JPH0212980B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polyester resin composition that has excellent flame retardancy, no bleeding of flame retardant, high mechanical strength and heat resistance, and good moldability. To make polyester flame retardant, the flame retardant does not transfer to the surface of the molded product in a high-temperature atmosphere, so-called non-bleed formulation. Alternatively, a method of copolymerizing glycol with polyester is known. A particularly preferred glycol containing halogen in polyester is 2,2-bis(2
A method for copolymerizing -hydroxyethoxy)-3,5-dibromophenyl]propane (hereinafter abbreviated as TBA·EO) is known from JP-A-49-54494. However, in this method, since the reaction temperature when synthesizing this copolymer is very high at 230 to 300°C, the decomposition reaction also proceeds fairly quickly, making it difficult to obtain a product with a high molecular weight. Further, even if a high molecular weight copolymer is obtained, its mechanical strength is considerably lower than that of polyester not modified with the halogen-containing glycol, which is a practical drawback. Second, halogen-containing glycol-modified polyester has a lower melting point and lower heat distortion temperature than unmodified polyester as usual for copolymers, so it is difficult to use it in applications that require heat resistance. Furthermore, it is difficult to crystallize and requires a large amount of cooling time during injection molding, resulting in poor productivity.
It is difficult to release from the mold because the shrinkage during cooling is small. In addition, brominated epoxy resin, which is one of the polymer type flame retardants, has been designated as a highly practical
It is added to PBT as shown in No. 53-18068. However, such brominated epoxy resins
Since the molding temperature of PBT is generally 230 to 260°C, the brominated epoxy resin used in combination with PBT becomes crosslinked three-dimensionally, and when the PBT containing the epoxy resin is retained in the cylinder of the molding machine. The disadvantage is that the melt viscosity of the resin increases, making molding difficult. As a result of extensive research by the present inventors in order to improve the above-mentioned drawbacks, blending a copolymerized polyester with a high reaction ratio of the halogen-containing glycol to polyalkylene terephthalate not only improves the above-mentioned drawbacks, but also The present inventors have discovered that mechanical strength can be further improved when an epoxy compound or a polyfunctional isocyanate compound is used as a third component. That is, in the present invention, the following (a) and (b) are added to 100 parts by weight of polyalkylene terephthalate obtained using glycol having 2 to 4 carbon atoms.
5 to 6 parts by weight of a halogen-containing polyester flame retardant with a halogen content of 10% by weight or more obtained by reacting (c) or/and (d) as necessary; (a) R: Alkylene group SO ₂ - group (b) dicarboxylic acid (c) glycol (d) at least one selected from tricarboxylic acid, tetracarboxylic acid, triol, and tetraol 0.5 to 30 parts by weight of an inorganic flame retardant aid and an epoxy compound or Polyfunctional isocyanate compound 0.1
~30 parts by weight of a high strength composition. To explain the present invention in detail, the polyalkylene terephthalate used in the present invention is a polyester consisting of terephthalic acid or a terephthalic acid alkyl ester and a glycol having 2 to 4 carbon atoms. Such glycols include ethylene glycol, 1,3-propylene glycol, 1,
Examples include glycols having 2 to 4 carbon atoms such as 4-butanediol, 1,2-propylene glycol, 1,3-butanediol, and 1,2-butanediol. It is also possible to copolymerize a part of this polyester with other dicarboxylic acids or/and diols, each containing 40% of the acid component and the glycol component.
Substitution may be made up to mol%. Examples of other dicarboxylic acids include phthalic acid, isophthalic acid, naphthalene dicarboxylic acid, adipic acid, and sebacic acid. Examples of other glycols include glycols other than those mainly used among the above-mentioned glycols, or 1, These include 6-hexanediol, cyclohexane dimethanol, etc. Also, it is manufactured from terephthalic acid or its alkyl ester and glycol such as ethylene glycol or 1,4-butanediol, and most of the terminal groups are hydroxyl groups, molecular weight 3000-20000, hydroxyl value 40-40.
