JPH0258562A - Flame-retardant polyester composition - Google Patents

Abstract

PURPOSE:To obtain the subject flame-retardant composition having excellent flame-retardance, mechanical properties, electrical properties, moldability and heat-resistance, free from bleed-out tendency and emitting little gas in use by compounding a halogenated phenoxy resin and an antimony compound to a polyester. CONSTITUTION:The objective resin contains (A) 100 pts.wt. of an aromatic polyester, (B) 1-50 pts.wt. of a halogenated phenoxy resin having the recurring unit of formula (X is Cl or Br; Y is 1-10C alkylene, alkylidene, cycloalkane, carbonyl, -O-, -S- or -SO2-) and (C) 0.1-30 pts.wt. of an antimony compound. The halogenated phenoxy resin of the component B has a number-average polymerization degree (Pn) of 6-50, a weight-average polymerization degree (Pw) of 15-150 and a ratio of the weight-average polymerization degree to the number-average polymerization degree (Pw/Pn) of 1.25-5.0. The number-average particle diameter of the halogenated phenoxy resin is 0.05-2mum.

Description

[Detailed description of the invention] [Industrial application field] The present invention has excellent M flammability, mechanical properties, electrical properties, moldability, and heat resistance, and also has no bleed-out and generates little gas during use. 51tm polyester composition.

[Conventional technology]

Aromatic polyesters, such as polyethylene terephthalate and polybutylene terephthalate, are finding use in mechanical parts, electrical parts, automobile parts, etc. by taking advantage of their excellent properties. On the other hand, in addition to the general balance of chemical and physical properties, these industrial materials are also required to have strong flame safety, that is, flame retardancy. It is necessary that the flame retardant has good mechanical properties and does not bleed out even when the flame retardant is used.Various flame retardants such as brominated polycarbonate oligomers and brominated epoxy oligomers have been studied to meet these requirements. Ta.

However, since brominated polycarbonate oligomers are carbonate esters, transesterification reactions occur between aromatic polyesters that similarly have ester bonds, resulting in lower mechanical properties of aromatic polyesters and poor molding retention stability. There were problems such as the molded product becoming easily bleed out as a white powder during heat treatment of the molded product.

In addition, regarding brominated epoxy oligomers, they thicken during molding, resulting in poor fluidity, low impact resistance, and those with a low degree of polymerization do not produce white powder, but do not completely eliminate bleed-out. There were other problems.

For this reason, JP-A-58-118849 discloses the application of a brominated phenoxy resin having an average degree of polymerization of 11 or more.
Furthermore, JP-A-62-169847 discloses that the degree of polymerization is 20.
Brominated phenoxy resin with a high degree of polymerization and a degree of polymerization of 0-1
The combined use of brominated epoxy compounds with a low degree of polymerization of 0 is disclosed.

[Problem to be solved by the invention]

However, in the composition described in JP-A-58-118849, when a brominated phenoxy resin having an average degree of polymerization of 11 or more and less than 20 is used, the impact resistance and heat resistance are still unsatisfactory. If a polymer having an average degree of polymerization of 20 or more is used, there are problems such as poor molding fluidity and decreased retention stability.

Furthermore, according to the technology disclosed in JP-A-62-169847, it is true that the balance between mechanical properties such as impact resistance, molding retention stability, molding fluidity, and thermal properties of i5 is relatively good. However, the use of brominated epoxy with a low degree of polymerization causes the generation of non-white powder-like bleed-out substances and the amount of gas generated during actual use, making it difficult to apply to parts with contacts such as connectors. The problem was that it was difficult.

[Means for Solving the Problems] Therefore, the present inventors conducted extensive studies to solve the above problems. As a result, mechanical properties such as flame retardancy and impact resistance can be improved by containing a specific proportion of halogenated phenoxy resin having a specific polymerization degree range, weight average molecular weight, and polymerization degree distribution together with an antimony compound in aromatic polyester. We have discovered that it is possible to obtain a polyester composition that has excellent electrical properties such as tracking resistance, mold retention stability, mold fluidity, and heat resistance, does not bleed out, and generates little gas during use, and has developed the present invention. Reached.

