JPH0415258B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a modified polyester resin composition having a high degree of flame retardancy. More specifically, the present invention relates to flame retardation of a modified polyalkylene terephthalate resin modified to rapidly crystallize by polycondensing or mixing a polyalkylene compound having an organic acid metal salt. Polyalkylene terephthalate has a high softening point and has excellent electrical, physical and mechanical properties, including heat resistance, chemical resistance, and light resistance, so it is widely used in fibers, films, and molded products. ing. Such polyalkylene terephthalate,
In particular, polyethylene terephthalate has a slow crystallization rate and requires high mold temperature during molding. The present inventors first improved the crystallization rate by copolymerizing or mixing a polyoxyalkylene compound having an organic acid metal salt with polyalkylene terephthalate, and achieved mold releasability even at a mold temperature of 100°C or less. It has been found that a molded article with excellent surface gloss, mechanical strength, and heat resistance can be obtained. However, such modified polyalkylene terephthalate resins have poor flame retardancy, causing problems especially when applied to building material parts and electrical parts, and may be subject to significant limitations in terms of use. Traditionally, methods for making plastics flame retardant include:
It is known that organic halogen compounds, organic phosphorus compounds, organic nitrogen compounds, etc. are used together with flame retardant additives, but extremely highly crystalline resins such as the modified polyalkylene terephthalate resin of the present invention,
When such flame retardants are used, poor dispersion may occur, resulting in a decrease in physical properties such as the Izot impact value, and so-called bleeding, where the flame retardant leaches onto the surface of the molded product. Many of them had the disadvantage of not being able to withstand use as resins. As a result of intensive studies based on this viewpoint, the present inventors have found that by closely blending a specific halogen-containing polymer into a modified polyester resin that has been modified into a polyoxyalkylene compound having an organic acid metal salt, Even at mold temperatures below 100℃,
The present invention was achieved by discovering that it is possible to obtain a molded article with excellent mold release properties, virtually no bleeding, and a high degree of flame retardancy without impairing mechanical strength or heat resistance. . That is, the present invention provides (A) a polyalkylene terephthalate polymer 99.9
~70% by weight, molecular weight is 400~20000, general formula
(1) R ¹ − [(-OR ² −) _l OR ³ ] _n ...(1) [In the formula, R ¹ is hydrogen or an aliphatic hydrocarbon group having a hydroxyl group, and R ² is an aliphatic group having 2 to 4 carbon atoms. polyoxyalkylene compound represented by a group hydrocarbon group, l is an integer of 5 to 400, ^R3 is an acyl group having one or more COOM, M is an alkali metal, and m is an integer of 1 to 6] 98 to 20 parts by weight of a modified polyester modified with 30% by weight, (B) Softening point of 100°C or higher, average molecular weight of 1000 to 20,000,
1 to 35 parts by weight of a halogen-containing polymer having a halogen content of 50% by weight or more and a weight loss rate of 5% by weight or less at molding temperature, (C) 1 to 20 parts by weight of an antimony compound, and (D) Reinforcement. A flame-retardant polyester resin composition containing 0 to 65 parts by weight of a filler. The polyalkylene terephthalate polymer referred to in the present invention is a dicarboxylic acid component in which at least 80 mol% is terephthalic acid, and at least 80 mol% is ethylene glycol, propane-1,3-diol, butane-1,4 -diol, pentane-1,5-diol, hexane-
It is obtained by direct esterification or transesterification with a diol component such as 1,6-diol or cyclohexane-1,4-dimethanol, followed by polycondensation. From an industrial standpoint, polyethylene terephthalate and polybutylene terephthalate are particularly preferred. 0 to 20 mol% of the dicarboxylic acid component of polyalkylene terephthalate is other aromatic dicarboxylic acid having 6 to 14 carbon atoms, aliphatic dicarboxylic acid having 4 to 8 carbon atoms, or alicyclic dicarboxylic acid having 8 to 12 carbon atoms. It may be hot. Examples of such dicarboxylic acids include phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, adipic acid, sebacic acid, cyclohexanedicarboxylic acid, and the like. Furthermore, 0 to 20 mol% of the diol component may be other aliphatic diols having 3 to 10 carbon atoms, other alicyclic diols having 6 to 15 carbon atoms, or aromatic diols having 6 to 12 carbon atoms. . Examples of such diols include 2,2-
