JPH0468057A - Flame-retardant polyester resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. excellent in wet heat resistance, flame retardance, and flowability by compounding a polybutylene naphthalenedicarboxylate with a brominated polystyrene flame retardant and, if necessary, a specific auxiliary flame retardant and an inorg. filler. CONSTITUTION:30-99.5wt.% polybutylene naphthalenedicarboxylate, 0.5-25wt.% brominated polystyrene flame retardant, 0-15wt.% at least one auxiliary flame retardant selected from the group consisting of Sb2O3 and xNa2O.Sb2O5.yH2O (wherein (x) is 0-1; and (y) is 0-4), and 0-50wt.% inorg. filler (pref. glass or carbon fibers) are compounded to give the title compsn., which is excellent in wet heat resistance, flame retardance, and flowability.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to polybutylene naphthalene dicarboxylate (
Hereinafter, it will be abbreviated as PBN and may be referred to as polybutylene naphthalate. ), brominated polystyrene R refueling agent, Sb2
03 and XNa20 ・Sb20s ・yH20(x
=O~1. The present invention relates to a flame-retardant polyester resin composition which is composed of a flame-retardant aid represented by V=O~4) and an inorganic filler and has excellent moist heat resistance, flame release properties, and fluidity.

[Prior art and its problems] In general, compositions made of polybutylene terephthalate (hereinafter abbreviated as PUT) containing a flame retardant such as brominated epoxy, 5b2o3, and optionally an inorganic filler are flame retardant. Due to its excellent mechanical strength, electrical insulation, chemical resistance, etc., it is widely used in electrical and electronic parts, home appliance lighting parts, automobile parts, machine parts, etc. Conventionally, general-purpose plastics such as polypropylene and thermosetting resins such as phenolic resins have been used as materials for these parts, but as higher functionality, higher performance, and improved moldability are required, PBT It is starting to be replaced.

However, in recent years, PBT molded parts have been increasingly used in harsher environments such as high temperatures, and conventional flammable PBTM products are no longer able to meet the required quality.

In the first place, PBT has an ester bond in its main chain, so its heat-and-moisture resistance is generally inferior to that of polyamides, etc., and attempts have been made to improve its resistance to heat and humidity. As a measure for this purpose, it is known that reducing the concentration of carboxyl groups at the terminals of the PBT polymer is effective. Solid phase polymerization is generally proposed as a means for reducing the terminal carboxyl group concentration. A method has also been proposed in which a compound having a functional group that reacts with a carboxyl group, such as an epoxy group or an isocyanate group, is added to PUT.

However, even with the use of PBT that has been improved in this way, the moist heat resistance of compositions with added retardants, retardants, and inorganic fillers is not sufficiently improved, and the strength is significantly lower after hot water deterioration tests. Therefore, there is a high possibility that the lifespan and reliability of the component will decrease.

Furthermore, if a flame retardant or flame retardant is added to PBT or a composition of PBT and an inorganic filler, the screws and barrels of extruders and molding machines, as well as the molds, will be severely corroded, and the molded products will be burnt. It is better to add as little amount as possible because it often increases the amount of carbon dioxide and decreases strength, elongation, etc.

In addition, molded products are becoming smaller and thinner recently as the functionality of parts improves. Therefore, resin compositions that have high fluidity are required.

The inventor of the present invention has conducted intensive studies on improving such characteristics and has arrived at the present invention.

[Means for Solving the Problems] The present invention provides polybutylene naphthalate (PBN) and brominated polystyrene flame retardants, Sbz 03 and/or XNaz O.5t)z Os.VHzO (X =
O~1.

The present invention relates to a flame retardant polyester resin composition comprising a combustion aid represented by y=o to 4) and an inorganic filler.

In the present invention, -PBN refers to a polyester containing naphthalene dicarboxylic acid, preferably naphthalene-2,6-dicarboxylic acid as the main acid component and 1,4-butanediol as the main glycol component, that is, all or most of the repeating units. Partially usually 90 mol% or more, preferably 95 mol%
Above) is a polyester which is butylene naphthalate.

