JPS591420B2 - Flame retardant polyester composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame-retardant polyester composition, and its purpose is to blend a specific amount of a halogen-containing aromatic polycarbonate having a specific structure and an organic crystallization accelerator having a specific structure into a polyester. The object of the present invention is to provide a flame-retardant polyester composition which has improved low-temperature moldability and has excellent flame retardancy and physical properties.

In recent years, the use of plastics in fields such as electrical equipment parts, automobile parts, and building materials has gradually increased, and the plastics used in these fields meet the UL standard JfO. 94 (Und.
erwrllersLabO. nc. Bulletin
A high degree of flame retardancy as shown in U-94) is required.

Polyethylene terephthalate is useful as a molding material due to its excellent mechanical properties, electrical properties, thermal properties, chemical resistance, etc., but it is also flammable, and molded products with excellent dimensional stability under heat can be obtained. However, the field of application is severely limited due to drawbacks such as the need for molding in high-temperature molds, and improvement of flame retardance and moldability has become a major issue. For flame retardation of combustible resins, methods of copolymerizing halogen-containing compounds, phosphorus-containing compounds, etc., methods of blending these compounds, and the like are known.

However, when such a method is used for a resin with a high melting temperature such as polyester, not only is the compound itself required to have high thermal stability, but also copolymerization and blending may cause the polyester to be colored or deteriorate in physical properties. It is necessary that this does not occur. When flame retardants with active groups such as hydroxyl and carboxyl groups are added to polyester, the viscosity of the polyester decreases significantly, and halogenated aromatic compounds generally sublime easily, resulting in white powder adhering to the mold surface during injection molding. This has the drawback of contaminating the mold and deteriorating the appearance of the molded product. In addition, many flame retardants have poor heat resistance, which leads to decomposition due to high temperature retention during melt molding, resulting in coloring of molded products and deterioration of physical properties, which poses a major problem in industrialization in that stable molded products cannot always be obtained. are doing. Furthermore, due to the special crystallization behavior of polyethylene terephthalate, special molding conditions such as a mold temperature of 14°C or higher may be required to obtain a molded product with excellent heat resistance, dimensional stability, surface gloss, etc. The use of polyester for molding purposes is restricted. It is also known that crystallization can be promoted by adding solid inorganic fillers such as talc and clay, and organic compounds such as fatty acid metal salts and organic acid esters, but even if large amounts of these compounds are added, The drop in crystallization initiation temperature is at most about 10'C, and it is impossible to obtain a molded product with excellent dimensional stability, heat resistance, and surface gloss by lowering the mold temperature to 100°C or less. .
The present inventors have conducted extensive research into polyester compositions that do not have disadvantages such as coloration or deterioration of physical properties, and can be molded in low-temperature molds to yield molded products with excellent heat resistance, dimensional stability, surface gloss, etc. As a result, the composition of the present invention was achieved. That is, the present invention uses polyethylene terephthalate or 80
% or more of ethylene terephthalate repeating units, (a) containing 25% by weight or more of an aromatic polycarbonate having repeating units represented by the following general formula [I] and/or units represented by the general formula [1] Aromatic copolycarbonate 5 to 50 weight? and(
b) A flame-retardant polyester composition containing 0.1 to 15% by weight of an organic crystallization accelerator having a polyoxyalkylene chain and an epoxy group. Furthermore, a flame-retardant polyester composition is prepared by adding 1 to 100% by weight of a solid inorganic filler and/or a fibrous reinforcing agent to the polyester. , concerning. [However, in the formula, X1, X2: bromine atom and/or chlorine atom, p, q: an integer of 1 to 4,
n: an integer of 2 to 4, r, t: an integer of 0 or 1 to 20, Y: alkylene group, halogenated alkylene group, alkylidene group, -O-, -CO-, -S-, -SO-, - S
O2- or - (two benzene rings directly bonded)] The fabric of the present invention has significantly improved moldability by incorporating a specific organic crystallization promoter, and can be molded at a low mold temperature of 70 to 100°C. The molded product has excellent mold releasability and surface properties, and the resulting molded product has excellent thermal dimensional stability even when exposed to a high temperature atmosphere of 100'C or higher.

