JPH02308848A - Flame-resistant polyester resin composition - Google Patents

Abstract

PURPOSE:To provide a flame-resistant resin composition having excellent molding thermal stability, etc., by comprising a terephthalic acid series thermoplastic polyester resin, an aromatic halogen-containing flame retardant, an antimony compound and a hydrotalcite compound. CONSTITUTION:A flame-resistant resin composition comprises (A) 100 pts.wt. of a terephthalic acid series thermoplastic polyester resin having an intrinsic viscosity of 0.5-1.5 (<=40wt.% of other polymers, elastomers, rubbers, etc., may be added), (B) 3-50 pts.wt., preferably 5-30 pts.wt., of an oligomer or polymer type compound halogen-containing flame retardant having a halogen content of >=30wt.% (e.g. a halogenated phenoxy resin), (C) 1-30 pts., preferably 3-20 pts.wt., of an antimony compound, (D) 0.01-10 pts.wt. preferably 1-5 pts.wt., of a hydrotalcite and, if necessary, an antioxidant, a reinforcing filler, etc.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a flame-retardant thermoplastic polyester resin composition, and more specifically, to a molded article thereof that has excellent thermal stability during molding. The present invention relates to a resin composition which has excellent heat resistance, flame retardancy and mechanical strength, and which does not cause flame retardant to bleed out onto the surface of the molded product.

(Conventional Wave) Thermoplastic polyester resin synthesized from terephthalic acid or its ester and glycol, such as polyethylene terephthalate resin (hereinafter abbreviated as PET).
, polybutylene terephthalate resin (hereinafter abbreviated as PBT) has excellent mechanical properties, electrical properties, physical properties, chemical resistance, dimensional stability, etc., and is used in a wide variety of electrical and mechanical parts. ing. However, thermoplastic polyester resins are flammable polymers as they are, and are not suitable for applications that require flame retardancy.

By the way, recently, especially in the field of electrical and electronic components,
With the increasing demand for fire safety, there is an urgent need to make such resins flame retardant.

Generally, to make thermoplastic polyester resin flame retardant, low molecular weight organic halogen compounds such as hexabromobenzene and decabromo biphenyl ether are added as a flame agent, and antimony-based compounds such as antimony trioxide are added to make the thermoplastic polyester resin flame retardant. By using it together as an auxiliary agent, some flame retardant effect can be observed.

However, flame retardant using low-molecular-weight flame retardants as mentioned above has negative effects on secondary processability, such as the flame retardant bleed onto the surface of the molded product, impairing its appearance, and reducing adhesion with adhesives. Furthermore, if it is left at high temperatures for a long time, the flame retardant effect may be lost and it may return to flammability.

Therefore, in order to solve the problem of flame retardant bleeding, various oligomer and polymer-type halogen-based flame retardants are blended into thermoplastic polyvinyl sulfate resin, and halogen-containing carboxylic acids, esters, and glycols are blended into thermoplastic polyester resin. The method of copolymerization is
Proposed.

For example, as a method for blending oligomer and polymer type halogenated flame retardants with thermoplastic polyester resin, a method has been proposed for blending brominated epoxy resin, brominated polycarbonate resin, brominated polystyrene, etc. As a method for copolymerizing halogen-containing carboxylic acid, its ester, and glycol into thermoplastic polyester resin, 2,2-bis(4-(2-hydroxyethoxy)-3,5-dibromophenyl) is used as the glycol. There is a method of copolymerizing propane (hereinafter abbreviated as TBA-EO).

However, flame retardant formulations using these formulations significantly reduce thermal stability during molding (especially when used in combination with antimony-based compounds); for example, retention at high temperatures during injection molding may cause discoloration and strength. In many cases, a practical molded product cannot be obtained due to deterioration. In addition, in order to provide a high degree of flame retardancy that clears ■-0 of the U.S. safety standard, it is essential to use antimony-based compounds in combination, but thermoplastic polyester resins do not contain antimony. When used in combination with other thermoplastic resins, the thermal stability during molding is significantly reduced compared to other thermoplastic resins, and restrictions on molding are extremely large.

On the other hand, molded products are becoming lighter, thinner, shorter, and smaller year by year, and molded products are becoming thinner, smaller, and are now using multi-cavity molds. This tends to result in very harsh injection molding conditions for the molding abrasive. In other words, ■Higher molding temperature, ■Longer residence time in the injection molding machine, ■High-speed molding, ■
This indicates high-cycle molding, which is only possible through a high degree of thermal stabilization of the molding material during molding.