dimethylpropane-1,3-diol, 2,2-
Bis-(4'-hydroxycyclohexyl)-propane, 2,2-bis-(4'-hydroxyphenyl)
Examples include propane and hydroquinone. Furthermore, oxycarboxylic acids such as ε-oxycaproic acid, hydroxybenzoic acid, etc. may be copolymerized in an amount of 20 mol% or less of the dicarboxylic acid component and diol component. Of course, the polyalkylene terephthalate may also be branched with trihydric or tetrahydric alcohols or tribasic or tetrabasic acids. Examples of suitable branching agents include trimesic acid, trimellitic acid, trimethylolpropane, pentaerythritol, and the like. In the present invention, the polyoxyalkylene compound having at least one organic carboxylic acid alkali metal salt in one molecule has the following general formula (1) R ¹ −[(-OR ² −) _l OR ³ ] _n ... (1) [In the formula, R ₁ , R ₂ , R ₃ , l, and m are the same as above]. Such a polyoxyalkylene compound is produced by, for example, esterifying a monofunctional or polyfunctional alcohol of substantially polyoxyalkylene with a polyhydric carboxylic acid anhydride in the presence of a basic catalyst or an acid catalyst as necessary. Obtained by chlorination. Here, "substantially" means that a portion of the molecule may contain other elements or organic groups. Specific examples of such polyoxyalkylene compounds include monosuccinic acid ester potassium salts, monophthalic acid ester sodium salts, and mono(tetrabromo)phthalic acid such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and ethylene oxide-propylene oxide copolymers. ester sodium salt,
Dipotassium salt of monotrimellitic acid ester; sodium salt of mono- and diphthalic acid ester such as glycerin-alkylene oxide adduct, trimethylolpropane-alkylene oxide adduct, sodium salt of mono-, di(tetrabromo)phthalic acid ester, mono-, di-trimellitic acid Ester sodium salt; mono, di, triphthalic acid ester sodium salt, mono, di, tri(tetrabromo) phthalic acid ester sodium salt, mono, di, etc., such as pentaerythritol-alkylene oxide adduct;
Examples include tritrimellitic acid ester sodium salt. In addition, mono, di, and tri described in the specific examples indicate the number of esters. Of course, the polyoxyalkylene compound is not limited to those exemplified above. These may be used alone or in combination of two or more. Further, these can be used in combination with polyoxyalkylene itself such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. The crystallization rate of polyalkylene terephthalate is significantly improved by polycondensation and/or mixed dispersion of a polyoxyalkylene compound having an alkali metal salt of an organic carboxylic acid. This is due to polycondensation or mixed dispersion of polyoxyalkylene chains with a low glass transition point in polyalkylene terephthalate with good compatibility, which improves the mobility of polyalkylene terephthalate chains and improves the mobility of organic carboxylic acid alkali which is a nucleating agent component. It is presumed that this effect occurs in conjunction with the effect of the metal salt. The molecular weight range of polyoxyalkylene compounds is
400 to 20,000, particularly preferably 400 to 5,000 from the viewpoint of compatibility with polyester chains. Considering the level of crystallization promoting effect, the amount of polyoxyalkylene compound used is usually 0.1 to that of modified polyester.
-30% by weight, preferably 1-20% by weight. The metal content in the polyoxyalkylene compound varies depending on the type and molecular weight of the polyoxyalkylene, but is usually 0.01 to 20% by weight, preferably 1 to 5% by weight. Among the alkali metal salts of organic carboxylic acids, alkali metal salts of aromatic carboxylic acids are particularly preferred from the viewpoint of compatibility with polyester, crystallization promoting effect, thermal oxidation stabilizing effect, and the like. Furthermore, from the viewpoint of uniform dispersion of the polyoxyalkylene compound, it is particularly preferable that the polyoxyalkylene compound is polycondensed with a polyester. Further, polyoxyalkylene compounds having an alkali metal salt of a halogen-containing organic carboxylic acid such as tetrabromophthalic acid ester sodium salt are preferred because they have the effect of further improving flame retardancy as well as improving crystallization properties. It is something. Polycondensation and/or mixing of such polyoxyalkylene compounds can be carried out by adding the polyoxyalkylene compound during production of polyalkylene terephthalate and reacting or mixing it, or by mixing polyalkylene terephthalate with a kneading device such as an extruder. This can be achieved by a method of further performing a melt polycondensation reaction after mixing. Furthermore, it is also possible to subsequently subject the polycondensate or mixture to a solid phase polycondensation reaction. The halogen-containing polymer referred to in the present invention refers to a specific oligomer or high molecular weight flame retardant defined in (B) of claim 1. That is, the softening point is 100°C or higher, preferably 120°C or higher, and if it is significantly different from the melting point of the modified polyester,
