JPH0618997B2 - Flame-retardant polyester resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a flame-retardant polyester composition which gives a molded article having good moldability and excellent surface gloss and mechanical properties. More specifically, it has a high crystallization rate, provides excellent molded products even at a mold temperature of about 120 ° C or less during injection molding, and the molded products have excellent mechanical properties to prevent bleeding of flame retardants. The present invention relates to a flame-retardant polyester resin composition in which bleed-out of a flame retardant is suppressed.

(Prior Art) Polyethylene terephthalate has excellent mechanical properties, electrical properties, heat resistance, chemical resistance, etc. and is used in many industrial products as fibers and films. When it is used as a fiber or film as described above, it is usually stretched, but when it is intended to be used for plastics as an injection molded product, for example, the stretching treatment as described above is used. Since it is not done, it is known that various problems occur in molding and physical properties. That is, since polyethylene terephthalate has a low crystallization rate at low temperatures, the crystallization rate is insufficient at a mold temperature of 120 ° C or lower, which is usually used for injection molding of other plastics. A difference in crystallinity occurs between the surface and the inside, which makes the mechanical properties, dimensional stability, and shape stability uneven, and it is extremely difficult to obtain a molded product that can be used practically.

Conventionally, as a method for solving such a problem, many methods using a high temperature mold and adding a crystallization nucleating agent or a crystallization accelerator have been proposed.

The present inventors also filed Japanese Patent Application No. Sho 56-163821 (Japanese Patent Laid-Open No. Sho 58-63743).
No.), Japanese Patent Application No. 56-194003 (Japanese Patent Application Laid-Open No. 58-96648), Japanese Patent Application No. 57-10647 (Japanese Patent Application Laid-Open No. 58-127756), and the like, regarding a polyethylene terephthalate resin composition having a high crystallization rate. presentation.

(Problems to be solved by the invention) In recent years, polyethylene terephthalate reinforced with glass fiber or the like has been used in large quantities as an engineering plastic in the field of industrial parts such as electric parts, automobile parts, machine parts, etc. It is necessary to make the resin flame-retardant when it is used as
It is essential that no bleeding occurs, that is, no bleed-out occurs.

Conventionally, halogen compounds, organic phosphorus compounds, halogen-containing phosphorus compounds, etc. have been used to make resins flame-retardant, and the purpose has been considerably achieved. In thermoplastic polyesters, organic halogen compounds or organic halogen compounds and antimony-containing compounds have been achieved. The combination with and is said to be effective. However, these organic halogen compounds do not have sufficient compatibility with the thermoplastic polyester, and even if they seem to be well compatible with the resin at room temperature, if they are left at a high temperature, for example, in an atmosphere of 80 ° C or higher, Organohalogen compounds bleed out on the surface of a molded product, which not only deteriorates the appearance of the molded product but also often causes a serious problem especially when it is used as an electric component. Further, when the above-mentioned flame retardant is added to the polyethylene terephthalate resin composition improved so that the crystallization rate is increased, the crystallization rate of the polyethylene terephthalate resin composition is decreased and the moldability is improved. There may be a problem that it gets worse.

(Means for Solving Problems) The inventors of the present invention have earnestly studied to solve the problems of the flame-retardant polyethylene terephthalate composition as shown above, that is, a molded product having a high crystallization rate. As a result of diligent research to obtain a flame-retardant polyethylene terephthalate-based resin composition having excellent surface gloss and mechanical properties and suppressing the bleed-out of the flame-retardant, a specific flame retardant and a flame-retardant aid for polyethylene terephthalate-based resin have been obtained. It was found that the above object can be achieved by blending an agent and a specific nucleating agent with an ester plasticizer, and arrived at the present invention.

That is, the gist of the present invention is as follows.

Polyethylene terephthalate or at least 80 mol%
(B) 0.01 to 10 parts by weight of at least one of inorganic compounds having an average particle size of 50 μm or less, and (b) a polyester represented by the following general formula (I). Ester plasticizer
0.3 to 15 parts by weight, (c) 5 to 40 parts by weight of a halogenated bisphenol type polycarbonate compound represented by the following general formula (II), and (2) 1 to 1 of an organic or inorganic antimony-containing compound.
A flame-retardant polyester resin composition containing 15 parts by weight and (e) 0 to 175 parts by weight of a fibrous reinforcing material.

X: direct bond, alkylene group, -0-, -S -, - a group selected from - SO _2.

R ₄ , R ₅ : a group selected from an alkyl group, a benzyl group, a phenyl group or a derivative thereof, and R ₄ and R ₅ are the same or different groups.