A polyester urethane obtained by reacting the polyester of No. 5 with a polyfunctional isocyanate can also be used. Next, the halogen-containing polyester flame retardant in the present invention is obtained by copolymerizing the following components (a) and (b), or (a), (b), (c), or/and (d). ) and has a halogen content of 10% by weight or more. This component (a) has the general formula (The symbols in the formula are as described above.) Specifically, TBA・BO, 2,2-bis[4-(2-hydroxyethoxy)-3,5-dichlorophenyl]propane, 2, 2-bis [4-
(2-hydroxypropoxy)-3,5-dibromophenyl]propane, 2,2-bis[4-(3
-hydroxypropoxy)-3,5-dibromophenyl]propane, 2,2-bis[4-(2-hydroxypropoxy)-3,5-dichlorophenyl]propane, 2,2-bis[4-3-hydroxypropoxy )-3,5-dichlorophenyl]propane, 2,2-bis[4-(2-hydroxyethoxy)-3-bromophenyl]propane, 2,
2-bis[4-(2-hydroxyethoxy)-
2,3,5,6-tetrabromophenyl]propane, 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]sulfone,
2,2-bis[4-(2-hydroxyethoxy)
-3,5-dibromophenyl]ether and the like. Particularly preferred are TBA·EO and 2,2-bis[4-(2-hydroxyethoxy)-3,5-dibromophenyl]sulfone. Component (b) includes terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, adipic acid, sedicic acid, and the like. (c) Ingredients include ethylene glycol, 1,
3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,
3-butanediol, 1,2-butanediol,
Examples include 1,6-hexanediol and cyclohexanedimethanol. Particularly preferred are ethylene glycol and 1,4-butanediol. Ingredients (d) include trimethic acid, trimethic anhydride, pyromellitic anhydride, benzenetetracarboxylic acid, trimethylolpropane, glycerin,
Examples include pentaerythritol. Also, the molar ratio of (a) and (b) is usually (a):(b)=1:0.5
-2, preferably 1:0.7-1.4. When (c) or/and (d) are used together, hydroxyl group: carboxyl group = 1:0.5-2, preferably 1:0.6-1.4
(a), (b), (c), and (d) are used so that the halogen content of the flame retardant produced is
Component (d) is used in an amount of 10% by weight or more of the hydroxyl group- or carboxyl group-containing component. Such flame retardants are generally used at temperatures below the decomposition temperature of the halogen compound (a), e.g. 150°C.
It can be synthesized by a general method of polycondensation after transesterification in the presence of a transesterification catalyst at a temperature of ~300°C. Incidentally, the carboxyl groups of the alkyl esters or anhydrides of components (b) and (c) are calculated using the carboxyl groups constituting them. In the present invention, the flame retardant is added in an amount of 5 to 60 parts by weight, preferably 10 to 50 parts by weight, per 100 parts by weight of polyalkylene terephthalate (referred to as polyester). If the amount of such flame retardant is less than 5 parts by weight, sufficient flame retardancy will not be imparted, and if it exceeds 60 parts by weight, the strength of the composition will decrease. In particular, the effect on flame retardancy is most dependent on the proportion of halogen in the composition. In the case of bromine, the amount of halogen in the composition is usually 2 to 30% by weight, particularly preferably 3 to 30% by weight.
It is 20% by weight. In the present invention, an inorganic flame retardant aid is used in combination to increase the flame retardant effect. Such an auxiliary agent is Vb
Inorganic compounds of the group are suitable, for example compounds of antimony, arsenic, phosphorus, bismuth. Preferred for use are antimony trioxide, antimony tetroxide, antimony pentoxide, sodium pyroantimonate, arsenic oxide, bismuth oxide,
Phosphorus compounds are used. Furthermore, tin compounds such as zirconium oxide and tin oxide, boric acid compounds, and molybdenum compounds are also used. In particular, antimony compounds such as antimony trioxide are preferable because they have a large effect as an auxiliary agent. The amount of inorganic flame retardant aid used is 0.5 per 100 parts by weight of polyester.