Further, the following components can be copolymerized with this polyester as long as the physical properties are not impaired. That is, as an acid component,
Aromatic dicarboxylic acids other than naphthalene dicarboxylic acid, such as phthalic acid, isophthalic acid, terephthalic acid, diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenoxyethane dicarboxylic acid, diphenylmethane dicarboxylic acid, diphenylmethane dicarboxylic acid, diphenyl sulfide dicarboxylic acid, diphenyl sulfone dicarboxylic acid Examples include acids, aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid, tetralin dicarboxylic acid, decalin dicarboxylic acid, and the like.

Glycol components include ethylene glycol, propylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, neopentyl glycol, cyclohexane dimetatool, xylylene glycol, diethylene glycol, polyethylene glycol, bisphenol A, catechol, resorcinol. , hydroquinone, dihydroxydiphenyl, dihydroxydiphenyl ether, dihydroxydiphenylmethane, dihydroxydiphenyl ketone, dihydroxydiphenyl sulfide, dihydroxydiphenyl sulfone, and the like.

Oxycarboxylic acid components include oxybenzoic acid, hydroxynaphthoic acid, hydroxydiphenylcarboxylic acid,
Examples include ω-droxycaproic acid.

Further, a trifunctional or higher functional compound such as glycerin, trimethylpropane, pentaerythritol, trimellitic acid, pyromellitic acid, etc. may be copolymerized within a range where the polyester does not substantially lose its molding performance.

Such polyesters include naphthalene dicarboxylic acid and/or
Alternatively, it can be obtained by polycondensing a functional derivative thereof with butylene glycol and/or a functional derivative thereof using a conventionally known aromatic polyester manufacturing method. Further, although there is no particular restriction on the degree of crushing of the terminal carboxyl group of PBN used in the present invention, it is preferable that the degree of crushing is as small as possible.

The brominated polystyrene flame retardant used in the present invention has the following structure (I), and the amount of flame retardant added is 0.5 to 25
Weight%. The larger the amount of inorganic filler added in the entire composition, or when a flame retardant such as 5b203 is used together, the smaller the amount of flame retardant added can be, but it is still at least 0.5
The percentage by weight is necessary; if it is less than that, the resulting composition will have insufficient flame retardancy. On the other hand, if the amount is more than 25% by weight, the flame retardant will not be well dispersed, resulting in poor extrudability and formability, and the resulting molded product will have low strength, which is not preferable.

Next, 5b203 and/or xN used in the present invention
az O・Sb20s-VHzO(X=O~l,V
The combustion aid consisting of =0~4 is preferably blended in order to improve the combustion effect.The particle size is not particularly limited, but is preferably 0.02 to 5 .mu.m. In addition, epoxy compounds, silane compounds, isocyanate compounds,
The surface may be treated with a silane compound, a titanate compound, or the like. Addition of flame retardant aid 1 is 0 to 15% by weight, but if no flame retardant is added, it is necessary to add a large amount of flame retardant, so it is preferably 20 to 70% by weight of the flame retardant. It is better to add an auxiliary agent. Further, if the amount added is more than 15% by weight, the decomposition of the resin and compounding agents may be accelerated and the strength of the molded product may be reduced, which is not preferable.

Next, the inorganic filler used in the present invention is preferably blended in order to obtain a molded product with excellent performance such as mechanical strength, heat resistance, dimensional stability (deformation resistance, warping resistance), electrical properties, etc.
Fibrous, powdery, or plate-like fillers are used depending on the purpose.

Examples of fibrous fillers include glass fiber, carbon fiber, silica fiber, silica/alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, titanium potash fiber, stainless steel, aluminum, titanium, copper, brass, etc. Examples include inorganic fibrous materials such as metal fibrous materials. Particularly typical fibrous fillers are glass fibers or carbon fibers.