R ₆ , R ₇ : hydrogen, an alkyl group, or halogen for R
₆ and R ₇ are the same or different groups.

m, n: an integer of 1 or more X: bromine or chlorine atom R: group selected from direct bond, alkylene group, carbonyl group, ether group, thioether group, sulfone group n: integer of 2 or more (however, average value) p: integer of 1 to 5 q: 1 Integer of 4 (action) The present invention improves the moldability by increasing the crystallization rate of PET by adding a specific amount of the component (a) and the component (b) to the PET resin, and the surface gloss and the like. By improving the surface characteristics of the product and by blending a specific amount of component (c) and component (d), it imparts flame retardancy while maintaining excellent moldability and suppresses bleed-out of the flame retardant. The present invention also provides a composition useful as a molding material.

The polyethylene terephthalate used in the present invention is one obtained by a usual melt polymerization method from terephthalic acid or an ester of terephthalic acid and ethylene glycol, or one obtained by solid phase polymerization treatment. And a polyester having at least 80 mol% or more ethylene terephthalate repeating units means a copolymer comprising 80 mol% or more ethylene terephthalate repeating units and other repeating units, that is, other copolymerization components. As the other copolymer component, various acid components and glycol components can be used. For example, as the acid component, isophthalic acid, naphthalenedicarboxylic acid, diphenyletherdicarboxylic acid, diphenylmethanedicarboxylic acid, diphenylsulfonedicarboxylic acid, p- (2-hydroxyethoxy) benzoic acid, 5-sodiumsulfoisophthalic acid, adipic acid, azelaic acid, sebacine Acid, decane-1,10-dicarboxylic acid, undecane-1,11-dicarboxylic acid, dodecane-1,12-dicarboxylic acid, tridecane-1,13-dicarboxylic acid, tetradecane-1,14-dicarboxylic acid, pentadecane-1 , 15-Dicarboxylic acid, hexadecane-1,16-dicarboxylic acid, heptadecane-1,15-dicarboxylic acid, hexadecane-1,16-dicarboxylic acid, heptadecane-1,17-dicarboxylic acid, octadecane-1,18-dicarboxylic acid , Nonadecane-1,19-dicarboxylic acid, eicosane-1,20-dicarboxylic acid, hen Icosane-1,21-dicarboxylic acid, docosane-1,22-dicarboxylic acid, tetracosane-1,24-dicarboxylic acid, decane-1,6-dicarboxylic acid, 6-ethyl-hexadecane-1,16-dicarboxylic acid, 6 -Ethyl-dodecane-1,12-dicarboxylic acid and the like can be mentioned.

As the glycol component, propylene glycol, diethylene glycol, pentyl glycol, neopentyl glycol, hexamethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol or other polyalkylene glycol,
2,2-bis (p-hydroxyphenyl) propane, bis (p-hydroxyphenyl) sulfone, p, p'-dihydroxybiphenyl, bis (p-hydroxyphenyl)
Examples include bisphenol-containing polyalkylene glycols obtained by addition-condensing alkylene oxides such as ethylene oxide and pyropyrene oxide to bisphenols such as methane, bis (p-hydroxyphenyl) ether, and bis (p-hydroxyphenyl) ketone. You can

The inorganic compound used as the component (a) of the present invention has a different effect as a crystal nucleating agent depending on the particle size, and the effect becomes smaller when the average particle size exceeds about 50 μ. Inorganic compounds are useful.

Specific examples of the inorganic compound having an average particle size of 50 μm or less used in the present invention include carbon black, silica, calcium carbonate, synthetic silicic acid and silicate, zinc white, halosite clay, kaolin, basic carbonic acid. Magnesium, mica, talc, quartz powder, diatomaceous earth, dolomite powder, titanium oxide, zinc oxide, antimony oxide,
Examples thereof include barium sulfate, calcium sulfate, alumina, calcium silicate and the like, and one or more of these inorganic compounds can be used. Among them, mica, kaolin, talc and silica are useful in the present invention. is there.

In addition, a low molecular weight organic compound or a high molecular compound having a metal salt of a carboxyl group is generally used as a crystal nucleating agent. In the composition of the present invention, when the above metal salt, particularly an alkali or alkaline earth metal salt is added, However, foaming may occur during melt molding, which is not preferable.

In the present invention, the ester-based plasticizer which is the component (b) is represented by the general formula (I).

In the general formula (I), X is preferably an alkylene group such as methylene, ethylene or propylidene and -0-, and R ₄ and R ₅ are preferably an alkyl group having 5 or more carbon atoms, a benzyl group and a phenyl group, and m , n is preferably 1 to 10.

