JPS5930856A - Polyester resin composition - Google Patents

Abstract

PURPOSE:The titled flame-retardant composition having improved heat distortion properties and hydrolysis resistance free from bleeding of frame-retardant, obtained by blending a thermoplastic polyester with brominated polycarbonate, brominated epoxy resin, inorganic flame-retardant auxiliary, etc. CONSTITUTION:100pts.wt. thermoplastic polyester consisting of terephthalic acid or its ester and 2-4C glycol as main components is blended with 3- 50pts.wt. flame-retardant consisting of a low-molecular-weight brominated polycarbonate shown by the formula I (m is 1-4; n is 2-15; R1 is 1-5C lower alkyl), having end groups hindered with alkylphenols and 2-15 polymerization degree, and a brominated epoxy resin shown by the formula II (Z is H, or methyl; l<10), having <=10 polymerization degree, in a molar ratio of (90-50)/ (10-50), and 0.1-20pts.wt. inorganic flame-retardant auxiliary (e.g., especially antimony trioxide, etc.). The addition of 0-150pts.wt. reforcing filler (e.g., glass fiber, etc.) improves further mechanical strength and heat resistance.

Description

[Detailed description of the invention]

The present invention relates to flame-retardant polyester resin compositions. More specifically, the combination of a specific flame retardant improves heat resistance and mechanical properties! The present invention provides a composition with excellent t1 degree and hydrolysis resistance. Thermoplastic aromatic polyesters such as polybutylene terephthalate (hereinafter abbreviated as PBT) have excellent chemical resistance, mechanical properties, electrical and physical properties, as well as heat resistance, moldability, dimensional stability, etc. It is used in a wide variety of ways as a molding material. It is also known that when PBT is mixed with a reinforcing filler such as glass fiber, mechanical strength and heat resistance are dramatically improved. However, once PBT is ignited, it does not extinguish even if the fire source is removed and burns gradually. This is a fatal flaw from a fire safety perspective, and its use is prohibited, especially in applications in the electrical and communication equipment fields. I can't. Therefore, for the purpose of imparting release properties to PUT, organic halogen compounds such as hexabromobenzene and decabromo biphenyl ether are added, and reactive flame retardants such as tetrabromophthalic anhydride are added to the raw material components. A method of incorporating PBT into the skeleton by reaction has been carried out. However, products containing such organic halogen compounds have poor appearance because the organic halogen compounds bleed onto the surface of the molded product at high temperatures, and have poor moldability due to 1li4 thermal properties. It also has the disadvantage of yellowing and discoloration. In addition, electricity,
In the field of i-devices, its application is limited due to the deterioration of electrical properties under high temperature and high humidity conditions. As a result of intensive research, the present inventors have improved the bleed of the flame retardant, improved thermal deformability such as heat resistance stability and solder resistance, and in addition, developed a mechanical material with excellent hydrolysis resistance (moisture resistance). The present inventors have discovered a polyester composition with high strength and release properties, and have completed the present invention. That is, the present invention provides 100 parts by weight of a thermoplastic polyester formed mainly of terephthalic acid or its ester and glycol having 2 to 4 carbon atoms, with a polymerization degree of 2 to 15, the terminals of which are capped with alkylphenol. The ratio (A)/(B) of the low molecular weight brominated polycarbonate (A) and the brominated epoxy resin (B) with a degree of polymerization of 10 or less is 90.
~50/10-50 parts by weight of a flame retardant, 0.1 to 20 parts by weight of an inorganic combustion aid, and 0 to 150 parts by weight of a reinforcing filler.