In addition, certain flame retardants have good heat resistance, and even if molding has to be temporarily stopped, they may cause coloring of the molded product.
It has the characteristic that a molded article having stable and excellent flame retardance and physical properties can be obtained without causing any deterioration in physical properties. In a composition containing a solid inorganic filler, flame retardancy can be obtained with a relatively small amount of flame retardant, and fine and high crystallinity can be obtained through a synergistic effect with an organic crystallization accelerator. It is also possible to obtain molded products with excellent physical properties. Furthermore, since the surface gloss is good and stable, molded products with stable color tone can always be obtained even in products colored with dyes and pigments, which is advantageous in terms of quality. The reason why the composition of the present invention exhibits excellent moldability, flame retardancy, and physical properties is not only because the flame retardant used has excellent heat resistance, but also because the polyoxyalkylene chain of the organic crystallization promoter is a polyester glycol. It activates the mobility of the parts and promotes the crystallization of the surface layer of the molded product, and it also causes at least a partial reaction between the polyester and the epoxy groups to improve the molecular orientation of the polyester in the mold during injection molding. This is thought to be due to the fact that the organic crystallization promoter improves the dispersibility of the flame retardant in the polyester, distributes the flame retardant uniformly, and improves the affinity between both the polyester and the flame retardant.

The improvement in moldability can significantly shorten the molding cycle time in molding using conventional high-temperature molds.
The polyester used in the present invention is polyethylene terephthalene or a copolymerized polyester containing at least 80% or more, preferably 90% or more of ethylene terephthalene repeating units.

As the copolymerization component, acid components and/or glycol components can be widely used. For example, acid components include isophthalic acid, naphthalene dicarboxylic acid, diphenyl ether dicarboxylic acid, adipic acid, sebacic acid, etc.; glycol components include propylene glycol, butylene glycol,
Examples include diethylene glycol, neopentyl glycol, cyclohexanedimethanol, and 2,2-bis(4-hydroxyphenyl)propane. It is also possible to copolymerize oxyacids such as p-oxybenzoic acid and p-hydroxyethoxybenzoic acid. Polyester can be produced by a normal production method, using a phenol/tetrachloroethane mixed solvent (6/4 weight ratio) solution.
It is preferable that the intrinsic viscosity measured at °C is 0.5 or more, and particularly preferably 0.55 or more. However, the polyester may be partially branched as long as the moldability is not impaired. Further, the flame retardant used in the present invention is an aromatic polycarbonate having a repeating unit represented by the following general formula [I] or 25% by weight or more of the units represented by the general formula [I] and the remaining units are divalent phenol. It is an aromatic copolycarbonate composed of polybasic acid units, glycols, and/or polybasic acid units.

[However, the formula Xl, X2: bromine atom and/or chlorine atom, P, q: an integer of 1 to 4, n: an integer of 2 to 4, R,
t: 0 or an integer of 1 to 20, Y: alkylene group, halogenated alkylene group, alkylidene group, -0- -CO
-, -S-, -SO-SO2- or - (two benzene rings are directly bonded)] The flame retardant is usually a halogenated bisphenol or its alkylene oxide adduct with phosgeso or (or other carbonate) Either apply a precursor or
It can be produced by co-reaction by further adding halogen-free dihydric phenols, glycols, dibasic acid chlorides, phosphorus oxyhalides, phosphorus halides, etc. to the above composition.

During the reaction, if desired, an organic monohydric alcohol or monohydric phenol may be present to control the degree of polymerization by chain termination reaction. The number of repeating units is 2 or more, preferably 5 to 50, more preferably more than 10 and 16
The range is less than or equal to If the number of repeating units is 2, the melting point will be low and the heat resistance of the polyester will be lowered, while if it is too large, uniform blending will be difficult and physical properties will deteriorate. Is the amount of polycarbonate blended 5 to 50 times the amount of polyester? And preferably 10 to 30 cars? It is. If the weight is less than 50%, the flame retardancy is insufficient;
If the weight exceeds 7), it may cause problems such as sludge, coloring, deterioration of physical properties, and high cost.