[Problem to be solved by the invention]

The present invention makes flame retardant a terephthalic acid-based thermoplastic polyester resin without reducing the inherent excellent properties of the resin, such as mechanical properties, thermal properties, and physical properties, and also improves thermal stability during molding. In other words, it is a flame-retardant polyester resin that exhibits small changes in melt viscosity and discoloration even when kept for a long time at high temperatures of 250°C or higher, has a small decrease in mechanical strength, and does not bleed onto the surface of molded products. An object of the present invention is to provide a composition.

[Means to solve the problem]

The present invention provides: (A) 100 parts by weight of terephthalic acid plastic ester resin, (B) 3 to 50 parts of an oligomer-type and polymer-type aromatic halogen-containing flame retardant having a halogen content of 30% by weight or more.
The present invention relates to a flame-retardant polyester resin composition comprising 1 to 30 parts by weight of (C) an antimony compound, and 0.01 to 10 parts by weight of (D) a hydrotalcite compound.

The terephthalic acid-based thermoplastic polyester resin used in the present invention includes terephthalic acid or its esters, ethylene glycol, propylene glycol, butanediol, pentadiol, neopentyl glycol, hexanediol, octanediol, and decane. Synthesized from glycols such as diol, cyclohexane dimetatool, hydroquinone, bisphenol A, 2,2-bis(4=hydroxyethoxyphenyl)propane, 1,4-dimethyloltetrabromohenzene or TBA to EO. The intrinsic viscosity [η]
(Measured at 30'C in a mixed solution of phenol/ethane tetrachloride-6/4 (weight ratio)) is usually used. For example, the acid component may be an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, a ring dicarboxylic acid such as cyclohexanedicarboxylic acid, an aromatic dicarboxylic acid such as isophthalic acid, or On the other hand, alcohol components include ethylene glycol, aliphatic glycols such as 2-butanediol, L3-butanediol, and 1,6-hexanediol, alicyclic glycols such as 1,4-cyclohexadimethanol, 4. Aromatic glycols such as 4'-hydroxyethyl-oxyphenylpropane, polyalkylene ether glycols such as polyethylene glycol or poly(te-1-ramethylene ether glycol), and aliphatic polyesters having hydroxyl groups at both ends. - May be replaced with oligomer etc.

In addition, as a comonomer component, lactone compounds such as propiolactone, butyrolavukun, valerolactone, or caprolactone, or polymers thereof may be contained in an amount of 40% by weight or less in the total monomer component, or a comonomer component of methylolethane,
It may also contain polyfunctional ester-forming components such as trimethylolethane, glycerin, pentaerythritol, trimellitic acid, I-rimesic acid, pyromellitic acid, and the like.

Furthermore, the thermoplastic polyester resin may contain up to 40% by weight, such as polyolefins, ionomers, carboxylic acid-modified polyolefins, polystyrene, ASSAB
Other polymers such as SXAES, MBSXASA, acrylic resin, vinyl chloride, EVAc, polyacetal, polycarbonate, polyphenylene oxide, various polyamides, polyphenylene sulfide, polysulfone, polyether sulfone, polyimide, or acrylic rubber, styrene-butadiene rubber, Mixtures with various organic polymers such as elastomers such as ethylene-propylene rubber, polyester ether elastomer or polyamide ether elastomer, polyurethane, or rubber are also included in the present invention, and Low molecular weight polyalkylene terephthalate ([η)-0.1 to 0.5 with a hydroxyl group at the end
Also included are polyester polyurethanes obtained by increasing the molecular weight of (d, ff/g) with a polyfunctional isocyanate.

Next, examples of the oligomer type and polymer type halogen flame retardants used in the present invention include halogenated epoxy resins, halogenated phenoxy resins, halogenated polycarbonate resins, halogenated polystyrene resins, halogenated polyphenylene oxide resins, and halogenated polyesters. Examples include resins, halogenated acrylic resins, etc., and those with an average degree of polymerization of 2 or more are preferred.

For oligomer type and polymer type halogen flame retardants, the amount is 3 to 5 parts, preferably 5 to 3 parts, per 100 parts by weight (hereinafter abbreviated as parts) of the thermoplastic polyester resin.
A range of 0 copies is appropriate.

If the amount used is less than 3 parts, a sufficient flame retardant effect will not be obtained, and if it exceeds 50 parts, the mechanical strength and thermal properties of the flame retardant composition will decrease, which is not preferable.

Examples of the antimony compounds mentioned above include antimony trioxide, antimony tetroxide, antimony pentoxide, and sodium pyroantimonate.

The appropriate amount of the antimony compound used is 1 to 30 parts, preferably 3 to 20 parts. If the amount used is less than 1 part, sufficient flame retardant effect cannot be obtained, and 3
If it exceeds 0 parts, the mechanical strength and thermal properties of the flame retardant composition will decrease, which is not preferable.

