JP3081071B2 - Flame retardant polyester resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant polyester resin composition having excellent mechanical properties, especially impact resistance.

[0002]

2. Description of the Related Art Thermoplastic aromatic polyester resins typified by polybutylene terephthalate and polyethylene terephthalate have excellent mechanical strength, chemical resistance, electrical insulation, etc., and are used for electric, electronic parts, automobile parts and other machinery. Although widely used for parts and the like, flame retardancy of molding materials is required in order to improve the safety of products.
However, in general, when a resin material is made to be self-extinguishing, a large amount of a flame retardant and a flame retardant auxiliary must be added, and a decrease in mechanical properties cannot be avoided.

[0003] The inventors of the present invention have conducted intensive studies in order to suppress such deterioration in properties, and as a result, have found that thermoplastic aromatic polyesters
The present inventors have found that a flame-retardant composition comprising a polypropylene modified with a specific epoxy compound is not only flame-retardant but also excellent in mechanical properties, especially impact resistance.

[0004]

That is, the present invention has an intrinsic viscosity of 0.4 to
With respect to 100 parts by weight of a thermoplastic aromatic polyester of 1.2, the following general formula (I) per 100% by weight of polyolefin

[0005]

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Wherein R is H or an alkyl group having 1 to 6 carbon atoms, and Ar represents at least one glycidyloxy group.
An aromatic hydrocarbon group having 6 to 20 carbon atoms,
Represents an integer of 1 to 4) 3 to 30 parts by weight of a modified polyolefin obtained by graft polymerization of 0.01 to 30% by weight of a glycidyl compound represented by the following formula: and 0.5 to 2 of a brominated flame retardant.
It is a flame-retardant polyester resin composition containing 5 parts by weight.

The present invention will be described.

The thermoplastic aromatic polyester used in the present invention has terephthalic acid as an acid component and aliphatic as diol component such as ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol and the like. An aromatic polyester composed of at least one diol is used as a main component. Among these, polybutylene terephthalate, polypropylene terephthalate, polyethylene terephthalate and the like having a high crystallization rate are preferable, and polybutylene terephthalate is particularly preferable. The thermoplastic aromatic polyester may be a polyester obtained by substituting a part of the above polyester with a copolymer component. Examples of such a copolymer component include isophthalic acid, phthalic acid; methyl terephthalic acid,
Alkyl-substituted phthalic acids such as methyl isophthalic acid; 2,6
-Naphthalene dicarboxylic acids such as naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid and 1,5-naphthalene dicarboxylic acid; diphenyl dicarboxylic acids such as 4,4'-diphenyl dicarboxylic acid and 3,4'-diphenyl dicarboxylic acid; 4 Aliphatic or alicyclic such as aromatic dicarboxylic acids such as diphenoxyethane dicarboxylic acids such as 4,4'-diphenoxyethane dicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, decane dicarboxylic acid and cyclohexane dicarboxylic acid alicyclic diols such as 1,4-cyclohexanedimethanol; dicarboxylic acid hydroquinone, dihydroxybenzenes such as resorcinol, 2,2-bis (4-hydroxyphenyl) - propane, bi scan (4-hydroxyphenyl) - Bisphenol such as sulfone S, aromatic diols such as polyether diols obtained from such glycols bisphenol and ethylene glycol; .epsilon. hydroxycaproic acid, hydroxybenzoic acid, oxycarboxylic acid such as hydroxyethoxy benzoic acid.

Further, the above-mentioned aromatic polyester has, as a branching component, an acid having a polyfunctional ester form such as trimesic acid or trimellitic acid or a polyfunctional ester form such as glycerin, trimethylolpropane or pentaerythritol. The alcohol may be copolymerized in an amount of 1.0 mol% or less, preferably 0.5 mol% or less, more preferably 0.3 mol% or less.