On the other hand, the powdery fillers include carbon black, silica, quartz powder, glass peas, glass powder, calcium silicate, kaolin, talc, clay, diatomaceous earth, silicates such as wollastonite, iron oxide, titanium oxide, zinc oxide, Examples include metal oxides such as alumina, metal sulfates such as calcium carbonate and barium carbonate, curved silicon, silicon nitride, boron nitride, and various metal powders.

In addition, examples of the plate-like filler include mica, glass flakes, and various metal foils.

These inorganic fillers can be used alone or in combination of two or more. The combined use of fibrous fillers, especially glass fibers, and granular and/or plate-like fillers is a particularly preferred combination in terms of achieving both mechanical strength, dimensional accuracy, electrical properties, and the like.

When using these fillers, it is desirable to use a sizing agent or a surface treatment agent if necessary. Examples of this include functional compounds such as epoxy compounds, silane compounds, incyanate compounds, silane compounds, and titanate compounds. These compounds may be used after surface treatment or focusing treatment, or may be added at the same time when preparing the material.

In the present invention, the amount of inorganic filler added is 0 to 0 per total composition.
It is 50% by weight. If the amount is more than 50% by weight, dispersion will be poor and molding will be difficult, which is not preferable.

In order to impart desired characteristics to the polyester resin composition of the present invention according to its purpose, other additives such as stabilizers, colorants, ultraviolet absorbers, and mold release agents may be added to the extent that their physical properties are not significantly impaired. , antistatic agents, crystallization promoters, crystal nucleating agents, fillers, impact modifiers, etc. can be added.

The composition of the present invention can be easily prepared using known equipment and methods that are generally used for preparing conventional resin compositions. A method for preparing pellets and then molding them; ■ A method for preparing pellets with different compositions, mixing a predetermined amount of the pellets, and molding the pellets to obtain a molded product with the desired composition after molding; Any method can be used, such as a method of directly introducing one or more of the following. Further, it is a preferable method to mix and add a part of the resin component as a fine powder with other components in order to uniformly blend these components.

The flame-retardant polyester resin composition made of PBN of the present invention has high flammability and significantly improved heat-and-moisture resistance than conventional flame-retardant polyester resin compositions made of PBT. Also, when molding, generally PBT is molded into 25
It can be easily molded at temperatures of 0 to 300°C, and
Surprisingly, it has been found that not only does it have less vapor compared to PBT, but it also reduces the amount of white powder that adheres to the mold when continuously molded. As a result, the n-flammable polyester resin composition made of PBN not only provides molded products with excellent moisture and heat resistance, but also improves the continuous productivity of molded products by reducing the frequency of cleaning white powder that adheres to the mold. It can be said that this material is superior to combustible polyester resins and resin compositions made of PBT.

Furthermore, it has superior fluidity compared to when brominated polycarbonate is used as a flame retardant, and can be said to be a material suitable for thin molded products.

Next, the present invention will be further explained with reference to Examples.

The method for measuring the main characteristics is as follows.

(1) Terminal carboxyl group concentration (COOH) A-conics (^, Co old ×) method [HakrolloCh
En 26 226 (1958). Kai is the number of equivalents per 106g.

(2) Intrinsic viscosity Measured in orthochlorophenol 7BH at 35°C.

(3) Combustion Test (UL-94) Underwriters Laboratories Subject 9
4 (UL-94), five test pieces (thickness,
1/32 inch) to test for flammability.

(4) Tensile strength Conforms to ASTM D-638.

(5) Hot water deterioration test A tensile test piece was treated with hot water at 100'C for 2200 hours, and then its strength was measured.

(6) Fluidity Cylinder temperature 270 in accordance with ASTM D1238
The test was conducted at a temperature of 325 g at a temperature of 325 g, and the larger the value, the higher the fluidity.