The flame retardant used as the component (c) in the present invention is an oligomer or polymer flame retardant of halogenated bisphenol carbonate represented by the general formula (II)
It has characteristics that it is compatible with T resin and does not easily bleed out. X in the general formula (II) is a group consisting of bromine or chlorine, but bromine is preferable to chlorine in terms of imparting flame retardancy. n is an integer of 2 or more (however, average value)
However, if the value of n is too large, the compatibility with PET resin decreases, and conversely, if the value of n is small, heat treatment is applied to the molded product obtained from the flame-retardant polyester resin composition, depending on the heat treatment conditions. The flame retardant may come out bleeding out, though slightly.

Therefore, the value of n is preferably 2 to about 30, more preferably about 3 to 20.

The component (d) used as the flame retardant aid in the present invention is an organic or inorganic antimony-containing compound, and examples thereof include antimony trioxide, antimony phosphate, triphenylantimony, etc., and antimony trioxide is particularly desirable. .

As the fibrous reinforcing material used in the present invention, for example, glass fiber, carbon fiber, aromatic polyamide fiber, silicon carbide fiber, titanic acid fiber and the like can be mentioned as specific examples, but usually glass fiber is often used. It The diameter and length of each fiber are not particularly limited, but if the fiber length is too long, it should be uniformly mixed and dispersed with PET resin and other compounding agents, that is, (a) to (d) components. However, if the fiber length is too short, on the other hand, the effect as a reinforcing material will be insufficient, so a fiber length of 0.1 to 10 mm is usually used, especially when the fibrous reinforcing material is glass fiber. The fiber length is preferably 0.1 to 7 mm, more preferably 0.3 to 4 mm. The fibrous reinforcement is PET
If necessary, various compounds can be used for the purpose of improving the interfacial adhesion with the resin and enhancing the reinforcing effect. However, when glass fiber is used as the fibrous reinforcing material, various materials can be used. Surface treating agents such as vinyltriethoxysilane, γ-methacryloxypropylmethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltrisilane. Ethoxysilane,
Those treated with a silane-based treatment agent such as γ-chloropropylmethoxysilane or γ-mercaptopropyltrimethoxysilane or a chromium-based treatment agent such as methacrylate chromic chloride are used.

Regarding the blending amount of each component in the flame-retardant polyester resin composition of the present invention, if the amount of the component (a) is less than 0.01 parts by weight with respect to 100 parts by weight of the PET resin, the effect as a crystal nucleating agent is small, and If more than 10 parts by weight is blended, the effect as a crystal nucleating agent does not improve with the blending amount, and the physical properties may deteriorate, which is not preferable. Therefore, the blending amount of component (a) is 0.01 to 10 parts by weight, preferably 0.3 to 7 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of PET resin.
5 parts by weight. Next, the amount of component (b), namely the ester plasticizer, varies depending on the type of ester plasticizer. Generally, if it is less than 0.3 parts by weight, the crystallization promoting effect is insufficient, and if it is more than 15 parts by weight. If it is compounded, mechanical and thermal properties are deteriorated, which is not preferable. Therefore, the blending amount of component (b) is 100 parts by weight of PET resin.
0.3 to 15 parts by weight, preferably 1 to 10 parts by weight, more preferably 3 to 7 parts by weight. And regarding the component (C), that is, the blending amount of the flame retardant represented by the general formula (II),
If it is less than 40 parts by weight, the effect of imparting flame retardancy is insufficient, and if it is more than 40 parts by weight, the mechanical properties are greatly deteriorated, which is not preferable.

Therefore, the compounding amount of the component (c) is 5 to 40 parts by weight, preferably 10 to 30 parts by weight, and more preferably 12 to 25 parts by weight, based on 100 parts by weight of the PET resin. The amount of the antimony-containing compound as the component (d) blended as the flame retardant aid is 1 to 15 parts by weight, preferably 2 to 10 parts by weight. Regarding the amount of the fibrous reinforcing material to be blended as necessary in the present invention, it is difficult to uniformly mix and disperse it in the resin when the amount is large, so it is usually desirable to keep it to 175 parts by weight or less. .

The composition of the present invention further comprises an antioxidant, if necessary.
Various inorganic or organic compounds such as an ultraviolet absorber, a colorant, a release agent, and a filler can be blended. In particular, when heat-kneading the PET resin and the bisphenol type polycarbonate compound in the present invention, a composition excellent in heat stability is obtained by adding phosphoric acid or a phosphorous acid derivative such as phosphoric acid ester or phosphorous acid ester. can get.