That is, the present invention provides (B) based on 100 parts by weight of (A) aromatic polyester.
1 to 50 parts by weight of a halogenated phenoxy resin having a repeating unit represented by the following general formula (I); group, cycloalkane group, carbonyl group, -O--S- or -
SO and - are shown respectively. ) (C) A composition containing 0.1 to 30 parts by weight of an antimony compound, wherein the number average degree of polymerization of the halogenated phenoxy resin as component (B) is 6 to 50, and the weight average degree of polymerization is 6 to 50. 4 is 15 to 150, and the ratio τ/■ of the weight average degree of polymerization to the number average degree of polymerization is in the range of 1.25 to 5.0, and the number average dispersed particle size of the halogenated phenoxy resin is 0. The present invention provides a flame retardant polyester composition characterized by having a thickness of .05 to 2 μm.

The aromatic polyester (A) used in the present invention is polyester having an aromatic ring in the chain unit of the polymer, and mainly contains an aromatic dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative). It is a polymer or copolymer obtained by a condensation reaction as a component.

The aromatic dicarboxylic acids mentioned here include terephthalic acid,
Isophthalic acid, orthophthalic acid, l.

5-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-
naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 3,3-biphenyldicarboxylic acid, 2,2'-
Biphenyl dicarboxylic acid, 4°4'-diphenyl ether dicarboxylic acid, 4. ．． 4'-diphenylmethanedicarboxylic acid, 4.4'-diphenylsulfonedicarboxylic acid,
4.4'-diphenylisopropylidenedicarboxylic acid,
1,2-bis(phenoxy)ethane-4,4'-, dicarboxylic acid, 2,5-tentracenedicarboxylic acid, 2,6
-anthracenedicarboxylic acid, 4.4'-p-terphenylenedicarboxylic acid, 2.5-pyridinedicarboxylic acid, etc., and terephthalphthalic acid is preferably used.

These aromatic dicarboxylic acids may be used as a mixture of two or more types.If the aromatic dicarboxylic acids are small, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid may be used together with these aromatic dicarboxylic acids. One or more kinds of acids and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid can be used in combination.

In addition, as diol components, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1
Preferred examples include aliphatic diols such as , 3-propanediol, diethylene glycol and triethylene glycol, alicyclic diols such as 4-cyclohexane dimetatool and 1,3-cyclohexane dimetatool, and mixtures thereof. It will be done.

In addition, if the amount is small, one or more types of long-chain diols having molecules of 1,400 to 6,000, such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, may be copolymerized.

Specific preferred aromatic polyesters include polyethylene terephthalate, polypropylene terephthalate,
Polyethylene terephthalate, polyhexylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene-1,2-bis(phenoxy)ethane-4,,4'-dicarboxylate, poly-1
, 4-cyclohexane dimethylene terephthalate, polyethylene isophthalate/terephthalate, polybutylene terephthalate/isophthalate, polybutylene terephthalate/decanedicarboxylate, poly-1,4-cyclohexane dimethylene terephthalate/
Examples include copolymerized polyesters such as isophthalate. Among these, polybutylene terephthalate, polyethylene terephthalate, and poly(1) 1,4-cyclohexane dimethylene terephthalate, which have well-balanced mechanical properties, moldability, etc., can be particularly preferably used.

Further, it is preferable that the terminal carboxyl group concentration of the aromatic polyester used in the present invention is 50 equivalents/10 6 g or less, since retention stability and heat resistance are improved. Particularly when a type of compound having a glycidyl group at the end group is used as the halogenated phenoxy resin, it is preferable that the end group concentration of the aromatic polyester is 50 equivalent ffi/l06 g or less, as this provides good fluidity during molding.

The aromatic polyester used in the present invention is 0.5%
The measured relative viscosity of 0-chlorophenol is 1.15 to 2. O, especially 1.3
~1.85 is preferred.

The halogenated phenoxy resin (B) used in the present invention is represented by the above general formula (I), and for example, halogenated bisphenol glycidyl ether and halogen in the presence of an appropriate catalyst and using a solvent if necessary. It is produced by a method such as reacting bisphenol.