Mixing is not possible. Average molecular weight is 1000-20000
and preferably 1500 to 10000. When the average molecular weight is less than 1,000, bleeding tends to occur due to high mobility, and when it exceeds 20,000, aggregation occurs, so dispersion in modified polyester cannot be carried out using normal methods. Can not. The halogen content used is 50% by weight or more. If the content is less than 50% by weight, the flame retardant effect may be insufficient, or the amount added must be increased to provide sufficient flame retardant effect, leading to a decrease in mechanical strength etc. Become. In addition, "stable at the molding temperature" means that the weight loss as determined by thermogravimetric analysis at the same temperature as the molding temperature is 5% by weight or less. The material becomes colored and cannot withstand use as a resin. Specific examples of such halogen-containing polymers are shown below. () A halogenated polyphenylene oxide compound derived from a halogenated phenol having a repeating structural unit represented by the following general formula (2). (Here, X represents Br or Cl, and a represents an integer of 1 to 4.) For example, a condensate of tribromophenol, a condensate of trichlorophenol, a condensate of tetrabromophenol, a condensate of tetrachlorophenol , a condensate of pentabromophenol, a condensate of pentachlorophenol, etc., but preferably a condensate of tribromophenol is used. () A halogen-containing S-triazine condensate having a structural unit represented by the following general formula (3), which is derived by a condensation reaction of a halogenated bisphenol and cyanuric chloride, and whose terminals are capped with a phenol. (In the formula, Y; lower alkylene group, halogenated lower alkylene group, alkylidene group, -SO ₂ -, -
Indicates SO-, -S-, -O-, -CO-, or a direct bond. X; Br or Cl, R ⁸ ; lower alkyl group or halogenated lower alkyl group, b, c, d, e;
Each integer from 0 to 4, b+c+d+e≦8, and 1+d+e≦2, R ^w is a hydroxyl group, Cl, R ⁴ below,
Represented by R ⁵ or R ⁶ . ) (R ⁷ ; lower alkyl group or halogenated lower alkyl group, f, g; integer from 0 to 4, f+g≦5) (Y, X, R ⁸ , b, c, d, e are the same as above) ^{( In} the formula, Y, Examples include dihalides and tetrahalides, with tetrabromobisphenol A and tetrabromobisphenol S being preferred. Phenols used to block terminals include phenol, monobromophenol,
Examples include tribromophenol, pentabromophenol, monochlorophenol, trichlorophenol, pentachlorophenol, tribromocresol, etc. Tribromophenol,
Particularly preferred is pentabromophenol. () A halogenated polycarbonate compound having a repeating structural unit represented by the following general formula (4). (In the formula, R ⁹ and R ¹⁰ are hydrogen, lower alkyl, or phenyl, X is Br or Cl, and h and i are integers from 1 to 4.) For example, bisphenol A, bisphenol S,
A polycarbonate obtained by adding phosgene to a halogenated bisphenol selected from dihalides or tetrahalides such as bisphenol F, and end-capped with phenol and a phenol halide, preferably end-capped with tribromophenol. It is a tetrabromobisphenol A type polycarbonate. () A halogenated bisphenol type epoxy resin represented by the following general formula (5). (In the formula,
Indicates SO ₂ -, -SO-, -S-, -O-, -CO- or a direct bond. ) For example, a bisphenol type epoxy resin obtained by condensing a dihalide or tetrahalide such as bisphenol A, bisphenol S, or bisphenol F with epichlorohydrin, preferably tetrabromobisphenol A or tetrabromobisphenol. Examples include epoxy resins using S. Although specific examples have been shown above, the halogen-containing polymer referred to in the present invention is not limited to these. Furthermore, the halogen-containing polymers may be used alone or in combination of two or more. Furthermore, other known flame retardants may be used in combination with these halogen-containing polymers to the extent that bleeding does not occur. The antimony compound referred to in the present invention refers to an inorganic antimony compound and an organic antimony compound,
A synergistic effect can be produced by using it in combination with a halogen-containing polymer. Specific examples include inorganic antimony compounds such as antimony trioxide, antimony pentoxide, and antimony phosphate; and organic antimony compounds such as antimony caproate, antimony tartrate, and triphenyl antimony. Particularly preferred. In order to exhibit a sufficient flame retardant effect when added to the composition, the halogen-containing polymer should be added in an amount of 1 to 35 parts by weight.
