JPS634587B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a flame-retardant ABS resin composition with excellent balance between heat resistance and fluidity. Conventionally, methods of mixing organic halogen compounds and inorganic flame retardant aids with resins have been known for the purpose of making them flame retardant, but these methods yield resin compositions with high oxygen indexes, such as those specified by the U.S. UL standards. It shows excellent flame retardancy even when subjected to tests. However, ABS resin is a highly flammable resin with a low oxygen index, and in order to make it flame retardant, it was necessary to add an extremely large amount of flame retardant. Specific examples of conventional flame retardants added to these are 2,2-bis-(3,5-dibromo-4-
hydroxyphenyl)-propane, 1,2-bis-(2,4,6-tribromophenoxy)-ethane, 2,2-bis-[4-(2,3-dibromopropoxy)-3,5 Examples include -dibromophenyl]-propane and 2,2-bis-[4-(2-bromoethoxy)-3,5-dibromophenyl]-propane, and antimony trioxide is an example of an inorganic compound. Widely used as a flame retardant. However, when large amounts of these flame retardants are used, although the fluidity of the resin is improved, the heat resistance is reduced, which poses a problem in practicality. In addition, from the viewpoint of the fluidity of the resin, flame retardants with very high melting points are not preferable, and low molecular weight organic halogen compounds with melting points of about 250°C or less are preferable, but this has the contradictory property of reducing heat resistance. There is. Flame-retardant ABS resin is often used in household electrical appliances, etc., and some electrical equipment is used at relatively high temperatures.
ABS resins are often required to have heat resistance, and are required to have heat resistance without reducing fluidity. Generally, for the purpose of improving the heat resistance of flame-retardant ABS resins, low molecular weight organic halogen compounds with extremely high melting points and high molecular weight organic halogen compounds with high softening temperatures are used. However, even though the heat resistance is improved, the fluidity of the resin is insufficient, so when injection molding it is necessary to maintain the resin temperature at a high temperature, but in this case the flame retardant will thermally decompose, so the molded product Not only does this have an undesirable effect on the hue and surface condition of the molding machine, but in severe cases it also causes corrosion of the screw, cylinder, mold, etc. of the molding machine. Furthermore, organic halogen compounds inherently have poor thermal stability, and this tendency is further exacerbated by the addition of flame retardant aids such as antimony trioxide. In order to prevent this phenomenon, there is a method of adding a lubricant to give fluidity. However, this is not preferable because the flame retardancy of the ABS resin will be greatly reduced. The purpose of the present invention is to solve these drawbacks, and the purpose of the present invention is to add an ABS resin containing a high-molecular weight organic halogen compound with a high softening temperature to a melting point of 250.
The aim is to provide a flame-retardant ABS resin composition that satisfies flame retardancy and has an excellent balance between heat resistance and fluidity by blending a low molecular weight organic halogen compound with a molecular weight lower than about 0.degree. That is, the present invention provides the general formula 10 to 90% by weight of a compound represented by the general formula Compounds represented by and/or general formula A mixture of 90 to 10% by weight of the compound represented by 5 to 40
It is characterized by being blended with 100 parts by weight of ABS resin. [However, in the formula, X is -O-, -CO
--, --SO ₂ --, --OR ¹ O -- (R ¹ is an alkyl group having 1 to 4 carbon atoms),

[Formula] (R ² and R ³ are alkyl groups having 1 to 4 carbon atoms or hydrogen), -CH=CH- or -
(CH ₂ ) _n - (m is an integer of 1 to 4), Y is an integer of 1 to 4
Br or Cl, Z is hydrogen, OH, -OR ⁴ (R ⁴ is OH,
an alkyl group having 1 to 4 carbon atoms containing or not containing Br or Cl), -OCH ₂ CH=CH ₂ , Br or Cl, n represents an integer of 2 to 20] The present invention will be described in more detail below. In the present invention, the softening temperature of the compound represented by the general formula [] and/or [] is higher than around 150°C, and the melting point of the compound represented by the general formula [] is lower than around 250°C, so these are used in ABS resin. When added to a flame retardant, its heat resistance does not deteriorate and its fluidity improves, but if it is further combined with a flame retardant aid such as antimony trioxide, an even better flame retardant effect can be achieved. Next, the general formulas [], []
Specific examples of the compounds represented by and [ ] and preferred combinations thereof are as follows. The compound of general formula [] is 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane,
1,2-bis-(2,4,6-tribromophenoxy)-ethane, 2,2-bis-[4-(2,3
-dibromopropoxy)-3,5-dibromophenyl]-propane, 2,2-bis-[4-(2-
Bromoethoxy)-3,5-dibromophenyl]
-propane, hexabromodiphenyl oxide, the compound of general formula [] is polydibromophenylene oxide, and the compound of general formula [] is 2,2-bis-(3,5-dibromo-4-
Hydroxyphenyl-propane is a polycarbonate whose constituent unit is propane. Regarding the combination of compounds of the general formula [] and [] and/or [], 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane and polydibromophenylene oxide and/or ,2-bis-
(3,5-dibromo-4-hydroxyphenyl)
-Polycarbonate with propane as a constituent unit,
1,2-bis-(2,4,6-tribromophenoxy)-ethane and polydibromophenylene oxide and/or 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)- Polycarbonates containing propane as a constituent unit are preferred, but are not limited thereto. Further, as long as these compounds have the same general formula, two or more of these compounds may be used in combination in each general formula. In the present invention, the amount of the low molecular weight organic halogen compound represented by the general formula [] and the high molecular weight organic halogen compound represented by the general formula [] and/or [] is 90 to 10% by weight of the former, and 10 to 10% by weight of the latter. 90
% by weight, preferably 80-20% by weight of the former and 20-80% by weight of the latter. If it is outside this range, it is unfavorable in terms of the balance between heat resistance and fluidity. In the present invention, 5 to 40 parts of the above organic halogen compound is added to 100 parts by weight of ABS resin.