The halogenated bisphenol compound serving as a component of the halogenated phenoxy resin of the general formula (r) is 2
．． 2-bis(3,5-dibromo-4-hydroxyphenyl)propane, bis(3,5-dibromo-4-hydroxyphenyl)methane, bis(3,5-dibromo-4-hydroxyphenyl)phenylmethane, 1. 1-bis(3
゜5-Dibrom-4-hydroxyphenyl)ethane, bis(3,5-dibrom-4-hydroxyphenyl)sulfone, bis(3,5-dibrom-4-hydroxyphenyl)ether, bis(3,5-dibrom-4) -hydroxyphenyl)ketone, bis(3,5-dibromo-4-hydroxyphenyl)sulfide, 2,2-bis(3,5-dichlor=4-hydroxyphenyl)propane, bis(3
, 5-dichloro-4-hydroxyphenyl)methane, bis(3,5-dichloro-4-hydroxyphenyl)sulfone, bis(3,5-dichloro-4-hydroxyphenyl)sulfide, among others, Tetrabromobisulfate, 2,2-bis(called enol A)
Most preferred is the use of 3,5-dibromo-4-hydroxyphenyl)propane. Use of non-halogenated normal bisphenol compounds such as 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)methane, etc. together with halogenated bisphenol. Can be done.

The halogenated phenoxy resin of the present invention generally has a glycidyl group and/or a hydroxyl group as a terminal group, but it is also possible to use a resin in which these terminal groups are blocked with carboxylic acids, phenols, amines, or alcohols. You can also use things.

Further, the number average degree of polymerization of the halogenated phenoxy resin (B) used in the present invention is 6 to 50, preferably 8 to 40, more preferably 10 to 25, and the weight average degree of polymerization Pw is 15 to 150, preferably It is important that the number is more preferably 25-75 than 20-1OO1.

If the Pn of the halogenated phenoxy resin is less than 6 or 4 is less than 15, the fluidity and retention stability during molding will be poor, and further problems such as flame retardant bleed out and increased gas generation will occur. tends to occur. On the other hand, if the stiffness exceeds 50 or the film exceeds 150, problems such as poor fluidity and poor mechanical properties during molding tend to occur.

The halogenated phenoxy resin also has weight average polymerization and P
The ratio of w and number average degree of polymerization sieve/6 is 1.25 to 5.0, preferably 1.5 to 4.0, more preferably 1.75 to 3.
．． 5, most preferably in the range of 2.0 to 3.0. When the ratio of 9°/1.25 is less than 1.25, the retention stability, heat resistance and electrical properties tend to deteriorate, while when the ratio of 9°/1.25 exceeds 5.0, the fluidity during molding tends to deteriorate. Both of these are unfavorable, as they tend to deteriorate the electrical properties.

Generally speaking, the dispersed particle size (number average particle size) of the halogenated phenoxy resin in the matrix resin is 0, . 05~2μ
m, preferably 0.10 to 1 μm, more preferably 0.1 μm.
It is desirable that the thickness be in the range of 15 to 015 μm. If the dispersed particle size is less than 0.05 μm, there will be a decrease in fluidity and mold release properties during molding, and a decrease in electrical properties, while if it exceeds 2 μm, the mechanical properties and appearance of the molded product will deteriorate. Both are unfavorable. Such a range of particle diameters can be achieved by appropriately selecting the degree of polymerization and the amount of terminal groups of the aromatic polyester and the degree of polymerization and degree of polymerization distribution of the halogenated phenoxy resin within the above ranges.

Note that when the phosphorus content of the halogenated phenoxy resin used in the present invention is 0.2% by weight or less, more preferably 0.1% by weight or less, the amount of gas generated is further reduced, and the halogenation of the terminal glycidyl group is When a phenoxy resin is used, the fluidity during molding is particularly good.

The amount of halogenated phenoxy resin added in the present invention is
1 to 50 parts by weight, preferably 3 to 40 parts by weight, more preferably 5 to 3 parts by weight based on 100 parts by weight of aromatic polyester
0 parts by weight is desirable. If the amount of halogenated phenoxy resin added is less than 1 part by weight, the flame retardant improvement effect will not be sufficient, while if it exceeds 50 parts by weight, the mechanical properties and moldability will be significantly reduced. Undesirable.

In addition, the phosphorus content in the composition of the present invention is 0 as phosphorus atoms.
．． It is desirable that the amount is 5% by weight or less, preferably 0.2% by weight or less, more preferably 0.1% by weight or less. If the phosphorus content in the composition exceeds 0.5% by weight in terms of phosphorus atoms, it is undesirable because it tends to thicken during molding, resulting in poor fluidity and increased gas generation.