It is preferable to use an antimony compound as an auxiliary agent in combination with the flame retardant of the present invention.

Antimony compounds that can be used include a wide range of inorganic and organic antimony compounds. Inorganic antimony compounds such as antimony trioxide, antimony phosphate, Sb-caproate, S
Organic antimony compounds such as b-polymethylene glycolate, triphenyl antimony are preferred, and antimony trioxide is particularly preferred. The amount used is usually 50 weight per flame retardant? or less, preferably 10 to 40
weight? It is. 10% by weight for polyester
It is preferable that it is below. The organic crystallization promoter used in the present invention is a compound having at least one polyoxyalkylene chain and at least one epoxy group in the molecule, preferably polyoxyalkylene glycol having a molecular weight of 5000 or less. mono- or polyglycidyl ethers of

Polyoxyalkylene glycols include polyethylene glycol, polypropylene glycol, polybutylene glycol, polyethylene glycol, polypropylene glycol copolymer, polyethylene glycol/polytetramethylene glycol copolymer, neopentyl glycol/alkylene oxide adduct, pentaerythritol/alkylene oxide Examples include adducts, polyethylene glycol monomethyl ether, polypropylene glycol monoethyl ether, and the like. The molecular weight of the polyoxyalkylene glycol is more preferably from 150 to 3,000, particularly preferably from 200 to 1,500. If the molecular weight is too high, the coexistence with polyester will decrease and the crystallization promoting effect will be lost. Further, it is particularly preferable that the compound has an average of 1.2 or more engineered poxy groups in the molecule. Historically, polyoxyalkylene glycol and polyepoxy compounds such as ethylene glycol diglycidyl ether and butanediol glycidyl ether are used together,
It may be a combination of compounds that produces a compound having a polyoxyalkylene chain and an epoxy group during kneading or molding. The blending amount of the organic crystallization promoter is usually 0.1 to 15% by weight, preferably 1 to 15% by weight based on the polyester.
10 weight? If it is less than 0.1% by mass, the improvement in moldability, surface properties and physical properties of the molded product are insignificant;
Moreover, if it exceeds 15% by weight, gelation may occur during molding, and physical properties may deteriorate. Historically, by incorporating a solid inorganic filler and/or a fibrous reinforcing agent into the composition of the present invention, a molded article having further improved physical properties can be obtained.

Solid inorganic fillers include talc, clay, kaolin,
Examples include silicates such as mica and asbestos, silica, and gypsum, with silicates being preferred, and talc being particularly preferred. The particle size of the solid inorganic filler is 80μ or less, preferably 15μ or less. Examples of the fibrous reinforcing agent include glass fibers, carbon fibers, metal carbide fibers, metal nitride fibers, whiskers, etc. Glass fibers are particularly preferred, and the diameter thereof is preferably 3 to 30 microns. Is the amount of solid inorganic filler and/or fibrous reinforcing agent blended 1 to 100% by weight based on polyester? and preferably 5 to 100% by weight, more preferably 10% by weight.
~80 weight? It is. Also, is the amount of solid inorganic filler blended 5 to 50% by weight based on polyester? is preferable, and more preferably 1
Particularly preferred is 0 to 40 weight. Further, the amount of the fibrous reinforcing agent added is preferably 5 to 50% by weight based on the polyester. By adding a solid inorganic filler, the thermal properties and dimensional stability of the molded product can be further improved, and the melting of ignitable materials can be improved. Since dripping is prevented and flame retardance can be further improved, the amount of flame retardant added can be reduced, and a flame retardant and heat resistant molding material with even greater strength can be provided. Furthermore, the impact strength and heat distortion temperature of the molded article can be improved by adding a fiber reinforcement agent. Furthermore, if desired, a mold release agent may be added to the composition of the present invention to further improve moldability.

Particularly preferred release agents include esters of higher fatty acids and metal salts of higher fatty acids, such as sodium stearate, magnesium stearate, calcium stearate, calcium montanate, and montanic acid esters. Is the blending amount 10% by weight of polyester? or less, preferably 0.01 to 3 weight? It is. The method for producing the composition of the present invention is not particularly limited, and any method may be used.