~30 parts by weight, especially 2 to 20 parts by weight are preferred. As the epoxy compound that can be used in the present invention, a compound having one or more epoxy groups is used.
Since the mechanical strength of the present composition is improved when an epoxy compound is used in combination, it is highly effective in improving the decrease in strength of the composition caused by the addition of a flame retardant. Of these epoxy compounds, 1 epoxy group
Examples of the compounds that have these properties include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl-triethoxysilane, β-(3,4
-Epoxycyclohexyl)ethyltrimethoxysilane, glycidylphenol, etc.
Particularly preferred are γ-glycidoxypropyltrimethoxysilane or γ-glycidoxypropyltriethexilane. Examples of compounds having two or more epoxy groups include bisphenol A
type epoxy resin, bisphenol F type epoxy resin, resorcin type epoxy resin, novolak type epoxy resin, vinyl cyclohexene dioxide,
Halogenated epoxy resins substituted with dicyclopentadiene dioxide, bromine or chlorine (halogenated bisphenol A type epoxy resin, halogenated bisphenol F type epoxy resin, halogenated resorcinol type epoxy resin, halogenated novolac type epoxy resin, etc.) Particularly preferred are bisphenol A type epoxy resins and halogenated bisphenol A type epoxy resins.
When a polyfunctional isocyanate compound is added to the present composition, effects similar to those of an epoxy compound are exhibited. Specifically, polyfunctional isocyanates include, for example, aliphatic diisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate; tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, m-
and aromatic diisocyanates such as p-phenylene diisocyanate and naphthalene-1,5-diisocyanate; and alicyclic diisocyanates such as dicyclohexylmethane diisocyanate. Furthermore, compounds having two or more isocyanate groups in one molecule such as crude diphenylmethane diisocyanate, dimers of tolylene diisocyanate, dimers of diphenylmethane-4,4'-diisocyanate, isocyanurate compounds, etc. can also be used.
The appropriate amount of the epoxy compound or polyfunctional isocyanate compound to be added is 0.1 to 30 parts by weight per 100 parts by weight of the polyester. Preferably 1~
20 parts by weight is good. One reason why the strength of the composition is improved by adding such an epoxy compound or polyfunctional isocyanate is that it promotes chain elongation of the polyester whose molecular weight has been reduced due to thermal deterioration of the polyester during molding. In particular, when antimony trioxide is used as a flame retardant aid, it has a great effect on lowering the molecular weight of polyester because antimony trioxide is a transesterification catalyst for polyester. Second, when reinforcing materials such as glass fibers, glass beads, and inorganic fillers are used together, they have the effect of improving the adhesion between polyester and these reinforcing materials, so the performance as a reinforcing material is fully demonstrated. It is thought that this is because the It is also possible to substitute less than 50% by weight of the polyester of the present invention with other polymers.
Examples of such other polymers include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer,
Ethylene-propylene copolymer, polystyrene,
AS resin, ABS resin, nylon, polyacetal, polycarbonate, thermoplastic polyester such as polyethylene terephthalate, polysulfone,
Examples include polyphenylene sulfide and thermoplastic polyester. In the present invention, glass fiber, carbon fiber,
Reinforcing materials such as glass powder, glass beads, talc, mica, calcium carbonate, calcium silicate, fillers, crystal nucleating agents, application materials, plasticizers, mold release agents, lubricants, heat stabilizers, antioxidants, ultraviolet absorbers , blowing agents, other flame retardants, etc. can be added. The glass fiber in the present invention is, for example, vinyl silane,
Those treated with an aminosilane or epoxysilane type coupling agent are used, and roving glass and chopped strands are used, and it is preferable that glass powder and glass beads are also treated with the same coupling agent. The amount of the above-mentioned reinforcing material and filler added is suitably 2 to 60% by weight, preferably 5 to 50% by weight. If this amount exceeds 60% by weight, molding processability will be poor;
If it is less than % by weight, it will not be effective as a reinforcing material or filler. This composition is prepared by a known manufacturing method. For example, all the raw materials are uniformly mixed in advance, then fed into a single-screw or twin-screw extruder, melted at 200 to 300°C, kneaded, and then cooled to prepare pellets. Examples are given below to explain the present invention in more detail. The flow rate in the example is according to ASTMD-1238,
As a guideline for measuring the viscosity of the amount of molten resin, it was expressed as the amount of resin (g per 10 minutes) that passed through a constant orifice, at a constant temperature (265°C), and under a constant load (2160 g). The larger this value is, the smaller the melt viscosity is. Furthermore, if the flow rate increases due to a long residence time, it means that the melt viscosity decreases. In the examples, % and parts clearly indicate weight % and parts by weight. Reference example 1 TBA/EO 1.1 mol, 1,4-butanediol
Pour 0.2 mol and 1 mol of dimethyl terephthalate into a flask with a stirrer and heat to 150℃ to uniformly dissolve.