The polyester composition of the present invention can be produced by mixing it by various methods, and the production method is not particularly limited, but usually a pellet of PET resin is mixed with a flame retardant and various additives. It is manufactured by a method of mixing using an extruder or a kneader. The composition of the present invention can be molded into various forms, for example, various molded products, sheets, fibrous products, tubular products and the like, and used.

(Example) Next, the present invention will be specifically described with reference to Examples and Comparative Examples. The "parts" shown in Examples and Comparative Examples are parts by weight.

Example First, polyethylene terephthalate and copolymerized polyethylene terephthalate shown in Table 1 were produced according to a conventional method. However, the relative viscosity ηrel is a value measured in a phenol / tetrachloroethane = 6/4 solvent at a concentration of 0.5% and a temperature of 20 ° C.

Various polyethylene terephthalate or copolymerized polyethylene terephthalate with a certain amount of various additives, and glass fiber [3 mm long chopped strand made by Asahi Fiber Glass Co., Ltd., product number No. 429] and a flame retardant represented by structural formula (V). A fixed amount was compounded and melt-extruded with a 65 mmφ extruder to produce pellets. Partially quenched pellets were collected at the time of pellet production, and the pellets were subjected to a differential calorimeter (DSC-1 type manufactured by Perkin Elmer Co., Ltd.) to determine the crystallization temperature THC when the temperature was raised from room temperature at 20 ° C / min. . It can be evaluated that the lower the THC value, the higher the crystallization rate in the low temperature region. The results are summarized in Table 2.

n: 5 (average value) Meanwhile, after drying the obtained pellets, the cylinder temperature was 24
0-260-270 ℃, mold temperature 95 ℃, injection holding time 10 seconds, cooling time 20 seconds, injection pressure 300 to 600kg / cm ² 1/2 inch × 1/4 inch × 1/32 inch The test piece was molded, the surface of the molded product was observed, and the flame retardancy was evaluated according to UL94.

Furthermore, the bending strength and flexural modulus of a 1/2 inch x 5 inch x 1/4 inch test piece and the heat distortion temperature at 1/2 inch x 5 inch x 1/16 inch (under a load of 18.56 kg / cm ² )
Was measured. We also investigated whether the flame retardant bleeds out when the molded product is heated at 130 ° C for 24 hours. The results are summarized in Table 3.

The plasticizer is an ester compound represented by the following formula.

(Effects of the Invention) From these, a composition in which a specific nucleating agent, an ester plasticizer, and a halogenated bisphenol-type polycarbonate-based compound are mixed in a PET resin shows excellent physical properties and appearance even when molded by a low-temperature mold, It can be seen that a flame-retardant polyester resin composition with suppressed bleed-out property can be obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location // (C08L 67/02 69:00) (56) References JP-A-58-157851 (JP, A) JP-A-59-96159 (JP, A) JP-A-59-217738 (JP, A) JP-A-54-103459 (JP, A) JP-A-52-151346 (JP, A) JP-A-59 -206458 (JP, A) JP-A-60-84352 (JP, A) JP-A-60-20954 (JP, A)

Claims (1)

[Claims] 1. To 100 parts by weight of polyethylene terephthalate or polyester having at least 80 mol% of ethylene terephthalate repeating units, 0.01 to 10 parts by weight of (a) at least one of inorganic compounds having an average particle size of 50 μm or less, (B) an ester plasticizer represented by the following general formula (I)
0.3 to 15 parts by weight, (c) 5 to 40 parts by weight of a halogenated bisphenol type polycarbonate compound represented by the following general formula (II), and (d) 1 to 1 of an organic or inorganic antimony-containing compound.
A flame-retardant polyester resin composition containing 15 parts by weight and (e) 0 to 175 parts by weight of a fibrous reinforcing material. X: direct bond, alkylene group, -0-, It is a group selected from -S- and -SO _2- . R ₄ , R ₅ : a group selected from an alkyl group, a benzyl group, a phenyl group or a derivative thereof, and R ₄ and R ₅ are the same or different groups. R ₆ and R _{7 are} hydrogen, an alkyl group, or halogen, and R ₆ and R ₇ are the same or different groups. m, n: an integer of 1 or more X: bromine or chlorine atom R: group selected from direct bond, alkylene group, carbonyl group, ether group, thioether group, sulfone group n: integer of 2 or more (however, average value) p: integer of 1 to 5 q: 1 ~ 4 integer