Example 1 A brominated polystyrene flame release agent was added to PBH having an intrinsic viscosity of 0.79 and a terminal carboxyl group concentration of 40 equivalents/ton in an amount of 12% by weight based on the total composition, and after tri-blending,
It was extruded into pellets using a single screw extruder.

Extrudability was good. Furthermore, a test piece for a tensile test was prepared by injection molding this pellet, and a hot water deterioration test was conducted. In addition, a test piece for a combustion test was prepared in the same manner, and a combustion test was conducted.

The results are shown in Table 1.

Comparative Example 1 The same PBN as in Example 1 was extruded into pellets using a single-screw extruder without adding a flame retardant. Other than that, the test was conducted in the same manner as in Example 1. Extrudability was good.

Comparative Example 2 A test was conducted in the same manner as in Example 1 except that 30% by weight of flame retardant was added.

Comparative Example 3: 20% by weight of flame release agent, 2% of Sbz 03 as combustion aid
The test was conducted in the same manner as in Example 1 except that 0% by weight was added.

From Table 1, it was found that PBN has low flammability when the amount of flame release agent added is less than 0.5% by weight.

Also, if the amount of flame retardant added is more than 25% by weight, or if the amount of flame retardant added is less than 25% by weight but the n-combustion additive is more than 15% by weight, not only will extrudability be poor, but the strength of the molded product will also be low. understood.

(The following is a blank space) Comparative Example 4 A test was conducted in the same manner as in Example 1 except that PBT having an intrinsic viscosity of 1.07 and a terminal carboxyl group concentration of 42 equivalents/ton was used. The results are shown in Table 2.

Comparative Example 5 In Comparative Example 4, the flammability was V-2, and in order to make it 2-0, the amount of flame retardant was increased to 18% by weight. Other than that, the test was conducted in the same manner as in Comparative Example 4.

Extrudability was poor.

Comparative Example 6 A test was conducted in the same manner as in Comparative Example 5 except that PBT having an intrinsic viscosity of 0.88 and a terminal carboxyl group concentration of 17 equivalent jl/ton was used. Extrudability was poor.

From Table 2, the flame-retardant polyester resin composition made of PBN of the present invention has higher flame retardancy and moist heat resistance than the resin composition made of PBT having a similar composition.

Furthermore, when the amount of flame retardant is increased to maintain the same level of flame retardancy, extrudability deteriorates. Furthermore, even if a polymer with a low concentration of terminal carboxyl groups was used as PBT to improve heat and humidity resistance, a sufficient improvement effect could not be obtained.Based on the above, the flame-retardant polyester resin composition of the present invention It is clear that it has excellent heat and humidity resistance.

(The following is a blank space) Example 2 A brominated polystyrene flame retardant was added in an amount of 8% by weight based on the total composition to PBH having an intrinsic viscosity of 0.79 and a terminal carboxyl group concentration of 40 equivalents/ton. Furthermore, as a flame retardant aid, 5
4% by weight of b203 was added. After triblending these, they were extruded into pellets using a single screw extruder. Extrudability was good. Other tests were conducted in the same manner as in Example 1.

The results are shown in Table 3.

Comparative Example 7 A test was conducted in the same manner as in Example 2 except that PBT having an intrinsic viscosity of 1°07 and a terminal carboxyl group concentration of 42 equivalents/ton was used. Extrudability was good.

Comparative Example 8 Since the flame retardance was V-2 in Comparative Example 7, 11% by weight of a flame release agent and 5.5% by weight of a flame retardant aid were added to make it VO. Other than that, the test was conducted in the same manner as in Comparative Example 7.

Comparative Example 9 A test was conducted in the same manner as Comparative Example 8 except that PBT having an intrinsic viscosity of 0.88 and a terminal carboxyl group concentration of 17 equivalents/ton was used. Extrudability was good.