The thermoplastic aromatic polyester used in the present invention has an intrinsic viscosity of 0.4 to 1.2. If it is less than 0.4, sufficient properties cannot be obtained, and if it is more than 1.2, the melt viscosity is high, the flowability is reduced, and the moldability is impaired. Here, the intrinsic viscosity number (the same as the intrinsic viscosity) is measured at 35 ° C. using orthochlorophenol as a solvent.

The above-mentioned thermoplastic aromatic polyester can be produced by a conventional production method, for example, a melt polycondensation reaction or a method combining this with a solid-phase polymerization reaction. For example, a production example of polybutylene terephthalate will be described. Terephthalic acid or an ester-forming derivative thereof (for example, a lower alkyl ester such as dimethyl ester or monomethyl ester) and tetramethylene glycol or an ester-forming derivative thereof are reacted in the presence of a catalyst. The reaction can be carried out by heating, and then the resulting glycol ester of terephthalic acid is polymerized to a predetermined polymerization degree in the presence of a catalyst.

As the polyolefin as a raw material of the modified polyolefin used in the present invention, a random or block copolymer with another polyolefin component containing 50 mol% or more, preferably 80 mol% or more of a main polyolefin component can be used. The main polyolefin components include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 5-methyl-1-hexene and the like.

The following general formula (II)

[0014]

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(Wherein, R _{1 to} R ₄ are hydrogen or carbon atom 1)
And m represents an integer of 1 to 20)
May be copolymerized. here,
Non-conjugated diene comonomers include 2-methyl-1,4
-Pentadiene, 1,4-hexadiene, 4-methylidene-1-hexene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,4-heptadiene, 4-ethyl-1,4 -Hexadiene, 4,5
-Dimethyl-1,4-hexadiene, 4-methyl-1,
4-heptadiene, 4-ethyl-1,4-heptadiene, 5-methyl-1,4-heptadiene, 5-methyl-
1,4-octadiene, 1,5-heptadiene, 1,5
-Octadiene, 5-methyl-1,5-heptadiene,
2-methyl-1,5-hexadiene, 1,6-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 2-methyl-1,6-heptadiene, 1,9- Decadiene, 1,13-tetradecadiene and the like can be mentioned. Among them, 1,4-hexadiene, 2-methyl-1,5-hexadiene, 7-methyl-1,6-octadiene, 1,9-decadiene, 1,
Preferred is 13-tetradecadiene. Two or more of these non-conjugated diene comonomers may be used.

In order to randomly copolymerize the polyolefin and the non-conjugated diene comonomer, an ordinary copolymerization method using a Ziegler-Natta catalyst may be applied. In this case, the ratio of the non-conjugated diene is desirably 0.05 to 10 mol%. When the content of the non-conjugated diene is less than 0.05 mol%, a high graft ratio cannot be obtained in a subsequent graft reaction. If it exceeds 10 mol%, the crystallinity of the copolymer will be significantly reduced.

The modified polyolefin modifying monomer used in the present invention has the following general formula (I):

[0018]

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Wherein R is hydrogen or an alkyl group having 1 to 6 carbon atoms, Ar is an aromatic hydrocarbon group having 6 to 20 carbon atoms having at least one glycidyloxy group, and n is 1 to 6 A glycidyl compound represented by the following formula:

Preferred glycidyl compounds include:
And those represented by the following general formula (III).

[0021]

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(Wherein R ₅ represents hydrogen or an alkyl group having 1 to 6 carbon atoms.) Such a glycidyl compound is disclosed in, for example, JP-A-60-1.
It can be produced by the method disclosed in Japanese Patent No. 30580. The modified polyolefin can be produced by graft-polymerizing the glycidyl compound represented by the general formula (I) to the polyolefin. In the case of the solution method or the melt kneading method, the polyolefin and the above-mentioned glycidyl compound, and a catalyst are charged into an extruder or the like in the case of a solution method or a melt kneading method, and 200 to 300 ° C, preferably 220 to 260 ° C
The mixture can be manufactured by kneading for 0.1 to 20 minutes while heating and melting. In the case of the solution method, the starting material is dissolved in an organic solvent such as xylene, and the solution is stirred at 90 to 200 ° C. for 0.1 to 100 hours. In each case, a normal radical polymerization catalyst can be used as a catalyst, for example, benzoyl peroxide, lauroyl peroxide,
Di-t-butyl peroxide, acetyl peroxide, t-butylperoxybenzoic acid, dicumyl peroxide, peroxybenzoic acid, t-butylperoxypivalate, 2,5-dimethyl-2,5-di-t-butylperoxy Peroxides such as hexine and diazo compounds such as azobisisobutyronitrile are desirable. The amount of the catalyst is about 0.1 to 10 parts by weight based on 100 parts by weight of the glycidyl compound. In the present invention, a phenolic antioxidant can be added during the graft reaction. However,
When the radical polymerization catalyst is not added, it is preferable not to add it.