Tetraisopropyl titanate catalyst was added at 200 ppm based on the total feedstock. As the by-product methanol was distilled off, the temperature of the system was gradually raised to 180°C. When the distillation of methanol has stopped approximately 6 hours after the introduction of the catalyst, the inside of the system is maintained at a vacuum of approximately 100 mmHg.
Distillation of methanol was promoted, and the pressure was returned to normal after 2 hours. The produced resin was put into a cooling vat, cooled, and then ground into powder. The resulting resin has a bromine content
40.7%, an acid value of 0.6, and a softening point of 102 to 115°C, and the diluted solution viscosity of 2 parts of resin diluted with 1 part of toluene showed J in terms of Gardner viscosity at 25°C. still,
This resin is called flame retardant FR-A. Reference example 2 TBA・EO 1.5 mol, 1,4-butanediol
Pour 0.4 mol and 1 mol of dimethyl terephthalate into a flask with a stirrer and heat to 150℃ to uniformly dissolve.
Tetraisopropyl titanate catalyst was added at 200 ppm based on the total feedstock. As the by-product methanol was distilled off, the temperature of the system was gradually increased to 180°C after 3 hours, and the process was continued at that temperature for an additional 2 hours. Thereafter, 0.1 mol of trimellitic acid was added and the reaction was continued for 2 hours. The resulting resin had a bromine content of 39.4%, an acid value of 3.0, a softening point of 105 to 110°C, and a solution dilution viscosity of UV.
This resin is referred to as flame retardant FR-B. Reference example 3 Same as reference example 2, TBA・EO 1 mol, 1,4
-0.4 mol of butanediol, 1 mol of dimethyl terephthalate, and 0.15 mol of trimellitic acid were reacted. The resulting resin has a bromine content of 37.6% and a softening point of 121~
It exhibited a temperature of 126°C, an acid value of 5, and a solution dilution viscosity of _Z2 . still,
This resin is called flame retardant FR-C. Comparative example 1 100 parts of PBT with intrinsic viscosity [η] 0.8, flame retardant FR―
A23 parts, antimony trioxide 11 parts, Glassron
After uniformly mixing 58 parts of MA-03-419 (chopped strand glass fiber manufactured by Asahi Glass Fiber), it was put into a 50 mm single-screw vented extruder with a cylinder heated to 240°C, and the temperature was increased to 80 rpm. The mixture was kneaded and cooled to obtain pellets. Using a 3-ounce injection molding machine, this pellet was subjected to tensile testing using a cylinder temperature of 250°C and a mold temperature of 80°C.
638 Type I dumbbell specimens, ASTM D-256 specimens for Nottsu Izotsu impact testing, ASTM D-648 specimens for heat distortion temperature measurement, and Subject 94 of the U.S. Undan Lighters Laboratories (UL) standard. Samples with a thickness of 1/16 inch were prepared for each combustion test. When these specimens were subjected to physical property tests according to their respective standards, the tensile strength (hereinafter abbreviated as TS) was 1000Kg/cm ² and the notched isot impact strength (hereinafter abbreviated as II) was 5Kg/cm 2 .
cm/cm, heat distortion temperature (hereinafter abbreviated as HDT) 210
℃, flammability V-O performance. Comparative Example 2 In Comparative Example 1, when the flame retardant FR-A was changed to FR-B, TS: 1100Kg/cm ² , HDT: 210
℃, showed the properties of combustible V-O. Also, ASTM
D-1238, the resin at 265°C/5 minutes and at 265°C.