Table 3 shows that even when 5b203 is used not only as a flame retardant but also as a flame retardant aid, the flame retardant polyester resin composition made of PBN of the present invention has a higher resistance than the resin composition made of PBT with the same composition. Highly flame retardant and moist heat resistant. Furthermore, even if the amount of flame retardant added was increased to improve flame retardancy and moist heat resistance, and PBT with a low terminal carboxyl group concentration was used, sufficient improvement effects could not be obtained. From the above, it is clear that the flame-retardant polyester resin composition of the present invention has excellent flame retardancy and moist heat resistance.

(The following is a blank space) Example 3 A brominated polystyrene flame retardant was added in an amount of 8% by weight based on the total composition to PBH having an intrinsic viscosity of 0.79 and a terminal carboxyl group concentration of 40 equivalents/ton. Furthermore, as a flame retardant aid, 5
5% by weight of b20r was added. After triblending these, they were extruded into pellets using a single screw extruder. Extrudability was good. Other tests were conducted in the same manner as in Example 1.

The results are shown in Table 4.

Comparative Example 10 A test was carried out in the same manner as in Example 3, except that PBT having an intrinsic viscosity of 1.07 and a terminal carboxyl group concentration of 42 equivalent jL/ton was used. Extrudability was good.

Comparative Example 11 Since the flame retardance was V-2 in Comparative Example 10, 12% by weight of a flame retardant and 6% by weight of a flame retardant auxiliary agent were added in order to achieve 0. Other than that, the test was conducted in the same manner as Comparative Example 10. Extrudability was good.

Comparative Example 12 A test was conducted in the same manner as Comparative Example 11 except that PBT having an intrinsic viscosity of 0.88 and a terminal carboxyl group concentration of 17 equivalents/ton was used. Extrudability was good.

Table 4 shows that not only when Sbz Oa is used as a flame retardant auxiliary agent, but also when 5b20s is used, the flame retardant polyester resin composition made of PBN of the present invention has a similar composition as the resin made of PBT. It has higher flammability and moist heat resistance than other compositions. In addition, in order to improve flame retardation and moist heat resistance, the amount of flame retardant added was increased, and even if PBT with a low concentration of terminal carboxyl groups was used, sufficient improvement effects were not obtained1.
From the above, it is clear that the flame-retardant polyester resin composition of the present invention has excellent flame retardancy and moist heat resistance.

(The following is a blank space) Example 4 A test was conducted in the same manner as in Example 3 except that 5b2oG.2■20 was used as a combustion aid in an amount of 5.5% fi. Extrudability was good. The results are shown in Table 5.

Example 5 A test was conducted in the same manner as in Example 3 except that 6% by weight of 0.5Na20/Sb20s was used as a combustion aid. Extrudability was good.

Example 6 0.75Na20・5b20. as a combustion aid. The test was conducted in the same manner as in Example 3, except that 6% by weight of . Extrudability was good.

Example 7 A test was conducted in the same manner as in Example 3 except that 6.5% by weight of Na2O.5b205 was used as a combustion aid. Extrudability was good.

From Table 5, not only SbzOs but also xNa can be used as a combustion aid.
20 ・Sb20s-VHzO (x = O ~ 1, y =
It was found that the flame-retardant polyester resin composition of the present invention has excellent flame retardancy and heat-and-moisture resistance even when the compound o to 4) is used.

(Left below) Example 8 Glass chopped strands with a diameter of 10 μm and a length of 3 nn were added in an amount of 30% by weight based on the total composition to PBH having an intrinsic viscosity of 0.79 and a terminal carboxyl group concentration of 40 equivalents/ton. . Brominated polystyrene retardant for all compositions
% by weight was added. In addition, Sb203 was added as a flame retardant aid.
% by weight was added. After triblending these, they were extruded into pellets using a single screw extruder. Extrudability was good.

Other tests were conducted in the same manner as in Example 1. The results are shown in Table 6.

Comparative Example 13 A test was conducted in the same manner as in Example 8 except that PBT having an intrinsic viscosity of 1.07 and a terminal carboxyl group concentration of 42 equivalents/ton was used. Extrudability was good.

