JPH0212979B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to flame retardant resin compositions. More specifically, the present invention relates to a flame-retardant resin composition containing a polycarbonate oligomer obtained from brominated bisphenols and a specific brominated monoepoxy compound as a flame retardant. Thermoplastic polyesters, represented by polyethylene terephthalate, polybutylene terephthalate, etc., are widely used in electrical and electronic parts, mechanical parts, automobile parts, etc. due to their excellent mechanical, electrical, and thermal properties. ing. Incidentally, in addition to the above properties, flame retardancy is also strongly required for these uses, and attempts to make thermoplastic polyester flame retardant have been made for a long time. Halogen compound flame retardants are mainly used to make thermoplastic polyester flame retardant, but these flame retardants generally have low heat resistance, cause coloring or deterioration of the physical properties of the resin, or are difficult to heat when heated. It sometimes deposits on the surface of the resin (cheeking), resulting in poor appearance and corrosion of the contacts of electrical parts. For example, when a halogen compound having an active group such as a hydroxyl group or a carboxyl group is blended into polyethylene terephthalate, the viscosity of the polymer decreases significantly, and when a halogen compound with a relatively low molecular weight such as hexabromobenzene or decabromodiphenyl ether is blended. During injection molding, sublimated products of these compounds adhere to the surface of the mold and molded product, greatly reducing the product value. Examples of flame retardants that have a relatively high molecular weight and therefore do not cause the yoking phenomenon include polycarbonate oligomers obtained from brominated bisphenols (e.g., JP-A-48-52884, JP-A-Sho 48-52884;
49-14568, etc.) and diglycidyl ether compounds obtained from brominated bisphenols (e.g., Japanese Patent Publication No. 53-18068, Japanese Patent Publication No. 53-11017, etc.)
is typical. When the former is added to a thermoplastic polyester, it is accompanied by a decrease in toughness and greatly reduces the heat resistance stability during molding. Moreover, the latter has the disadvantage that its moldability is not quite satisfactory, and that it is accompanied by coloring or gelation, especially when the molding temperature is high. As a result of intensive studies to find flame retardants free from such disadvantages, the present inventors found that polycarbonate oligomers obtained from brominated bisphenols, specific brominated monoepoxy compounds, and specific organometallic compounds were selected from the group consisting of polycarbonate oligomers obtained from brominated bisphenols. The present invention was achieved by discovering that a compound containing a specific proportion of the compound is an excellent flame-retardant resin composition that has high toughness, improved heat resistance, and does not cause yoking. That is, the present invention comprises (A) thermoplastic polyester, (B) general formula () [However, in the formula, R ₁ is an alkyl group or a bromine atom, p is 0 or an integer of 1 to 5, and m
is a number of 2 or more, and n is a number of 0 or 1 or more, satisfying 2m+n40. ] Compound (C) having a carbonate unit represented by general formula () [However, in the formula, R ₂ is an alkyl group or a bromine atom, k is 0 or an integer of 1 to 5,
R ₃ and R ₄ are each hydrogen or methyl group,
q represents the average degree of polymerization and is a number from 1 to 10. ] Monoepoxy compound (D) A composition consisting of one or more compounds selected from the group consisting of calcium stearate, sodium terephthalate, and sodium montanate, per 100 parts by weight of component (A).