Preferably 5 to 25 parts by weight of antimony compound 1
~20 parts by weight, preferably 2 to 15 parts by weight, with an atomic ratio of halogen to antimony of 0.1 to 10,
It is necessary to add preferably 0.5 to 5. If the amount added is smaller than this, the flame retardant effect will be small, and if the amount is larger than this, the mechanical strength will drop significantly and the resin will not be able to withstand use. In the present invention, the reinforcing filler refers to fibrous,
It refers to plate-shaped or granular inorganic fillers, and when these are blended, mechanical strength, heat resistance, and dimensional stability can be further enhanced. Specific examples include glass fiber, mineral fiber, carbon fiber, silicon carbide fiber, boron carbide fiber, potassium titanate fiber, gypsum fiber,
Examples include mica, talc, kaolin, clay, asbestos, calcium silicate, calcium sulfate, calcium carbonate, etc., but especially glass fiber,
Mica, talc and mineral fibers are preferred. These may be used alone or in combination of two or more, and may be surface-treated with a silane coupling agent or the like to improve affinity with the resin. The amount added is 0
The amount is preferably 10 to 55 parts by weight in consideration of mechanical strength, heat resistance, and fluidity, and can be determined based on quality settings. To produce the flame-retardant modified polyester composition of the present invention, a halogenated diphenyl ether compound, antimony trioxide, a reinforcing filler, and a modified polyester resin may be mixed by a known method, and the modified polyester resin Examples include a method of mixing and extruding the modified polyester resin with an extruder, a method of simply mixing with the modified polyester resin and directly injection molding, and a method of adding and blending at the time of manufacturing the modified polyester resin. The thus obtained composition of the present invention is particularly suitable for injection molding, but it can also be made into a molded article by extrusion molding or other molding methods. As is clear from the examples described below, the molded product obtained by molding the composition of the present invention has excellent mold releasability even at a mold temperature of 100°C or less, and virtually no bleeding occurs. Moreover, it has a high degree of flame retardancy without compromising mechanical strength or heat resistance. The composition of the present invention may contain other known nucleating agents, thermal oxidation stabilizers, light stabilizers, and other additives such as plasticizers, lubricants, and colorants. Furthermore, a small proportion of other types of thermoplastic resins can be blended, and a small proportion of a rubber component can also be introduced in order to improve impact resistance. The composition of the present invention can be widely used for molding various molded parts, pipes, containers, etc., and can be particularly suitably used for electrical parts, building material parts, automobile parts, etc. In some cases, it can also be used for fibers, films, and sheets. The present invention will be explained below with reference to Examples. In the examples, the intrinsic viscosity of the polymer was 25% in phenol/tetrachloroethane (1:1 parts by weight).
It was determined from the logarithmic viscosity measured at 0.5 g/dl concentration at °C. The melting point Tm, cooling crystallization temperature Tc (C) from a molten state, and heating crystallization temperature Tc (H) from a glass state of the modified polyester were measured using a Perkin-Elmer Model DSC-1B. The tensile strength of the molded product is
ASTM-D638, bending strength and bending modulus are
ASTM-D79C, Izotsu impact resistance value is ASTM-
D256, heat distortion temperature (18.6Kg/cm ² ) is ASTM-
D648 and flame retardancy were measured in accordance with the UL94 vertical test method. [Simple Bleeding Evaluation Method] A 5″ x 1/2″ x 1/16″ injection molded body was colored black using paint, and after air drying, the lightness L ₁ was measured using a photometer.Next, After heating the sample piece at 140°C under reduced pressure for 15 hours, the lightness L ₂ was measured and the lightness difference ΔL = L ₂ - L ₁ was calculated.The lightness difference when no flame retardant was added was set as ΔL ₀ . , the bleeding index was defined as ΔL ₁ −ΔL ₀ , and each sample piece was evaluated. Production of modified polyester: Reference example 1 1942 g (10 moles) of dimethyl terephthalate and ethylene glycol were placed in a 4-autoclave equipped with a stirrer.
1366 g (22 mol), 1.2 g of zinc acetate as a transesterification catalyst, and heated at 160 to 210℃ under nitrogen atmosphere for 3 hours.
Transesterification was carried out by heating and stirring for hours. After distilling off methanol, 226 g (0.13 mol) of polyethylene glycol monotrimellitic acid ester disodium salt having an average molecular weight of 1740 and 0.7 g of antimony trioxide as a polycondensation catalyst were added. After raising the temperature and reducing the pressure to 270°C and below Torr, a polycondensation reaction was carried out for 3 hours. Table 1 shows the properties of the obtained modified polyester. Reference Example 2 Instead of polyethylene glycol monotrimellistate disodium acid in Reference Example 1, the average molecular weight
A similar operation was carried out using 448 g (0.1 mol) of pentaerythritol-ethylene oxide adduct-ditrimellitic acid ester tetrasodium salt of 4480 to obtain a modified polyester. Its characteristics are shown in Table-1.