Comparative Example 14 Since the flame retardance was V-2 in Comparative Example 13, 9% by weight of a flame retardant and 4.5% by weight of a flame retardant auxiliary agent were added in order to achieve 0. Other than that, the test was conducted in the same manner as Comparative Example 13. Extrudability was good.

Comparative Example 15 A test was conducted in the same manner as Comparative Example 14 except that PBT having an intrinsic viscosity of 0.88 and a terminal carboxyl group concentration of 17 equivalents/ton was used. Extrudability was good.

Comparative Example 16 A test was conducted in the same manner as in Example 8 except that 55% by weight of glass fiber, 3% by weight of a flame retardant, and 2% by weight of a flame retardant aid were added. Extrudability was poor.

Table 6 shows that even when glass fiber is used as an inorganic filler, the flame retardant polyester resin composition made of PBN of the present invention has higher flame retardancy and moist heat resistance than a resin composition made of PBT with a similar composition. I understand that. Further, in order to improve flame release properties and moist heat resistance, the amount of flame release agent added was increased, and even if PBT with a low terminal carboxyl group concentration was used, sufficient improvement effects could not be obtained. From the above, it is clear that the flame-retardant polyester resin composition of the present invention has excellent flame retardancy and moist heat resistance.

Furthermore, if more than 50% by weight of glass fiber is added as a filler, the extrudability will deteriorate, so the amount added should be 50% by weight or less, or less.

Example 9 A brominated polystyrene retardant was added to PBT having an intrinsic viscosity of 0.79 and a terminal carboxyl group concentration of 40 equivalents/ton in an amount of 9% by weight based on the total composition. Furthermore, as a combustion aid, 5
4.5% by weight of b203 was added. After triblending these, they were extruded into pellets using a single screw extruder. Extrudability was good. 270℃ using pellets, load 32
Melt flow rate was measured at 5 g. Other tests were conducted in the same manner as in Example 1. The results are shown in Table 7.

Comparative Example 17 A test was conducted in the same manner as in Example 9, except that brominated bisphenol A type polycarbonate retardant was used in an amount of 9% by weight based on the total composition. Extrudability was good.

From Table 7, it was found that the fluidity was higher when brominated polystyrene was used as in the present invention than when brominated bisphenol A type polycarbonate was used as a flame retardant. From this, it is clear that the flame-retardant polyester resin composition of the present invention is excellent not only in flame-retardant properties and heat-and-moisture resistance but also in fluidity, and is particularly suitable for small, thin-walled parts.

(Blank below) Procedural Amendment 1990 Special Remarks To the Commissioner of the Agency 1, New Patent Application No. 2002 2, Title of Invention: Flammable Polyester Resin Composition August 2/I Patent Claims + 1) A) Polybutylene naphthalene dicarboxylate 30-99.5% by weight, (B)
Brominated borinutylene flammability agent 0.5-25% by weight, (C) Sb203 and xNaz O-Sb205.
V) 0-15% by weight of at least one type of auxiliary combustion agent selected from the group of 12° (×-〇~1.V=O~4), and (D) 0-50% by weight of an inorganic filler. Flame-retardant polyester resin composition (2) consisting of polybutylene naphthalene dicarboxylate containing polybutylene-2,6
- The flame retardant polyester resin composition according to claim 1, which is naphthalene dicarboxylate.

Claims (2)

[Claims] (1) (A) 30-99.5% by weight of polybutylene naphthalene dicarboxylate, (B) 0.5-25% by weight of brominated epoxy flame retardant, (C) Sb_2O_3 and xNa_2O・Sb_2O
0 to 15% by weight of at least one flame retardant aid selected from the group of _5・yH_2O (x = 0 to 1, y = 0 to 4), and (D) 0 to 50% by weight of an inorganic filler, Flame retardant polyester resin composition (2) The flame-retardant polyester resin composition according to claim 1, wherein the polybutylene naphthalene dicarboxylate is polybutylene-2,6-naphthalene dicarboxylate.