It is preferable to blend the resin in parts by weight, preferably 10 to 35 parts by weight. If it is less than 5 parts by weight, the flame retardant effect will be insufficient, and if it exceeds 40 parts by weight, the strength of the resin will decrease. The ABS resin used in the present invention includes nitrile monomers such as acrylonitrile and methacrylonitrile,
Diene monomers such as butadiene, isoprene, chloroprene, styrene monomers such as styrene, α-methylstyrene, vinyltoluene, and in some cases methyl methacrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate It is a composite resin consisting of a rubber component and a resin component, which contains ester monomers such as ester monomers as structural units. The rubber component does not have to consist only of diene monomers, but may be a copolymer of these and other monomers copolymerizable with them. ABS resin is not particularly limited by its manufacturing method, including emulsion polymerization, suspension polymerization,
It may be produced by a polymerization method such as a bulk polymerization method, or a combination of these methods. It is also possible to use ABS resin with a high rubber component content diluted with separately manufactured AS resin. In the present invention, antimony trioxide, metastannic acid, magnesium stannate, zinc stannate, barium stannate, zinc borate, magnesium borate, barium borate, etc. can be used alone or in combination as the inorganic flame retardant aid. These inorganic compounds are preferably contained in an amount of 20 parts by weight or less, particularly 0.5 to 10 parts by weight, based on 100 parts by weight of the ABS resin. If it exceeds 20 parts by weight, the strength of the resin decreases, which is not preferable. There are no particular restrictions on the method of mixing the organic halogen compound, inorganic flame retardant aid, and ABS resin, and known methods and devices can be used. To explain the mixing method, the organic halogen compound, inorganic flame retardant aid, and ABS resin are mixed using a Henschel mixer, etc., and then melt-kneaded using a Banbury mixer, intensive mixer, mixtruder, co-kneader, extruder, roll, etc. A method of directly melting and kneading without going through the mixing process with a Henschel mixer, etc., and a method of directly melting and kneading without going through the mixing process with a Henschel mixer, etc., and a method of directly melting and kneading without going through the mixing process with a Henschel mixer etc.
There is a method in which a master batch with a high flame retardant content is created by melting and kneading the resin, and then mixed with ABS resin again. An example of this method is to mix using a mixer or the like and melt-mix this with ABS resin. Furthermore, in the present invention, it is also possible to add other additives, such as pigments, dyes, stabilizers, dispersants, reinforcing materials, fillers, weathering agents, antistatic agents, foaming agents, and lubricants. be. As explained above, the present invention is an ABS resin composition containing a specific high molecular weight organic halogen compound and a low molecular weight halogen compound, and a molded product made from this composition has high heat resistance and is difficult to deform due to heat. Not only that, its excellent moldability suppresses external defects such as partial or total discoloration and/or flashing, and also prevents corrosion of the screws, cylinders, molds, etc. of the molding machine. It is difficult to mold, so it can be suitably used for molding parts of household appliances, etc. This effect is achieved by using a high molecular weight organic halogen compound with a high softening temperature and a low molecular weight halogen compound with a low melting point, combining the heat resistance improving effect of the high molecular weight halogen compound and the lubricity effect of the low molecular weight halogen compound. This can only be achieved by combining them. The present invention will be further explained below with reference to Examples. However, all parts and percentages described in the examples are expressed on a weight basis. Example 1 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane and polydibromophenylene oxide were added to 100 parts of ABS resin consisting of 21% acrylonitrile, 22% butadiene, and 57% styrene. were added in the amounts shown in Table 1, and 4 parts of antimony trioxide were added, mixed in a Henschel mixer, and melt-kneaded in an extruder to obtain pellets. The results are shown in Table 1 Experiment Nos. 1 to 9. In addition, in the tables of Examples and Comparative Examples, the following abbreviations were used for organic halogen compounds. A: 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane B: 2,2-bis-[4-(2,3-dibromopropoxy)-3,5-dibromophenyl ]-Propane C: 2,2-bis-[4-(2-bromoethoxy)-3,5-dibromophenyl]-Propane D: 1,2-bis-(2,4,6-tribromophenyl) c)-Ethane E: Hexabromodiphenyl oxide F: Polydibromo phenyl oxide (n=