For example, polyester and all other components are mixed in advance and compounded using an extruder, or polyester and all components except the fibrous reinforcing agent are mixed and fed into an extruder, and the melt is poured around glass roping, etc. After coating, cooling and cutting into suitable lengths, the so-called wire coating method, wax fiber reinforcement extraction and/or addition of solid inorganic fillers during or after the polymerization of the polyester, to which all other compositions are added. Examples include a method of mixing a polyester chip containing a flame retardant and a method of kneading a polyester chip containing an organic crystallization accelerator/strengthening agent. It is also possible to mix the entire composition and mold it directly. In any case, the mixing method, mixing time, etc. may be arbitrary. Depending on the use and purpose, the composition of the present invention may contain stabilizers for polyester and flame retardants, such as antioxidants and ultraviolet absorbers, as well as plasticizers, lubricants, antistatic agents, antifouling agents, etc.
Additives such as colorants, impact-modifying rubbery substances, and flame retardants other than those of the present invention may also be included.

The composition thus obtained provides molded products with excellent moldability and surface properties not only in high-temperature molds but also in low-temperature molds, so it is suitable for various molded parts, sheet-like products, and tubes. It can be widely used for molding objects, laminates, various containers, etc., but considering its excellent flame retardancy, heat resistance, and electric resistance, it is particularly suitable for molding electrical parts, automobile parts, etc.

The present invention will be explained below with reference to Examples. In addition, parts and percentages in the synthesis examples and examples are based on weight unless otherwise specified. In addition, the molding of the test pieces and various evaluations of the obtained molded products in the examples were conducted according to the following methods. (1) Molding of test piece Predetermined amounts of polyethylene terephthalate (intrinsic viscosity 0.60, melting point 264°C) and other compounding agents were weighed and mixed in a tumble blender.

Next, this was put into the hopper of a 40m111φ vented extruder, and the cylinder temperature (from the hopper side) was 250-
Compound chips of each composition were produced by melt-kneading at 275-280°C. 1 of the obtained compound chips
2. After drying under reduced pressure for 4 hours, each test piece was molded using an injection molding machine. The molding machine used was a Nippon Steel Ankelberg model N-95, and the molding conditions were a cylinder temperature of 270-265-
Molding was carried out at 275° C., mold temperature 85° C., injection holding time 12 seconds, cooling time 15 seconds, and injection pressure 35 to 80 k/Cd. (2) Flame retardancy A 1/16 inch x 1/2 inch x 5 inch test piece was molded and tested for flammability based on the UL-94 test method.

V-0 acceptance criteria: Satisfy all of the following requirements.

a: The burning time of all test pieces after contact with the flame was within 10 seconds.

b: The total burning time after 10 times of flame contact with 1 set of 5 pieces is 5
Within 0 seconds.

c: There is no combustion or residue up to the clamp.

d: Do not drop flaming particles that will ignite the cotton below 12 inches.

e: The residue after removing the second flame is within 30 hours.

(3) Mold releasability, surface characteristics of molded products Judgments were made based on mold separation and spool slippage when molding a disk with a diameter of 100 mm and a thickness of 3 mm.

In addition, the surface characteristics were judged by the surface gloss and flow pattern of the disc. ◎・・・Very good ●・・・Good △・・・
Fairly good X...poor XX...extremely poor (4)
Thermal deformation consistency measured according to ASTM D-648, with a test piece thickness of 1/8 inch and a load of 18.6 mm/C77i.

(5) Heat shrinkage rate Diameter: 100mf Then, it was calculated using the following formula.

(6) Synthesis example of flame retardant 1 544 parts of tetrapromobisphenol A and p-Te
3,000 parts of a 10% aqueous sodium hydroxide solution and 2,000 parts of 1-hymethylene salt were added and dissolved in 24 parts of rt-butylphenol, and while maintaining the temperature at 25±5°C and the pH at about 12, phosgene ganic acid was added. Approximately 300 copies were published.