This invention relates to a polyester resin composition with a heavy background area. The end-blocked low molecular weight brominated polycarbonate (8) used in the present invention is represented by the following general formula. (In the formula, nl represents an integer of 1 to 4, n represents 2 to 15, and 1?+ does not represent a lower argyl group having 1 to 5 carbon atoms.) Such an end-capped brominated polycarbonate For example, dissolve monofunctional alkylphenol into tetrabromobisphenol by adding a 10% aqueous solution of caustic soda and methylene chloride, blow in phosgene while keeping pl+ around 12 at a temperature of 20 to 30 °C, and after the blowing of phosgene is finished. , 30% trimethylamine added, 2
After finishing the reaction by keeping it at 0-30℃ for 1 hour, purification,
Obtained by separation. As monofunctional alkylphenols, p-tertbutylphenol and other lower alkylphenols are used. It is known that brominated polycarbonates with a degree of polymerization of 16 or higher are used as combustible components, but as polycarbonate increases in viscosity as the degree of polymerization increases, it is difficult to handle it as a flame retardant. difficult and impractical. Furthermore, the brominated epoxy resin (B
) is represented by the following general formula. (In the formula, Z is hydrogen or a methyl group, and ■ is an integer of 10 or less.) Such brominated epoxy resins are generally obtained by condensation of brominated bisphenol A and epichlorohydrin, For example, it can be easily obtained by heating tetrabromobisphenol A diglycidyl ether and tetrabromobisphenol 8 to 80 to 250°C in the presence of a catalyst. In the present invention, it is necessary to set the usage ratio of the pre-separation component (A)/(B> to 90-50/10-50, and when the amount of B) used relative to (A) increases, At a temperature of 230 to 270° C., which is the pre-molding temperature of polyester, the brominated epoxy oil becomes three-dimensional and crosslinks, increasing the melt viscosity of the resin, making it difficult to mold. On the other hand (I
If the amount of 3) used is too small, the effects of mechanical strength and moisture resistance cannot be obtained. The amount of flame retardant used is 5 parts by weight per 100 parts by weight of polyester.
-60 parts by weight, preferably 10-50 parts by weight. As the flame retardant aid used to achieve the flame retardant effect, any of those known to be used in this type of polyester composition are effective, but inorganic compounds of the VB group are suitable, including antimony, Compounds of arsenic, phosphorus, and bismuth are used. Preferred for use are antimony dioxide, antimony tetroxide, antimony pentoxide, sodium pyroantimonate,
They are arsenic oxide, bismuth oxide, and phosphorus compounds. Also used are dirheconium oxide, tin oxide, boric acid compounds, and molybdenum compounds. In particular, antimony compounds such as antimony trioxide are preferred. The amount used is 0.5 to 30 parts by weight, preferably 2 to 20 parts by weight, per 100 parts by weight of polyester. The thermoplastic polyester targeted by the present invention includes terephthalic acid or a terephthalic acid alkyl ester and a carbon number of 2 to 4.
It is a polyalkylene terephthalate consisting of glycol. Glycol components include ethylene glycol, 1.3-propylene glycol, 1.4-butanediol, 1,2-propylene glycol, and 1.3-propylene glycol.
-butanediol and 1,2-butanediol are used. A part of the acid component and/or glycol component of the polyester can be replaced with other dicarboxylic acids and/or other glycols, each of which accounts for 40 mol% of the main raw material.
You can replace up to Other dicarboxylic acids include phthalic acid, isophthalic acid,
Naphthalene dicarboxylic acid, adipic acid, sebacic acid, etc. Other glycols other than the main raw materials include ethylene glycol, 1,3-propylene glycol,
．． Examples include 2-propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol or 1,6-hexanediol, and cyclohexanedimethanol. Also, it is a polyester made from terephthalic acid or its alkyl ester and glycol such as ethylene glycol or 1,4-butanediol, most of which have both terminal groups as hydroxyl groups and have a molecular weight of 3,000 to 3,000.
20,000 and a polyester urethane obtained by reacting a polyfunctional incyanate with a hydroxyl value of 40 to 5 can also be used as a subject of the present invention. Furthermore, the present invention can be applied even if the remaining 40% by weight or less of 100 parts by weight of polyester is replaced with other organic polymers. For example, polyolefin, borisdylene, ΔS1ΔB
