound, and a halogenated phenol compound.

That is, an amine (for example, triethylamine or pyridine) is added and stirred in a solvent such as methylene chloride, and a halogen-containing bisphenol compound, a bisphenol compound, and a halogenated phenol (for example, tribromophenol) are added and dissolved at a predetermined molar ratio. Phosgene gas is then introduced into such a reaction mixture to an excess. At that time, the temperature is about 30 to 60 ° C., and the reaction time is within 1 hour.

Recovery of the copolycarbonate oligomers, for example, involves washing the reaction mixture with water, dilute acid and water, then pouring into a large amount of non-solvent for the polymer (eg, methanol). The precipitated copolycarbonate oligomer is filtered and dried.

As another method, it is also possible to react in a water-organic solvent two-phase system (for example, water-methylene chloride system),
In that case, alkali metal hydroxides are used instead of amines.

The halogenated phenol is, for example, phenol such as 2,4,5-tribromophenol or 2,4,5-trichlorophenol, which serves as a terminal group forming component of the copolymerized polycarbonate oligomer.

The halogen-containing bisphenol type copolycarbonate oligomer (B) has a degree of polymerization of 2 ≦ m + n ≦ 20 (m ≧ 1,
n is an integer of 0), especially 2
It is preferable that ≦ m + n ≦ 20. When the degree of polymerization exceeds 20, it causes a problem in moldability and is not preferable.

Further, when the halogen-containing bisphenol-type copolymerized polycarbonate / oligomer (B) has too little halogen-containing bisphenol component, the halogen content of the oligomer becomes low, and a large amount of the oligomer is required for flame retarding the polyetheresteramide, Since the mechanical properties of the obtained flame-retardant polyesteramide tend to be inadequate, it is usually n /
m is preferably 40 or less, and particularly preferably 19 or less.

The halogen-containing bisphenol compound used as a raw material when synthesizing the above halogen-containing bisphenol-type copolycarbonate oligomer (B) is 2,2-bis (3,5
-Dibromo-4-hydroxyphenyl) propane, 2,2
-Bis (3,5-dichloro-4-hydroxyphenyl) propane, bis (3,5-dibromo-4-hydroxyphenyl) methane, bis (3,5-dibromo-4-hydroxyphenyl) phenylmethane, 2,2 -Bis (3,5-dibromo-4-hydroxyphenyl) ethane, bis (3,5-dibromo-4-hydroxyphenyl) ketone, bis (3,5-
Dibromo-4-hydroxyphenyl) ether, bis (3,5-dichloro-4-hydroxyphenyl) ether, bis (3,5-dichloro-4-hydroxyphenyl)
Examples thereof include ketones, and 2,2-bis (3,5-dibromo-4-) usually called tetrabromobisphenol A.
Most preferred is the use of hydroxyphenyl) propane.

Further, as the bisphenol compound, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl)
Examples include ethane, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ether and the like, and the use of 2,2-bis (4-hydroxyphenyl) propane, which is usually called bisphenol A, is most preferable. The halogen-containing bisphenol component and the bisphenol component may be any of a random copolymer, a block copolymer and an alternating copolymer.

The amount of the halogen-containing bisphenol type copolymeric polycarbonate / oligomer (B) represented by the general formula (I) is 1 to 60 parts by weight, preferably 5 to 60 parts by weight, particularly preferably 10 to 60 parts by weight. If the amount is less than 100 parts by weight, the flame retardancy is not sufficient, and if it exceeds 60 parts by weight, the mechanical properties of the polyether ester amide are impaired, which is not preferable.

At the same time, flame retardant aids such as antimony trioxide, boron oxide, zirconium oxygen, and iron oxide may be used in combination.

For example, the flame-retardant effect of halogen-containing bisphenol-type copolycarbonate / oligomer is remarkably enhanced by the combined use of antimony trioxide. The added amount is 40 parts by weight or less, preferably 35 parts by weight or less, relative to 100 parts by weight of the polyether ester amide, and when it exceeds 40 parts by weight, the mechanical properties of the polyether ester amide tend to be impaired. More preferably, it is added at a ratio of 1 antimony atom in antimony trioxide to 2 to 5 halogen atoms in the added halogen-containing bisphenol-type copolycarbonate oligomer.

The resin composition of the present invention is usually produced by a known method.

For example, polyetheresteramide (A), halogen-containing bisphenol type copolycarbonate oligomer
Method of melt mixing (B) and other necessary additives in an extruder or kneader, or method of uniformly mechanically mixing particles and then directly mixing with an injection molding machine to simultaneously mold, polymerization of resin Examples include a method of directly adding the additives into the kettle and mixing. The order of addition at this time may be arbitrary.

In addition, the resin composition of the present invention includes known antioxidants, thermal decomposition inhibitors, ultraviolet absorbers, hydrolysis resistance improvers, colorants (pigments, dyes), antistatic agents, conductive agents, reinforcing agents, and fillers. , A lubricant, a nucleus, a release agent, a plasticizer, an adhesion aid, an adhesive and the like can be optionally contained.

<Examples> The present invention will be described in detail below with reference to Examples.

All percentages and parts in the examples are by weight. The relative viscosity is a value obtained by measuring a 0.5% polymer solution using O-chlorophenol as a solvent at 25 ° C.