1 to 50 parts by weight of component (B) and 0.01 to 2 parts by weight of component (D), and the weight ratio of component (B) to component (C) is 1:0.01 to
The present invention relates to a flame retardant resin composition characterized in that the ratio is 1:5. The thermoplastic polyester of component (A) used in the present invention is a polyester consisting of a dicarboxylic acid component and a diol component, or a polyester consisting of an oxycarboxylic acid component or this and a diol component, particularly terephthalic acid or 2,6-naphthalene dicarboxylic acid component. Polyalkylene terephthalate or polyalkylene naphthalate obtained from an acid component and an aliphatic glycol component having 2 to 6 carbon atoms is preferably used. Of course, polyesters other than the above-mentioned polyalkylene terephthalate or polyalkylene naphthalate can also be used, such as polyesters obtained by copolymerizing these with other third components, or polyesters obtained by combining other dicarboxylic acids or diols. Among these polyesters, preferred are polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and those copolymerized with another third component, and particularly preferred are polyethylene terephthalate and polybutylene terephthalate. These polyesters have an intrinsic viscosity of 0.4
Above, more preferably 0.5 or more. The compound (B) component used as a flame retardant in the present invention is a polycarbonate oligomer obtained from brominated bisphenols, that is, the general formula () [However, in the formula, R ₁ is an alkyl group or a bromine atom, p is 0 or an integer of 1 to 5, and m is 2
The above numbers and n are 0 or 1 or more, and 2
Satisfies m+n40. ] It is a compound having a carbonate unit shown in the following. This compound is usually obtained by reacting and polymerizing halogenated bisphenol A or a mixture of this and bisphenol A, a carbonate precursor (for example, phosgene, diphenyl carbonate, etc.), and a phenol compound. m+n represents the average degree of polymerization of the compound, and is preferably in the range of 2 to 40, more preferably 3 to 30. Since the flame retardant effect mainly depends on the halogenated bisphenol component, that is, m, it is desirable that m>n. The brominated epoxy compound of component (C) used in the present invention has the general formula () [However, in the formula, R ₂ is an alkyl group or a bromine atom, k is 0 or an integer from 1 to 5, and R ₃ ,
R ₄ is hydrogen or a methyl group, and q is an average degree of polymerization and is an integer from 1 to 10. ] It is a monoepoxy compound represented by brominated bisphenol A diglycidyl ether and brominated phenol or brominated alkyl, which is usually obtained from tetrabromobisphenol A and epihalohydrin such as epichlorohydrin or methyl epihadohydrin. Phenol can be obtained by heating reaction at 80 to 25°C using a catalyst such as an alkali metal hydroxide, halide, or tertiary amine. Furthermore, using brominated phenol glycidyl ether or brominated alkylphenol glycidyl ether as a starting material, brominated bisphenol A is added thereto, and then a glycidyl etherification reaction is carried out using epihalohydrin and sodium hydroxide or potassium hydroxide. Alternatively, it can also be obtained by addition reaction with brominated bisphenol A diglycidyl ether. In the general formula (), R ₂ is preferably a bromine atom. It is preferable that k is 1-5, more preferably 2-3. Furthermore, q represents the average degree of polymerization and must be in the range of 1 to 10, preferably 1 to 5. The amount of these flame retardants added is 1 to 50 parts by weight of component (B) per 100 parts by weight of thermoplastic polyester component (A).
Preferably it is 3 to 30 parts by weight, and the amount of component (C) added is such that the weight ratio of component (B) to component (C) is 1:0.01 to 1:5.
must be within the range. More preferably, the weight ratio of component (B) to component (C) is in the range of 1:0.1 to 1:2. In this weight ratio, the amount of component (C) is 1:0.01
If the amount is less than 1, the objective of the present invention, which is to improve toughness and heat resistance, will be impaired, which is not preferable. on the other hand
Even if the ratio of component (C) exceeds 1:5, it is not preferable because a decrease in toughness is observed. Component (D) used in the present invention is an organic acid metal salt such as calcium stearate, sodium terephthalate, and sodium montanate. The addition ratio of component (D) is per 100 parts by weight of component (A).
The amount is 0.01 to 2 parts by weight, preferably 0.02 to 1 part by weight. (D) If the amount of component added is less than 0.01 part by weight, the heat resistance improving effect is insufficient, and if it exceeds 2 parts by weight, no heat resistance improving effect is observed.
This is not preferable because it causes foaming etc. during molding. Other additives can be added to the flame-retardant resin composition of the present invention as long as they do not impair the purpose of the present invention. In particular, it is desirable to add a compound of a group B metal of the periodic table to the composition of the present invention for the purpose of further improving flame retardancy. Particularly preferred as this compound is an antimony compound. The antimony compound is preferably one that does not decompose or react with other compounds in the system at temperatures below 300°C, and antimony trioxide is particularly preferred. The amount added is suitably in the range of 10 to 200 parts by weight based on 100 parts by weight of the total weight of components (B) and (C). Further, it is desirable to add a phosphorus compound to the composition of the present invention in order to further improve the melt stability of the resin. Phosphorus compounds include phosphoric acid, trimethyl phosphate, dimethylethyl phosphate,
Phosphate esters such as triethyl phosphate, triisopropyl phosphate, tributyl phosphate, triphenyl phosphate, tribenzyl phosphate, tricyclohexyl phosphate, etc., phosphorous acid, triethyl phosphite, trimethyl phosphite, triethyl phosphite ,
Triphenyl phosphite, tris(2,4-di-t)
Phosphite esters such as -butylphenyl) phosphite; phosphoric acid derivatives such as phenylphosphonic acid, phenyl phenylphosphonate, and the like. These phosphorus compounds are 1
Only seeds may be used or two or more types may be used. The amount of phosphorus compound added is 0.01 to 5 parts by weight of component (D).