S, acrylic resin, vinyl acetate resin, polyester cetal, polycarbonate, polysulfone, polyphenylene oxide, various nylons, polyurethanes, ethylene-vinyl acetate copolymers, other saturated polyesters, and other thermoplastic resins can be substituted. The mechanical strength and heat resistance of the polyester resin composition of the present invention can be further improved by adding a filler. Examples of such reinforcing fillers include glass fibers, carbon glass beads, glass powder, and the like. The glass fibers used in the present invention are preferably treated with a strength/knobbling agent of the vinyl silane, aminosilane, or epoxy silane type, and are used in the form of roving glass or chopped strands. glass peas,
It is preferable that the glass powder is also treated with a similar coupling agent. Reinforcing fillers can be used in amounts up to 150 parts by weight per 100 parts by weight of polyester. The amount of reinforcing filler is 1
If it exceeds 50 parts by weight, the moldability of the composition will be poor, which is not preferable. The composition of the present invention may contain other additives such as crystal nucleating agents, pigments, dyes, plasticizers, mold release agents, lubricants, heat stabilizers, antioxidants, ultraviolet absorbers, blowing agents, coupling agents, etc. It may be added or a flame retardant other than those mentioned above may be used in combination. The method for obtaining the composition of the present invention includes adding a flame release agent during or after polymerization of polyester and uniformly melt-mixing the polyester.
Method of adding flame release aid and reinforcing filler: After uniformly melting and mixing molten polyester and flame release agent, cooling, solidifying, and pulverizing the obtained granules and combustion release aid, if necessary, "C reinforcement" There are various known methods, such as kneading the filler with an extruder, or mixing all of the polyester pellets, flame retardant, combustion aid, and reinforcing filler uniformly at room temperature and then heating with an extruder. Also applicable. Melt mixing or mixing in an extruder at 180-300°C, preferably 180-250°C.
The appropriate mixing time is 0.2 to 30 minutes. Prolonging the mixing time at high temperatures tends to cause decomposition of the flame retardant, so care must be taken. The thus obtained flame-retardant polyester resin composition of the present invention has no bleeding of the flame retardant, has excellent moldability, and has particularly excellent various mechanical properties and hydrolysis resistance (moisture resistance). There is. In each of the following examples, the dielectric breakdown voltage after hydrolysis promotion treatment, which represents moisture resistance, was determined by subjecting a test piece of one fin thickness prepared in advance to a steam pressure of 124°C/2.3 kg/cl. The dielectric breakdown voltage was measured after 10 hours after being placed in a pot and expressed as PCT/1011. The PCT/101r of the compositions of the present invention measured in this manner is all 24 KV/dragon or higher, which is extremely excellent. Decrease in fluidity during injection molding has a large effect on molding processability, especially during continuous molding.
However, the major feature of the polyester resin composition of the present invention is that while it has the above-mentioned moisture resistance properties, its fluidity stability is not impaired in the slightest. . In each of the following examples, melt index (Ml) was used to measure flow stability. The test method measures the amount of material filled in a cylinder with a set temperature of 265°C that flows out of an orifice of 1 dragon diameter and 10 lengths within a certain time under a load of 2160 gr. Therefore, the larger the Ml, the higher the fluidity, and the smaller the MI, the worse the fluidity L). Here, Ml was measured when the material was allowed to stay in the cylinder for 20 minutes and 30 minutes, respectively. As the residence time increases, Ml decreases, which indicates that the fluidity decreases, which is a disadvantage in terms of injection molding. The present invention will be explained in detail below with reference to Examples. OR in each example
and % represent parts by weight and % by weight, respectively, and volume 1 is in the relationship of 1 to parts by weight. Reference Th+'tr end-capped brominated polycar Δ