After the blowing was completed, 2.5 ml of 30% triethylamine aqueous solution was added as a catalyst and reacted at 20 to 30°C for 2 hours.
After the reaction was completed, the methylene chloride layer was separated, thoroughly washed with water, and then poured into 10 times the weight of methanol to precipitate the product.Then, the precipitate was filter-dried to obtain a white powder product. Ta. The aromatic polycarbonate thus obtained had an average number of repeating units of about 14, a softening point of about 260° C., and a bromine content of 53.6%. Synthesis Example 2 Tetrapromobisphenol A and bisphenol A were used instead of tetrapromobisphenol A in Synthesis Example 1.
Synthesis Example 1 was repeated except that 1 mol of a 75:25 molar ratio mixture of 1 mol and 0.16 mol of tripromophenol was used instead of p-tert-butylphenol, with a bromine content of 511%, a molecular weight of about 8000, Softening point is approximately 250'C
An aromatic copolycarbonate was obtained.

Synthesis Example 3 An aromatic polycarbonate was obtained in the same manner as in Synthesis Example 1 except that 1 mole of the ethylene oxide adduct of tetrapromobisphenol A (molecular weight approximately 1000) was used instead of tetrapromobisphenol A in Synthesis Example 1. Ta.

Synthesis Example 4 For 1 mole of tetrapromobisphenol A, p-T
The repeating unit was about 5 on average (
Softening point: approx. 23'C), approx. 10.5 (softening point: approx. 250 soft C)
), and aromatic polycarbonates of about 19,5 (softening point: about 295°C) were synthesized.

Example 1 Polyethylene terephthalate, length 3m! n
glass chopped strand (Glass Ron Chopped Strand 486A1 Asahi Fiber Glass Co., Ltd.), talc with an average particle size of 10 μm (Talcan Powder PKl Hayashi Kasei Co., Ltd.)
, various female refueling agents, antimony trioxide (Nippon Seiko Co., Ltd.) and polyethylene glycol (di-glycidyl ether of EO4 mono(c) (Dinacol EX82l, Nagase Sangyo Co., Ltd.)
were mixed in the proportions shown in Table 1, and the thickness was 3 at a mold temperature of 85°C.
Disc-shaped test piece and 1/16 inch thick x 1/2 width
inches x 5 inches long or 1/8 inch thick x 1/8 inch wide
2 inches x length 5? A test piece was molded.

The releasability, surface properties, heat distortion temperature, and flame retardance of the obtained molded article were evaluated, and the results are shown in Table 1.

In order to test the stability of the flame retardant, the color development of the molded product was also observed when the molded product was allowed to remain in the cylinder for 5 minutes during molding. As is clear from Table 1, the composition of the present invention containing the flame retardant obtained in Synthesis Example 1 and polyethylene glycol diglycidyl ether has excellent mold release properties, surface properties, flame retardance, and high thermal change temperature. A molded product was obtained which had good stability and was always stable, with no coloring due to the retention test.

On the other hand, a comparative example in which polyethylene glycol diglycidyl ether was not blended had poor mold releasability and surface properties, as well as poor heat distortion temperature. In addition, a comparative example containing decapromodiphenyl ether, dechlorane, tetrapromobisphenol A diglycidyl ether/tetrabromo phthalic anhydride oligomer and brominated paravinylphenol polymer showed significant color decomposition in the retention test. As is clear, the molded product not only had the drawback of large color tone fluctuations, but also was inferior in mold releasability, surface properties, and heat distortion temperature.

In addition, the properties of a molded article obtained with the same composition as Black 4 using the flame retardant obtained in Synthesis Example 2 were also evaluated, and showed similar properties.

Example 2 The same compounding agents as in Example 1 were used except that the type of organic crystallization promoter was changed, and molding was performed in the same manner as in Example 1 at the compounding ratio shown in Table 2, and the characteristics of the molded articles were evaluated.

As is clear from Table 2, the composition of the present invention containing a flame retardant and a specific organic crystallization promoter has excellent mold release properties, surface properties, heat resistance, and dimensional stability when molded in a low-temperature mold. and a flame-retardant molded article.