After heating and residence for 15 minutes, the flow rate was measured. 265℃
The flow rate after 5 minutes of residence at 265°C (hereinafter referred to as FR ₅ ) was 80 g/10 minutes, and the flow rate after 15 minutes of residence at 265°C (hereinafter referred to as FR ₁₅ ) was 150 g/10 minutes. . Comparative Example 3 A polymer obtained by polycondensing TBA/EO, 1,4-butanediol and dimethyl terephthalate by transesterification contained 7.4% bromine,
[η]; 123 parts of copolyester of 0.8, 11 parts of antimony trioxide, glass fiber (Glasron MA-03
-419) 58 parts were kneaded and pelletized in the same manner as in Comparative Example 1. The resulting resin composition is TS; 900Kg/cm ² , II;
It showed 6Kg·cm/cm, HDT: 180°C, and flammability V-O. Comparative Example 4 In Comparative Example 1, when the flame retardant was changed to FR-C, TS: 1200 Kg/cm ² , II: 7 Kg·cm/cm, and combustibility VO was shown. Example 1 In Comparative Example 2, a part of the flame retardant FR-B was brominated with an epoxy equivalent of 1654 and a bromine content of 51% obtained by the reaction of tetrabromobisphenol A diglycidyl ether and tetrabromobisphenol A. It was carried out by replacing it with an epoxy resin (hereinafter referred to as X). That is, FR-B was 16 parts and X was 7 parts.
The resulting resin composition is TS: 1350Kg/cm ² , II: 9Kg・
cm/cm, HDT: 210°C, showed flammability V-O.
Further, the decrease in melt viscosity due to retention was small, with FR ₅ : 60 g/10 minutes and FR ₁₅ : 75 g/10 minutes (the larger the FR number, the lower the melt viscosity of the resin). Comparative Example 5 In Example 4, when all flame retardants were changed to X, TS: 1200Kg/cm ² , II: 7Kg・cm/cm,
HDT: 208°C, showed flammability V-O. or,
The initial melt viscosity was very high at FR ₅ ; 14 g/10 min, and the FR ₁₅ after residence was 1 g/10 min, which is presumed to be due to a three-dimensional crosslinking reaction of the brominated epoxy resin, making injection molding very difficult. It became difficult. Example 2 In Comparative Example 2, 0.3 part of silane coupling agent A-187 (γ-glycidoxy propyltrimethoxysilane) from Nippon Unicar Co., Ltd. was used.
TS: 1300Kg/cm ² , II: 8Kg・cm/cm, Flammability V
- Showed O. Example 3 In Comparative Example 2, when 4 parts of flaky diphenylmethane-4,4'-diisocyanate was used in combination, TS: 1340 Kg/cm ² , II: 8 Kg cm/cm, and flammability V-O was shown. . Comparative Example 6 In Example 3, when carried out without adding the flame retardant FR-B, TS: 1450Kg/cm, II: 9Kg・
cm/cm, showed flammability HB.

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Claims (1)

[Scope of Claims] 1. The following (a) and (b) are added to 100 parts by weight of polyalkylene terephthalate obtained using a glycol having 2 to 4 carbon atoms, and (e) as necessary.
5 to 60 parts by weight of a halogen-containing polyester flame retardant with a halogen content of 10% by weight or more obtained by reacting with or/and (d) in combination, and 0.5 parts by weight of an inorganic flame retardant aid.
30 parts by weight and 0.1 to 30 parts by weight of an epoxy compound or a polyfunctional isocyanate compound. A flame-retardant polyester resin composition having high strength, heat resistance, and good moldability. Record [R: Alkylene _group Acid (c) Glycol (d) At least one selected from tricarboxylic acid, tetracarboxylic acid, triol, and tetraol.
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