In addition, as a hydrotalcite compound, the following formula (1
) % formula % (1) However, in the formula, A''- represents a zero-valent anion, and χ and m each represent the numbers expressed by the following formulas, 0 < x <
0.5, more preferably 0.2≦χ≦0.40 <m<
Hydrosaltites represented by 1 can be mentioned. Preferred examples of n-valent anions represented by A in the above formula include GO3"-, llPO4"-1SO,"
-, 011-, etc. can be mentioned.

The amount of hydrosartites used is 0.01
A range of 1 to 10 parts, preferably 1 to 5 parts is suitable. If the amount used is less than 0.01 part, sufficient thermal properties will not be obtained, and if it exceeds 10 parts, the mechanical strength of the flame retardant composition will decrease, which is not preferable.

In addition to the above-mentioned components, the composition of the present invention also includes a reinforced flame-retardant composition reinforced with the following reinforcing fillers, and the reinforcing fillers include those commonly known and commonly used. Typical examples include glass fiber, carbon fiber, potassium titanate fiber, metal fiber, ceramic fiber, rhusium carbonate, calcium acid, magnesium acid, calcium sulfate, halium sulfate, iron oxide, and graphite. , carbon black, mica, asbestos, wollastonite, ceramic powder, metal flakes, glass beads, etc.

In addition, these reinforcing materials are preferably surface-treated with a silane-based camping agent, a titanium-based coupling agent, or the like.

For example, γ-aminopropyltrimethoxysilane, N-
Aminosilane series such as β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-T-aminopropyldimethoxymethylsilane, etc.: γ-glycidoxypropyltrimethoxysilane sidoxyprobil Epoxysilanes such as ethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; isopropyl tristearoyl titanate, isoprobyl tridodecylbenzenesulfonyl titanate, tetraisopropyl bis(dioctylphosphite l-) titanate 1- Titanium-based coupling agents such as

Furthermore, it is preferable to add a hindered phenolic antioxidant and a phosphite antioxidant to the composition of the present invention.

The binder phenol antioxidant is a hindered phenol compound having a group represented by the following formula in its molecule, and is triethylene glycol-bis(3-
(3-tert-butyl-5-methyl-4-hydroxydiphenyl)propionate], 1,6-hexanediolubis[, 3-(3.5-di-tret-butyl-4-hydroxyphenyl)propionate], 2,4 −
Bis(n-octylthio)-6-(4-hydroxy-3
,5-tert-butylanilino)-L3,5-
1-Ryazine, penquerythrityl-tetrakis (3-
(3.5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis(1-(3.5-di-tert-butyl-4-hydroxyphenyl)propionate), octadecyl-3
-(3,5-tert-butyl-4-hydroxyphenyl)propionate, 2,2-thiobis(4-methyl-6-tert-butylphenol), N. N'
-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 3,5-
Ditret-butyl-4-hydroxy~penzylphosphonate diethyl ester, L3,5-,)limethyl-2,4,6-1-lis(3,5-ditert)
Examples include t-butyl-4-hydroxyhenzyl)benzene, bis(ethyl 3,5-di-tret-butyl-4-hydroxyhenzylbosboxate)calcium, and the like.

In addition, a bosphite antioxidant is a compound having a group represented by the following formula (in the formula, the atom adjacent to 0 is a carbon atom (C)) in the molecule, and a compound represented by the following formula. is exemplified. In addition, in the formula, t -Bu is t
er represents a t-butyl group.

+1. ,C.

(In the formula, R is an alkyl group of CI2 to CI5) t'+O-C
+oHz+)3 Furthermore, 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. may be used, or other flame retardants may be used in combination.

The composition of the present invention can be prepared, for example, by uniformly mixing all the ingredients fried above in advance, feeding the composition into a single-screw or multi-screw extruder, melt-kneading it at 200-300'C, and then
It is cut with a cutter and served as a beret.

The thus obtained composition of the present invention not only has excellent flame retardancy, but also has excellent thermal stability during molding, and the molded product does not bleed to the surface, and also has mechanical and thermal properties. It has excellent physical properties, etc., and its industrial value is extremely large.It can be used not only for LJ, which is used for molding mechanical parts, electrical and electronic parts, and automobile parts, but also for fibers, films, adhesives, etc.

[Example] Next, the present invention will be explained using specific examples and comparative examples.

Example 1 100 parts of PBT resin with [η] of 0.9, brominated epoxy resin (EP-30 manufactured by Dainippon Ink & Chemicals Co., Ltd., molecular weight: 3000, hereinafter abbreviated as Br-epoxy) 2
0 parts, antimony trioxide (manufactured by Nippon Seiko Co., Ltd.), 10 parts, and hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd., Alkamizer 2) 1 part were uniformly mixed in advance, and then 40 parts of
After kneading at 230 to 250°C in an extruder with a mm single screw hem, the mixture was drawn out as a strand, cooled, and then cut with a cutter to obtain resin pellets.