Various kinds of antimony compounds can be used as the antimony compound (C) used in the present invention. Specifically, antimony oxides such as antimony dioxide and antimony pentoxide, antimony phosphate, sodium antimonate, KSb (OH) potassium antimonyl tartrate, 5b (QC) lx C113)!
, Sb COCH (CHs>CHzCHz) z, triphenylstibine, etc., and antimony oxide can be preferably used.

The amount of the antimony compound added in the present invention is 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the aromatic polyester. If it is less than 0.1 part by weight, the effect of improving flame retardancy will not be sufficient. However, if it exceeds 30 parts by weight, the mechanical properties of the aromatic polyester will be impaired. More preferably, it is added at a ratio of 1 antimony atom in the antimony compound to 2 to 5 halogen atoms in the added flame retardant. At the same time, other flame retardant aids such as boron oxide, zirconium oxide, iron oxide, barium sulfate, etc. may be used in combination.

Note that, although not particularly essential, when fibrous and/or granular fillers are further added to the composition of the present invention, the rigidity can be significantly improved without deteriorating other properties. Such fillers include glass fibers, carbon fibers, metal fibers, aramid fibers, ceramic fibers, asbestos, potassium titanate whiskers, wollastenite, gypsum fibers, sepiolite, glass peas, glass flakes, talc, mica, clay, carbonate. Examples include calcium, barium sulfate, titanium oxide, aluminum oxide, etc. Among them, chopped strand type glass fiber can be preferably used. The amount of these additives is usually 3 to 80 parts by weight per 100 parts by weight of the aromatic polyester.

Furthermore, the composition of the present invention may contain conventional additives such as antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, mold release agents, colorants including dyes and pigments, and nucleating agents, to the extent that the purpose of the present invention is not impaired. One or more types of additives can be added. Additionally, small amounts of other thermoplastic resins (e.g. polycarbonate, polyphenylene oxide, polyamide, polypropylene, polyethylene, ethylene/propylene copolymer, ethylene/butene-1 copolymer, ethylene/propylene/non-conjugated diene copolymer, ethylene/ Ethyl acrylate copolymer, ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, ethylene/propylene-g-maleic anhydride M4 polymer, etc.) can also be added.

Although the method for producing the composition of the present invention is not particularly limited, aromatic polyester, a specific halogenated phenoxy resin, an antimony compound, and other additives as necessary are added to the aromatic polyester using an extruder. Examples include a method of melting and kneading at a temperature higher than the melting point of .

〔Example〕

EXAMPLES The effects of the present invention will be explained in further detail with reference to Examples below.

Examples 1 to 6, Comparative Examples 1 to 8 Relative viscosity 1.77, terminal carboxyl group amount 21 equivalent/1
For 100 parts by weight of 0'g of polybutylene terephthalate, 8 parts by weight of antimony trioxide and the following halogenated phenoxy resin (81~(el) were mixed in a blender and then using a 401 mφ extruder. The pellets were melt-kneaded and pelletized at 250°C. After drying, AS
According to TM D-1238, the melt flow rate (MFR) was determined using a 5 oz. Molding was performed at a mold temperature of 80°C and a molding cycle (injection time/cooling time/intermediate time) of 10 seconds/10 seconds/10 seconds (molding cycle). An S-shaped dumbbell for impact testing and a combustion test piece (I/16'' x 172'' x 5'') were each obtained. Also, width 50mm, length 801m, depth 3011, wall thickness 2
(2) The force required to release the box-shaped molded product in step 1 from the mold was determined using a pressure sensor and was defined as the mold release force.

Furthermore, the molding cycle (injection time/cooling time/intermediate time)
A tensile impact test piece was obtained in the same manner as above, except that the time was changed to 10 seconds/10 seconds and 150 seconds (molding cycle (0)), and the other conditions were the same, and a tensile impact test (ASTM D1822) was performed.
I did it.

For the test piece of molding cycle (a), ui, 94m
Vertical combustion test according to IEC Publica
on112, therefore the rECl-rough king test (CTI
A tensile impact test was conducted in accordance with ASTFI 01822, and weight loss (heat loss) was measured after 40 minutes at 265° C. under a nitrogen stream using a DuPont thermogravimetric analyzer. In addition, after being treated for 24 hours while open at 130°C,
Reflection infrared spectra were measured to check for bleed-out, and after heat treatment in an oven at 190°C for 150 hours, a tensile impact test was conducted. Further, an ultrathin section was prepared from the ASTMI dumbbell of the molding cycle (a), and the dispersed particle diameter of the halogenated phenoxy resin was measured using a transmission electron microscope.