In the production of the modified polyolefin, the compounding ratio of the glycidyl compound is 100% by weight of the polyolefin.
0.01 to 30% by weight, preferably 0.1 to 1% by weight
0% by weight. The amount of the glycidyl compound is 0.01
If the amount is less than 30% by weight, the mechanical properties of the obtained resin composition will be low, and if it exceeds 30% by weight, the molecular weight of the resulting modified polyolefin will be low. The modified polyolefin thus obtained has a very small decrease in molecular weight, does not generate odor at the time of modification, and has no discoloration.

The compounding amount of the modified polyolefin of the present invention is
3 to 100 parts by weight of the thermoplastic aromatic polyester
30 parts by weight, preferably 3 to 20 parts by weight. If the modified polyolefin is less than 3 parts by weight, the impact resistance will not be improved. Conversely, if it exceeds 30 parts by weight, the rigidity is reduced.

Examples of the flame retardant used in the present invention include brominated bisphenol A compounds, vinyl polymer flame retardants having a brominated substituent, and the like. Suitable brominated bisphenol A-based compounds include brominated bisphenol A-based polycarbonates represented by the following general formula (IV) and brominated bisphenol A-based epoxy resins represented by the following general formula (V). Can be.

[0026]

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[0027]

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Although the terminal structure of the brominated bisphenol A-based polycarbonates (IV) is not particularly limited, 4-t-
Examples thereof include a butylphenyl group and a 2,4,6-tribromophenyl group. Examples of suitable vinyl polymer flame retardants having a brominated substituent include brominated polystyrenes represented by the following general formula (VI) and brominated benzyl acrylates represented by the following general formula (VII). Can be

[0029]

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[0030]

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The addition amount of the flame retardant is 0.5 to 25 parts by weight, preferably 3 to 20 parts by weight. The larger the amount of the inorganic filler in the entire composition, the smaller the amount of the flame retardant when a flame retardant auxiliary is used together, but even in that case, at least 0.5% by weight is necessary, If the amount is less than 0.5 part by weight, the resulting composition has insufficient flame retardancy. 2 added
If the amount exceeds 5 parts by weight, the dispersion of the flame retardant becomes worse, the extrudability and the moldability are lowered, and the physical properties of the obtained molded product are undesirably lowered.

Further, a flame retardant aid can be added for the purpose of promoting the flame retardant effect. Examples of suitable flame retardant aids include S
b ₂ O ₃ and / or _{xNa 2 O · Sb 2 O 5} · yH 2
O (x = 0 to 1, y = 0 to 4).
Although the particle size of the flame retardant aid is not particularly limited,
m is preferred. If desired, those surface-treated with an epoxy compound, a silane compound, an isocyanate compound, a titanate compound or the like can be used. The addition amount of the flame retardant aid is 0 to 15 parts by weight, but it is preferable to add the flame retardant to the flame retardant in an amount of 20 to 70 parts by weight in order to effectively impart the flame retardancy. If the added amount exceeds 15 parts by weight, decomposition of the resin and the compounding agent is promoted, and the properties of the molded product may be undesirably reduced.

The thermoplastic polyester composition of the present invention may contain other inorganic solids, for example, particulate or amorphous fillers such as calcium carbonate, titanium oxide, feldspar minerals, clay, white carbon, carbon black, and glass beads. Plate-like fillers such as kaolin, clay and talc; scaly fillers such as glass flakes, mica and graphite can also be added.