Reference Example (Production of Polyether Esteramide) Polymerization of Polymer (A-1) 81.9 parts of ω-aminododecanoic acid, 6.8 parts of dodecanedioic acid, and poly (tetramethylene oxide) having a number average molecular weight of 650.
Charge 19.3 parts of glycol together with 0.5 parts of “Irganox” 1098 (antioxidant) into a reaction vessel equipped with a helical ribbon stirring blade, purge with nitrogen and heat and stir at 260 ° C. for 1 hour to obtain a homogeneous transparent solution. Antimony oxide catalyst 0.
015 parts, monobutyl hydroxytin oxide catalyst 0.015 parts,
Phosphoric acid 0.005 parts (anti-coloring agent) was added and brought to a polymerization condition of less than 1 mmHg in 1 hour according to a vacuum program. When reacted for 2.5 hours under these conditions, a viscous colorless and transparent molten polymer was obtained, and when this polymer was discharged as gut into water, it was crystallized and whitened. The obtained polyether ester amide (A-1) had a relative viscosity (ηr) of 1.81 measured at a concentration of 25% at 25 ° C. in ortho and chlorophenol, and a crystal melting point by DSC of 167 ° C.
It was.

Polymerization of Polymer (A-2) 49.1 parts of ω-aminododecanoic acid, 7.9 parts of terephthalic acid, 48.8 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of 1020, 0.5 part of "Irganox" 1098, 0.015 part of antimony trioxide. , 0.015 parts of monobutyl monohydroxytin oxide, and 0.005 parts of phosphoric acid from the polymer (A-
Polymerized under the same conditions as 1), relative viscosity 1.93, melting point 154 ℃
To obtain a polyetheresteramide (A-2).

Polymerization of Polymer (A-3) 27.3 parts of ω-aminododecanoic acid, 5.7 parts of terephthalic acid, 70.5 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of 2060, 0.5 part of "Irganox" 1098, 0.015 part of antimony trioxide. , 0.015 parts of monobutylmonohydroxytin oxide, and 0.005 parts of phosphoric acid from the polymer (A
-1) Polymerization under the same conditions as above, relative viscosity 1.92, melting point 145 ° C
To obtain polyetheresteramide (A-3).

Polymerization of Polymer (A-4) Undecamethylenediamine-adipate 44.9 parts, terephthalic acid 12.8 parts, poly (tetramethylene oxide) glycol having a number average molecular weight of 650 50.0 parts, "Irganox" 1098 0.5 part, trioxide Antimony 0.015 parts, monobutylmonohydroxytin oxide 0.015 parts, and phosphoric acid 0.005
Polymerization was carried out from the part under the same conditions as for the polymer (A-1) to obtain a polyetheresteramide (A-4) having a relative viscosity of 1.80 and a melting point of 209 ° C.

Example 1 Polyether ester amide (A-
In 2), the following flame retardants (B-1), (B-2) and antimony trioxide (abbreviated as SBO) were mixed in a V-blender at a ratio shown in Table 1 and a twin-screw extruder having a screw of 45 mmφ was used. Melted and kneaded at 230 ° C to form pellets. After vacuum-drying the pellets at 80 ℃ for 12 hours, the combustion test pieces (1/16 ″ × 1/26 ″ ×) at the molding temperature of 230 ℃ and the mold temperature of 40 ℃.
5 ") tensile dumbbell specimens were molded.

Using the flammability test pieces, a vertical flammability test according to UL94 standard and a tensile physical property test according to ASTM D-638 were carried out.

The results are shown in Table 1.

Table 1 also shows an example using the flame retardant (B-3) for comparison.

Flame retardant (B-1), (B-2), (B-3) General formula In, the flame retardant (B-1) is m = 2, n = 1 (81.8% by weight of the repeating unit of tetrabromobisphenol A) The flame retardant (B-2) is m = 1, n = 2 (the repeating unit of tetrabromobisphenol A) The flame retardant (B-3) is m = 1, n = 50 (tetrabrom bisphenol A repeating unit is 4.3% by weight).

Example 2 Polyether ester amide (A-
1), (A-2), (A-3), and (A-4) 1
40 parts of the flame retardant (B-1) used in Example 1 in 00 parts,
14 parts of SBO were blended in the same manner as in Example 1 and a combustion test and a tensile test were conducted.

The results are shown in Table 2. As a comparative example, the case where no flame retardant is added is also shown.

From the results shown in Table 2, it is clear that the composition of the present invention has excellent flame retardancy even when a small proportion of the flame retardant is added, and has an excellent balance of mechanical properties.

<Effects of the Invention> The present invention provides a flame-retardant polyether ester amide exhibiting excellent mechanical properties by blending a halogen-containing bisphenol type copolycarbonate oligomer with a polyether ester amide. As a result, it is expected that the polyether ester amide will be expanded more and more, mainly for electric / electronic applications and automobile applications.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area C08L 77:12)

Claims (1)

[Claims] 1. An aminocarboxylic acid or lactam having 6 or more carbon atoms, or a salt (a) of a diamine and dicarboxylic acid having 6 or more carbon atoms, and a number average molecular weight of 300 to 6,000.
It is represented by the following general formula (I) with respect to 100 parts by weight of a polyether ester amide (A) composed of a poly (alkylene oxide) glycol (b) of 0 and a dicarboxylic acid (c) of 4 to 20 carbon atoms. Halogen-containing bisphenol type copolycarbonate oligomer (B)
A flame-retardant resin composition containing 1 to 60 parts by weight. (Wherein R represents an alkylene group in the formula, a carbonyl group, an ether group, -S- or SO 2 _-. The, R 'and R "are the halogenated phenyl group, X represents a bromine atom or a chlorine atom or, m , N is m ≧ 1, n ≧ 0, 2 ≦ m + n
It is an integer that satisfies ≦ 20)