4) G: Polycarbonate containing 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane as a constitutional unit (n=4 to 6) H: 2,2-bis-(3,5 -Dibromo-4-hydroxyphenyl)-polycarbonate with propane as a constituent unit (n=20) Example 2 To 100 parts of the ABS resin used in Example 1, the organic halogen compound shown in Table 2 was added, and further Pellets were obtained by adding 4 parts of antimony trioxide. The results are shown in Table 2 Experiment Nos. 10 to 17. Example 3 The same procedure was carried out as for the sample of Experiment No. 5 of Example 1 except that the amount of antimony trioxide added was changed. The results are shown in Table 3 Experiment Nos. 18-22. Example 4 Consisting of 19% acrylonitrile, 22% butadiene, 55% styrene, 4% butyl acrylate
2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane, 100 parts of ABS resin,
and polydibromophenylene oxide, 10 each
Then, 4 parts of antimony trioxide was added to obtain pellets. This resin had a melt flow index of 6.6 g/10 minutes, a heat deformation temperature of 86° C., an Izot impact strength of 12 Kgcm/cm, and a flame retardance of VO. Comparative Example 1 The organic halogen compounds shown in Table 4 were added to 100 parts of the ABS resin used in Example 1, and 4 parts of antimony trioxide were further added to obtain pellets. The results are shown in Table 4 Experiment Nos. 23-32. Comparative Example 2 To the sample of Experiment No. 28 of Comparative Example 1, 7 parts of ethylene bisstearamide (lubricant) was added. This resin had a melt flow index of 3.4 g/10 minutes, a heat deformation temperature of 84° C., an Izot impact strength of 17 Kgcm/cm, and a flame retardance of V-2 failure. Example 5 and Comparative Example 3 Experiment No. 5 of Example 1 and Experiment No. 28 of Comparative Example 1
A cassette tape housing was molded using a 5-ounce injection molding machine using the sample. experiment
In sample No. 5, a satisfactory molded product was obtained at a molding temperature of 220°C. On the other hand, the sample in Experiment No. 28 could not be molded at the same temperature, so the molding temperature was raised to 260°C. The resulting molded product had significant partial discoloration and flashing, and also had a strong odor during molding.

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[Table] (Note: Data marked with * in Table 4 indicates unfavorable values)
The physical properties shown in the Examples and Comparative Examples of the present invention were determined by the following method. 1 Melt flow index...JIS K7210 compliant. However, the temperature is 220℃ and the load is 5Kg. 2 Heating deformation temperature...JIS K7207 compliant. Bending stress 18.5Kg/cm ² . No annealing 3 Flame retardancy: UL (Underwriters Laboratory) 94 vertical combustion test method.

Claims (1)

[Claims] 1. General formula [] 10 to 90% by weight of a compound represented by the general formula [] Compounds represented by and/or general formula [] A mixture of 90 to 10% by weight of the compound represented by 5 to 40
A flame-retardant ABS resin composition made by blending 100 parts by weight of ABS resin. [However, in the formula, X is -O-,-
CO—, —SO ₂ —, —OR ¹ O— (R ¹ has 1 to 4 carbon atoms
(alkyl group), [Formula] (R ² and R ³ are alkyl groups having 1 to 4 carbon atoms or hydrogen), -CH=CH- or -(CH ₂ )m ^- (m is an integer of 1 to 4), Y is 1 to 4 Br or Cl, Z is hydrogen, OH,
-OR ⁴ (R ⁴ is an alkyl group having 1 to 4 carbon atoms containing or not containing OH, Br or Cl), -OCH ₂ CH=
CH ₂ Br or Cl, n is an integer from 2 to 20. ] 2 The compound represented by the general formula [] is 2,2-
Bis-(3,5-dibromo-4-hydroxyphenyl)-propane, 1,2-bis-(2,4,6
-tribromophenoxy)-ethane, 2,2-bis-[4-(2,3-dibromopropoxy)-
3,5-dibromophenyl]-propane, hexabromodiphenyl oxide and 2,2-bis-
The flame-retardant ABS resin composition according to claim 1, which is selected from [4-(2-bromoethoxy)-3,5-dibromophenyl]-propane. 3. The flame-retardant ABS resin composition according to claim 1, wherein the compound represented by the general formula [] is polydibromophenylene oxide. 4 The compound represented by the general formula [] is 2,2-
The flame retardant according to claim 1, which is a polycarbonate having bis-(3,5-dibromo-4-hydroxyphenyl)-propane as a constituent unit.
ABS resin composition. 5 The combination of compounds represented by the general formulas [], [] and [] is 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane and polydibromophenylene oxide and/or 2 , 2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane as a constituent unit or 1,2-bis-(2,
4,6-tribromophenoxy)-ethane and polydibromophenylene oxide and/or 2,2
The flame-retardant ABS resin composition according to claim 1, which is a mixture of polycarbonates having -bis-(3,5-dibromo-4-hydroxyphenyl)-propane as a constituent unit.