[Synthesis of Nate] To 54.4 parts (0.1 mol) of tetrabromobisphenol Δ, 6 parts (0.04 mol) of p-tert-butylphenol, add 300 parts of an aqueous solution of 10~caustic soda and 200 parts of meg-lene chloride to jJI+ 25 parts (0.25 mol) of phosgene was added to the mixture while stirring at a temperature of 20°C and a pH of 11 to 12.
Added 25 parts by volume of 0% trimethylamine aqueous solution (1) and kept at 20°C to 30°C for 30 minutes to 1 hour. After the reaction was completed, the aqueous layer was removed for 5 minutes, and the meg-lene chloride layer was washed with water.Next Then, water was added thereto and methylene chloride was distilled off by heating.The product was washed with water and dried. The obtained product has a degree of polymerization of 5, a softening point of 235°C, and a bromine content of 52
．． It was 7% end-capped odorless, II IJ carbonate. Hereinafter, this will be abbreviated as FR-PC. Reference Example 2 [Synthesis of brominated epoxy resin] Tetrabromobisphenol A diglycidyl ether (epoxy equivalent:
370) 11], 1L tetrabromobisphenol A3
44 parts and 1.6 parts of a 10% aqueous solution of tetramethylene ammonium chloride were charged into a flask (tetrabromobisphenol A diglycidyl ether/tetrabromobisphenol A, = 3/2 molar ratio) 150
'C, then gradually raised the temperature to 190t after 4 hours.
The temperature was kept at 190°C for 2 hours. After the reaction is completed, the product cooled and solidified is abbreviated as FR-Ep. Example 1 8 parts of polyethylene terephthalate [η)=0.8 obtained by polycondensation of dimedyl terephthalate and 1,4-butanediol according to a known method, FR-P of Reference Example 1
3 parts of Cl, 4 parts of FR-89 of Reference Example 2, and 3 parts of antimony dioxide were uniformly premixed. The premix was supplied to a 651-inch full-flight extruder with a vent heated to 250°C, and after being plasticized and kneaded, it was cooled and taken out in the form of a belent. A test piece with a thickness of 716 inches was made from this pellet, and its flammability was measured based on Subject 94 of Underwriters Laboratories of the United States, and it met the V-0 standard. Also, the dielectric breakdown voltage was initially 2
9 K V/u+, whereas PCT/IO
In H it was 25 K V/ma. Ml at 265° C. was 35 g/10 min for 10 minutes, 37 g/10 min for 20 minutes, and 40 g/10 min for 30 minutes, and no decrease in fluidity was observed. Comparative Example 1 A flammable PBT composition prepared in the same manner as in Example 1 except that 18 parts of FR-PC alone was used instead of 3 parts of FR-PCl and 4 parts of FR-894 in Example 1. A test similar to 1 was conducted. ? Regarding Li flammability and fluidity, almost the same results as Example 1 were obtained, but in terms of dielectric breakdown voltage, PCT/10II was IIKV/II
A significant decrease was observed. Example 2 52 parts of PUT used in Example 1, FR-PCl3
After homogeneously premixing 30 parts of Chiro-Nobutt strand type glass fiber treated with an aminosilane coupling agent in addition to 1 part of FR-EpU and 3 parts of antimony trioxide, reinforcing filling was performed in the same manner as in Example 1. PUT containing material
A test piece of the composition was prepared. As a result of measurement, PCT/IO
The decrease in dielectric breakdown voltage at Ml after 30 minutes residence also
Flame-retardant PUT with extremely high practical value, with no decrease in
It was confirmed that it was a composition. Example 3 In Example 2, the amount of F R-P C used was 10 parts, F
l? One pellet of the I'BT composition was given in the same manner as in Example 2, except that -Ep was used in an amount of 5 parts. It exhibited excellent properties in terms of both MΔ edge breakdown voltage and fluidity. Example 4 In Example 2, the amount of FR-PC used was 8 parts, FR-E
A pellet of a combustible PBT composition was obtained in the same manner as in Example σ2 except that the amount of P used was 7 parts. It is recognized that both dielectric breakdown voltage and fluidity are sufficiently practical. Comparative Examples 2 to 4 The usage amounts of FR-1) C and FR-IEp in Example 2 were changed to Fl'? -PCFR-Ep Comparative Example 2 A pellet of a combustible PBT composition was obtained in the same manner as in Example 2, except that 15 parts O part 3 0 15 4 3 12. In the composition according to Comparative Example 2, although no decrease in fluidity was observed, a significant decrease in dielectric breakdown tr1 pressure in PCT/1011 was observed. Compositions according to Comparative Examples 3 and 4)
Although a decrease in dielectric breakdown voltage cannot be overlooked, 265
℃G I'm watching Mu. Og/10 after staying for 30 minutes.
After a few minutes, it stopped flowing at all. This is thought to be due to the three-dimensional nature of the brominated epoxy. The practicality as a molding resin is extremely low (λ). Example 5 Instead of polybutylene terephthalate used in Example 2 (
This [η)=1. A pellet of a flame-retardant polyethylene terephthalate composition was obtained using polyethylene terephthalate (ffi) in the same manner as in Example 2.The dielectric breakdown voltage and fluidity were both highly practical. Table 1 summarizes the physical property values measured in each Example and Comparative Example.

Claims (1)

[Claims] Low molecular weight brominated polycarbonate with a polymerization degree of 2 to 15 and terminal-capped with alkylphenol is added to 100 parts by weight of a thermoplastic polyester formed mainly of terephthalic acid or its ester and glycol having 2 to 4 carbon atoms. Δ) and brominated epoxy cedar 1 fat with a degree of polymerization of 10 or less (B) <7) Ratio (A)/(B) 90 to 5o/1
A polyester resin composition containing 3 to 50 parts by weight of an o-5o Theal JII refueling agent, 0.1 to 20 parts by weight of an inorganic combustion aid, and 0 to 150 parts by weight of a reinforcing filler.