A range of parts by weight is desirable. Although it is possible to add these phosphorus compounds at the same time when producing the composition of the present invention, a particularly preferred method is
This is a method in which the components (A), (B), (C), and (D) are preliminarily mixed by heating and melting, and then the phosphorus compound is added. Furthermore, additives that can be blended into the flame-retardant resin composition of the present invention include fibrous fillers such as glass fibers, carbon fibers, and metal fibers, various inorganic fillers, nucleating agents, lubricants, and antioxidants. , ultraviolet absorbers, colorants, and antistatic agents. Furthermore, other thermoplastic resins may be contained within a range that does not impair the purpose of the present invention. Examples of these thermoplastic resins include polyethylene, polypropylene, ionic copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylic ester copolymers, polystyrene, acrylonitrile-styrene copolymers, and acrylonitrile-butadiene-styrene. Examples include copolymers, polyamides, etc.
In order to further improve the toughness, which is the objective of the present invention, it is effective to add various thermoplastic elastomers. Examples of thermoplastic elastomers include polyurethane elastomers, polyester elastomers, acrylic ester elastomers, and olefin elastomers. The compositions of the invention can be manufactured in a variety of ways. For example, the components may be placed together in an extruder to form moldable pellets. Alternatively, the composition obtained by dry blending each component is molded by direct injection molding or transfer molding. The present invention will be explained in detail with reference to Examples below. Note that parts in the examples are parts by weight. Further, the intrinsic viscosity of polyester was measured at 35°C using orthochlorophenol as a solvent. Examples 1 to 4 and Comparative Examples 1 to 5 Polybutylene terephthalate with an intrinsic viscosity of 1.10
Component (B) and (C) with the structure shown below per 100 parts by weight
Ingredients: Calcium stearate and antimony trioxide (component (D)) are blended in the proportions shown in Table 1,
Cylinder temperature using a 65mmφ vented extruder
Pellets were obtained by melt mixing and extrusion at 240°C. Test pieces suitable for the test methods shown in Table 1 were prepared from the pellets obtained using an injection molding machine at cylinder temperatures of 230°C and 260°C, and each was evaluated.
The results are shown in Table 1. [B] Component: General formula (B ₁ ); m=5, n=0 in the above general formula (B ₂ ); m=5, n=1 in the above general formula [C] component: (Br content 52.5%, softening point 102°C) Table 1 also shows an example in which tetrabromobisphenol A diglycidyl ether (epoxy equivalent 400) was used instead of the flame retardant component [C] as a comparative example. . From the results in Table 1, it is clear that the composition of the present invention has excellent toughness and heat resistance stability.

[Table] Examples 5 to 12 and Comparative Examples 6 to 8 Polybutylene terephthalate with an intrinsic viscosity of 1.03
The flame retardant (B ₁ ) used in Examples 1 to 4, the flame retardant (C), antimony trioxide (5 parts by weight), and the additive (D) shown in Table 2 were blended into 100 parts by weight, and a 65 mm
Pellets for injection molding were prepared using a φ extruder.
This pellet was injection molded and its physical properties were measured. In addition, some of the compositions were injection molded after the pellet surface was sprinkled with the stabilizer shown in Table 2. The results are shown in Table 2. It is clear from Table 2 that the flame retardant composition of the present invention has excellent toughness and heat resistance stability. In particular, when a phosphorus compound is used in combination with the composition of the present invention, the effect of improving heat resistance stability is particularly observed.

【table】

Claims (1)

[Claims] 1 (A) Thermoplastic polyester, (B) General formula () [However, in the formula, R ₁ is an alkyl group or a bromine atom, p is 0 or an integer of 1 to 5, and m
is a number of 2 or more, and n is a number of 0 or 1 or more, satisfying 2m+n40. ] A compound having a carbonate unit represented by (C) General formula () [However, in the formula, R ₂ is an alkyl group or a bromine atom, k is 0 or an integer from 1 to 5,
R ₃ and R ₄ are each hydrogen or methyl group,
q represents the average degree of polymerization and is a number from 1 to 10. ] A monoepoxy compound represented by: and (D) one or more compounds selected from the group consisting of calcium stearate, sodium terephthalate and sodium montanate, the composition comprising: 100 parts by weight of component (A) Hit,
1 to 50 parts by weight of component (B) and 0.01 to 2 parts by weight of component (D), and the weight ratio of component (B) to component (C) is 1:0.01 to
A flame retardant resin composition characterized in that the ratio is 1:5.