[Table] Examples 1 to 2, Comparative Example 1 0.5 parts by weight of Ionox 330 (manufactured by Ciel Chemical Co., Ltd.) was added as an antioxidant to the modified polyester pellets obtained in Reference Example 1, and glass fiber with a fiber length of 3 mm (Asahi Fiberglass) was added to the pellets of the modified polyester obtained in Reference Example 1. 03-486A), mineral fiber (processed mineral fiber manufactured by Jim Walter), condensate of cyanuric chloride, tetrabromobisphenol A, and tribromophenol (average molecular weight approximately 8000, softening point 220°C, bromine content 62 After mixing antimony trioxide in various ratios (weight %, weight loss rate at 300°C: 1% by weight or less), the mixture was melted into pellets using an extruder. Next, using this pellet, the cylinder temperature is C ₁ 250℃, C ₂ 260℃,
Injection molding was performed under the following molding conditions: C ₃ 260°C, mold temperature 100°C, cooling 30 seconds, and holding pressure 10 seconds to obtain a test piece. The molded product had excellent releasability from the mold and surface gloss. As shown in Table 2, the bleed index was small, indicating that there was virtually no bleeding of the flame retardant. Moreover, the mechanical strength, heat resistance, and flame retardance of the molded article showed excellent values. For comparison, when similar measurements were made using decabromodiphenyl ether instead of the above condensate, the bleed index was large and bleeding occurred. Comparative Example 1 100 parts of polyethylene terephthalate and 18.7 parts of ionomer resin (manufactured by Mitsui Dupont Polychemical Co., Ltd., ethylene/methacrylic acid copolymer Combined partial Na salt (Na content 17500ppm))
The test was conducted in the same manner as in Example 1. the result,
The heat distortion temperature decreased to 161°C, which was unsuitable for practical use.

[Table] Examples 3 to 4, Comparative Example 2 0.5 parts by weight of Ionox 330 (manufactured by Ciel Chemical Co., Ltd.) was added as an antioxidant to the modified polyester pellets obtained in Reference Example 2, and glass fiber with a fiber length of 3 mm (Asahi Fiber Glass) was added to the pellets of the modified polyester obtained in Reference Example 2. 03-486A), mineral fiber (processed mineral fiber manufactured by Jim Walter), tribromophenol condensate (average molecular weight approximately 6000, softening point 200°C, bromine content 65% by weight,
After mixing antimony trioxide in various ratios (weight loss rate at 300°C of 1% by weight or less), the mixture was melted into pellets using an extruder. Next, a test piece was obtained under the same conditions as in Example 1. The molded product had excellent releasability from the mold and surface gloss. As shown in Table 3, the bleed index was small, indicating that there was virtually no bleeding of the flame retardant. Moreover, the mechanical strength, heat resistance and flame retardance of the molded product showed excellent values. For comparison, a similar measurement was performed using a condensate of tribromophenol having an average molecular weight of about 750 instead of the above condensate, and the bleed index showed a large value of 10.0, indicating that bleeding occurred.

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Claims (1)

[Claims] 1 (A) Polyalkylene terephthalate polymer
99.9 to 70% by weight and a molecular weight of 400 to 20000, general formula (1) R ¹ − [(−OR ² −) _l OR ³ ] _n (1) (wherein R ¹ is hydrogen or an aliphatic group having a hydroxyl group) hydrocarbon group, R ² is an aliphatic hydrocarbon group having 2 to 4 carbon atoms, l is an integer of 5 to 400, R ³ is an acyl group having one or more COOM, M represents an alkali metal, m is 1 An integer of ~6) Polyoxyalkylene compound represented by 0.1~
Modified polyester obtained by modifying with 30% by weight
98-20 parts by weight, (B) Softening point 100°C or higher, average molecular weight 1000-20000,
1 to 35 parts by weight of a halogen-containing polymer having a halogen content of 50% by weight or more and a weight loss rate of 5% by weight or less at molding temperature, (C) 1 to 20 parts by weight of an antimony compound, and (D) reinforcing filler. A flame-retardant polyester resin composition containing 0 to 65 parts by weight of an agent. 2. The composition according to claim 1, wherein the polyalkylene terephthalate polymer is polyethylene terephthalate or polybutylene terephthalate. 3. The composition according to claim 1, wherein the halogen-containing polymer is a brominated polyphenylene oxide, a bromine-containing S-triazine compound, a brominated polycarbonate, or a brominated bisphenol type epoxy resin. 4. The composition according to claim 1, wherein the antimony compound is antimony trioxide. 5. The composition according to claim 1, wherein the reinforcing filler is glass fiber or mineral fiber.