These results are shown in Table 2.

[Flame retardant (al~(I)]

Flame retardant (al~(I1 each has the structure of the following general formula,
And it has the polymerization degree and polymerization distribution shown in Table 1.

Specific number average degree of polymerization (Pn) of the present invention from the examples in Table 2
and weight average degree of polymerization (Pw), and Pw/Pn
A specific amount of halogenated phenoxy resin having a ratio of 1.25 to 5.0 is added together with an antimony compound to the aromatic polyester, and the particle size of the halogenated phenoxy resin is in the range of 0.05 to 2 μm. In such cases, flame-retardant polyester compositions that not only have excellent flame retardancy, mechanical properties, electrical properties, moldability, and heat resistance, but also do not bleed out and generate extremely little gas during actual use are needed. You can see what you can get.

Examples 7 to 9, Comparative Examples 9 to 12 Relative viscosity 1.45, terminal carboxyl group amount 37 equivalents/1
To 100 parts by weight of polybutylene terephthalate (06 g), the flame retardant (al~(gl) 18 parts by weight of a type of flame retardant, 50 parts by weight of chopped strand type glass fiber (3 length) and trioxide. 8 parts by weight of antimony was triblended in a tumbler, and melt-mixed, injection molded (however, the molding temperature was 260° C.) and characterized in the same manner as in Example 1. The results are shown in Table 3.

As is clear from the examples in Table 3, even when glass fiber is blended, the composition of the present invention not only has excellent flame retardancy, mechanical properties, electrical properties, mold retention stability, and heat resistance, but also has excellent bleed resistance. It can be seen that a flame-retardant polyester composition with no outflow and an extremely small amount of gas generation during actual use can be obtained.

(Blank below next summer) Comparative Example 13 When the phosphorus atom concentration in Example 8 was measured by atomic absorption spectrometry, it was found to be 0.15% by weight. In contrast, PBT with a phosphorus content (added as trimethyl phosphate during polymerization) of 0.55% (relative viscosity 1.44
When extrusion compounding, molding, and physical property evaluation were carried out in the same manner as in Example 7 using a terminal carboxyl group amount of 40 equivalent it/106 g), the MFR was 21 g/10 minutes at a retention time of 8 minutes and 7 g/10 minutes at a retention time of 30 minutes. A significant increase in viscosity was observed, and the loss on heating was 0.
The CTI value increased to 24%, the CTI value increased to 230V, and the tensile impact strength (untreated product) of the molding cycle (a) also increased to 11.
The weight decreased to 0 kg·clll/cIi. The phosphorus content of this composition was 0.57% by weight in terms of phosphorus atoms, and it can be seen that as the phosphorus concentration in the composition increases, the properties of the composition of the present invention are impaired.

〔Effect of the invention〕

The present invention comprises an aromatic polyester containing an antimony compound and a halogenated phenoxy resin having a specific number average degree of polymerization, a specific weight average degree of polymerization, and a specific ratio of these in a specific dispersion size. The flame-retardant polyester composition not only has excellent moldability, but also the resulting molded products have good flame retardancy, good mechanical properties, and good electrical properties, and generates extremely little gas during actual use, resulting in no bleed-out. It is useful as electrical/electronic equipment parts, automobile parts, etc. because it can produce molded products with no pores.

Agent: Patent Attorney Nobuo Kogawa -

Claims (1)

[Claims] (A) (B) based on 100 parts by weight of aromatic polyester
There are 1 to 50 parts by weight of halogenated phenoxy resin having a repeating unit represented by the general formula (I) below, and ▲mathematical formulas, chemical formulas, tables, etc.▼(I) (In the above formula (I), X is a chlorine atom or a bromine atom. , Y is C_1_ to_1_0 alkylene group, alkylidene group, cycloalkane group, carbonyl group, -O-, -
S- or -SO_2- is shown respectively. ) (C) A composition containing 0.1 to 30 parts by weight of an antimony compound, wherein the halogenated phenoxy resin of component (B) has a number average degree of polymerization @Pn@ of 6 to 50,
The halogenated phenoxy A flame-retardant polyester composition characterized in that the number average dispersed particle size of the resin is 0.05 to 2 μm.