The thermoplastic polyester composition of the present invention may contain ordinary nucleating agents, lubricants, antioxidants, ultraviolet absorbers, heat stabilizers, pigments, modifiers and the like within a range not to impair the object of the present invention. Additives can be included.

The modified polyester resin composition of the present invention can be prepared by subjecting each component to a known method, for example, using a Banbury mixer, a heating roll, a single-screw or multi-screw extruder, and the like.
C., preferably from 220 to 270.degree. C. by melt-kneading.

[0036]

The present invention will be described in detail with reference to the following examples. Parts in the examples mean parts by weight. Further, the characteristics of the molded product were measured by the following methods. Impact strength: ASTM256 Combustion test: A flammability test was conducted using five test pieces (thickness: 1/16 inch) according to the method of Subject 94 (UL-94) of Underwriters Laboratories.

[0037]

Examples 1 to 3 and Comparative Examples 1 to 5 In these examples, the effect of improving the impact resistance of the resin composition was tested.

Glass fiber, impact modifier, flame retardant, flame retardant aid and other additives shown in Table 1 were added to polybutylene terephthalate, and the mixture was melt-kneaded and extruded at a cylinder temperature of 270 ° C. using a 68 mm diameter extruder. A pellet was obtained. A molded piece was prepared from the obtained pellets using an injection molding machine in accordance with the above test method, and the impact strength and the flame retardancy were examined. Table 1 shows the results.

As a comparative example, a molded piece containing an impact modifier other than the modified polyolefin or containing no impact modifier was prepared, and the impact strength and flame retardancy were measured in the same manner. Table 1 shows the results.

As is clear from the results shown in Table 1, the molded article obtained from the thermoplastic polyester composition of the present invention has a remarkable effect of improving impact resistance.

[0041]

[Table 1]

[0042]

Examples 4 to 5 and Comparative Examples 6 to 10 Melt kneading and extrusion were performed in the same manner as in Example 1 with the compositions shown in Table 2 to obtain pellets. A molded piece was prepared from the obtained pellet, and the impact strength and the flame retardancy were similarly examined. Table 2 shows the results.

As a comparative example, a molded piece containing an impact modifier other than the modified polyolefin or containing no impact modifier was prepared, and the impact strength and flame retardancy were measured in the same manner. Table 2 shows the results.

As is evident from the results in Table 2, molded articles obtained from the thermoplastic polyester composition of the present invention have a remarkable effect of improving impact resistance.

[0045]

[Table 2]

[0046]

Examples 6 to 10 Melt kneading and extrusion were performed in the same manner as in Example 1 with the compositions shown in Table 3 to obtain pellets. A molded piece was prepared from the obtained pellet, and the impact strength and the flame retardancy were similarly examined. Table 3 shows the results.

As is evident from the results in Table 3, it can be seen that the molded products obtained from the thermoplastic polyester composition of the present invention show good impact resistance.

[0048]

[Table 3]

Claims (3)

(57) [Claims] 1. A compound represented by the following general formula (I) per 100% by weight of a polyolefin with respect to 100 parts by weight of a thermoplastic aromatic polyester having an intrinsic viscosity of 0.4 to 1.2. (Wherein, R is H or an alkyl group having 1 to 6 carbon atoms,
Ar is an aromatic hydrocarbon group having 6 to 20 carbon atoms and having at least one glycidyloxy group, and n represents an integer of 1 to 4).
% By weight of a modified polyolefin obtained by graft polymerization
A flame-retardant polyester resin composition comprising 30 parts by weight and 0.5 to 25 parts by weight of a brominated flame retardant. 2. The flame-retardant polyester resin composition according to claim 1, wherein the thermoplastic aromatic polyester is polyethylene terephthalate or polybutylene terephthalate. 3. The flame-retardant polyester resin composition according to claim 1, wherein the flame retardant is a brominated bisphenol A-based compound.