It is also shown that 5% by weight of the retardant is required based on polyethylene terephthalate, and that 10% or more is preferable in order to pass the UL94V-0 standard with a thickness of 1/16 inch. Furthermore, the combination of solid inorganic fillers improves flame retardancy, moldability,
It also shows that the heat distortion temperature is further improved.

Example 3 The flame retardants of Synthesis Examples 3 and 4 were used, and the formulations shown in Table 3 were made using the same ingredients as in Example 1, except for using the organic crystallization accelerator and mold release agent shown in Cloth-8. The molded product was molded in the same manner as in Example 1, and the characteristics of the molded product were evaluated.

By using a compound with a polyoxyalkylene chain and an epoxy group in combination with a flame retardant, a molded article with excellent mold releasability, surface properties, flame retardance, and improved heat distortion temperature was obtained.

It is also shown that even better mold release properties and surface properties can be obtained by incorporating a mold release agent. Flame retardants with a repeating unit number of more than 10 and less than 16 have a softening point of about 2.
50 to .265, which is exactly close to the melting point of polyethylene terephthalate, indicating that it provides good physical properties. However, in the case of a flame retardant having 5 repeating units, the mold releasability and surface properties deteriorated to some extent, and some coloring was observed in the 5 minute retention test. In addition, Synthesis Example 3 with an alkylene oxide unit
Since the flame retardant improves the dispersibility in polyester, the halogen content of the flame retardant itself decreases, but since it has excellent flame retardancy and easily promotes crystallization, it is better to use a crystallization promoter. A molded article with good mold releasability and surface properties was obtained even if the amount was small.

Claims (1)

[Scope of Claims] 1. Polyethylene terephthalate or polyester having 80% or more of ethylene terephthalate repeating units, (a) aromatic polycarbonate having repeating units represented by the following general formula [I] and/or general formula [I] ] 5 to 50% by weight of an aromatic copolycarbonate containing 25% by weight or more of units represented by the formula and (b)
A flame-retardant polyester composition containing 0.1 to 15% by weight of an organic crystallization accelerator having a polyoxyalkylene chain and an epoxy group. ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] [However, in the formula, X^1, X^2: bromine atom and/or chlorine atom, p, q: an integer from 1 to 4, n: 2 an integer of ~4, r,
t: 0 or an integer of 1 to 20, Y: alkylene group, halogenated alkylene group, alkylidene group, -O-, -CO
-, -S-, -SO-, -SO_2- or - (two benzene rings directly bonded)] 2 For polyethylene terephthalate or 80% polyester, (a) repeating represented by the following general formula [I] 5 to 50% by weight of an aromatic polycarbonate having units and/or an aromatic copolycarbonate containing 25% by weight or more of units represented by the general formula [I], (b) organic crystallization having a polyoxyalkylene chain and an epoxy group; Accelerator 0.1-15% by weight
and (c) a flame-retardant polyester composition containing 1 to 100% by weight of a solid inorganic filler and/or a fibrous reinforcing agent. ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] [However, in the formula, X^1, X_2: bromine atom and/or chlorine atom, p, q: an integer from 1 to 4, n: 2 to 4 an integer of r,
t: 0 or an integer of 1 to 20, Y: alkylene group, halogenated alkylene group, alkylidene group, -O-, -CO
-, -S-, -SO-, -SO_2- or - (two benzene rings are directly bonded)]3 Claims in which the organic crystallization promoter is glycidyl ether of polyoxyalkylene glycol with a molecular weight of 5000 or less 2. The flame-retardant polyester composition according to item 2. 4 Claim 2 in which the solid inorganic filler is a silicate
The flame-retardant polyester composition described in . 5 Claim 2 in which the solid inorganic filler is talc
The flame-retardant polyester composition according to item 1 or 4. 6. The flame-retardant polyester composition according to claim 2, wherein the fibrous reinforcing agent is glass fiber. 7. The flame-retardant polyester composition according to claim 2, wherein the aromatic polycarbonate is an aromatic polycarbonate containing more than 10 and less than 16 repeating units.