This pellet was then molded into a 12.5 x 126. OX 1.6mm and 12
．． 5 x 126. OX 3. A rectangular test piece with a size of 0 mm was prepared. The injection molding conditions are: molding temperature: 275°C1 mold temperature = 60°C1 injection speed: medium speed, injection pressure crab primary pressure/secondary pressure -140/50 (k
g/cm2), and the normal molded product under these molding conditions is 1
Two types of test pieces were made, one for forced retention for 0 minutes.

Bending strength and bleed-out after being left at 150°C/24 hours were observed using a 3-body-thickness Test I piece of a normal molded product. In addition, the 1.6 mm mm test piece is UL-
94 combustion tests were conducted.

Furthermore, for those that had been forced to stay for 10 minutes, the color difference from a normal molded product was measured using a color machine, and the bending strength was also measured.

Note that the color difference is calculated using the following formula.

Color difference (ΔE) −(L−L′)”+(a−a′)2+
(bb') Evaluation of two color differences: Color difference Visual difference 0-0.5: Slightly 0.5-1.5: Slightly 1.5-3.0: Perceivable 3.0- 6.0: Medatsu 6.0-12.0: Much more than 12.0: Much The measurement results are shown in Table 1.

Example 2 A composition was obtained by adding 50 parts of glass fiber (Glaslon MA-03-419 manufactured by Asahi Glass Fiber Co., Ltd.) to Example 1, and its physical properties are shown in Table 1.

Example 3 A composition was obtained by performing the same operation as in Example 2, except that PET resin with (η) 0.65 was used instead of PBT resin,
Its physical properties are shown in Table 1.

Example 4 Brominated phenoxy resin (manufactured by Dainippon Ink and Chemicals Co., Ltd., EP-500 or less,
Abbreviated as Br-phenoxy. A composition was obtained by performing the same operation as in Example 2, except that molecular weight: 21000) was used.
Its physical properties are shown in Table 1.

Example 5 A composition was obtained by carrying out the same operation as in Example 2, except that a brominated polycarbonate resin (BC-58 manufactured by Great Lakes, hereinafter abbreviated as Br PC) was used instead of Br epoxy. The physical properties are shown in Table 1.

Example 6 A composition was obtained by carrying out the same operation as in Example 2, except that a brominated polyphenylene oxide resin (Po-64P manufactured by Great Lake Co., Ltd., hereinafter abbreviated as Br-based PPO) was used instead of Br-based epoxy, Its physical properties are shown in Table 1.

Example 7 A composition was obtained by carrying out the same operation as in Example 2, except that antimony tetroxide was used instead of antimony trioxide, and its physical properties are shown in Table 1.

Example 8 Hindered phenolic antioxidant (Irganox 1010 manufactured by Ciba Geigy, hereinafter abbreviated as IRIOIO).

) and 1 part of a phosphite antioxidant (Mark 1178, manufactured by Adeka Argus) were added in the same manner as in Example 2 to obtain a composition, the physical properties of which are shown in Table 1.

Comparative Example I Nylon 6 (C manufactured by TORAY) was used instead of PBT resin.
A composition was obtained by performing the same operation as in Example 2, except that M1017) was used, and the physical properties thereof are shown in Table 2.

Comparative Example 2 A composition was obtained by carrying out the same operation as in Example 2, except that decabromovinyl oxide (DE-83, manufactured by Great Lake Co., Ltd.) was used instead of Brized epoxy, and its physical properties are shown in Table 2. Shown below.

Comparative Example 3 A composition was obtained by performing the same operation as in Example 2, except that antimony dioxide was not added, and the physical properties thereof are shown in Table 2.

Comparative Example 4 A composition was obtained in the same manner as in Example 2, except that no hydrotalcite was added, and its physical properties are shown in Table 2.

Comparative Example 5 Except for not adding hydrotalcite and glass fiber,
A composition was obtained by performing the same operation as in Example 2, and its physical properties are shown in Table 2.

A7'/',/ [Effects of the Invention] The present invention can provide a composition that has excellent flame retardancy, has no surface bleed when molded, and has excellent mechanical properties.

Claims (1)

[Claims] (A) Terephthalic acid-based thermoplastic polyester resin 100
Part by weight (B) Oligomer-type or polymer-type aromatic halogen-containing flame retardant with a halogen content of 30% by weight or more 3-50
A flame-retardant polyester resin composition comprising: (C) 1 to 30 parts by weight of an antimony compound; and (D) 0.01 to 10 parts by weight of a hydrophthalcite compound.