JPH04337343A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To obtain a flame-retardant resin composition having excellent dispersibility of a flame-retardant, excellent flame-retardance even by using only a small amount of the flame-retardant and excellent physical properties by adding a specific flame-retardant and an antimony oxide to a polyolefin resin. CONSTITUTION:The objective composition is produced by compounding (A) 70-96wt.% of a polyolefin resin (e.g. high-density polyethylene) with (B) 20-3wt.% of a flame-retardant containing (B1) a halogenated phthalimide derivative of formula (X is Cl or Br; R is 1-12C substituted or unsubstituted hydrocarbon group) [preferably ethylenebis(tetrabromophthalimide)] and (B2) a brominated polystyrene (preferably having >=3 bromine atoms per one styrene unit) at a weight ratio (B1/B2) of (30-70)/(70030) and (C) 10-1wt.% of an antimony oxide (preferably antimony trioxide) as a flame-retarding assistant. The weight ratio (B/C) is (2-4)/1 and the sum of A to C is 100wt.%.

Description

[Detailed description of the invention]

0001

FIELD OF INDUSTRIAL APPLICATION The present invention relates to a flame-retardant resin composition, which can be used, for example, in home appliances, automobile parts, industrial parts, and the like.

0002

[Background Art] Polyolefins such as polypropylene (PP) and high-density polyethylene (HDPE) are excellent in terms of strength, processability, price, etc., so they are not only used for general purposes such as containers and films, but also for industrial use. It is also widely used as a material. Such polyolefins may be required to have flame retardancy depending on the intended use. Therefore, various resin compositions with enhanced flame retardancy have been proposed. For example, JP-A-50-9645 discloses the structure of a flame-retardant thermoplastic resin composition containing one or more halogen-substituted diimide compounds as a flame retardant.

0003

[Problem to be solved by the invention] The above-mentioned Japanese Patent Application Laid-Open No. 1983-1996
The resin composition according to Publication No. 45 has unstable flame retardancy because the halogen-substituted diimide compound has poor dispersibility. Therefore, in order to obtain good flame retardancy, it is necessary to increase the amount added, which causes mesh clogging during kneading, leading to instability in productivity. In addition, when pellets made of this resin composition were injection molded or formed into sheets, white spots from the flame retardant were noticeable and the appearance was poor.

[0004] In order to improve these drawbacks, rubber or a resin having rubber elasticity may be added, for example, PP.
It has also been proposed to create a master batch by adding 40 to 60 wt% of a flame retardant and a flame retardant aid to 60 to 40 wt% of HDPE, but it is still not possible to obtain satisfactory dispersibility of the flame retardant, and Flammability is also unstable. Therefore, the present invention provides good dispersibility of the flame retardant, thereby having excellent flame retardancy, and having excellent physical properties.
It is an object of the present invention to provide a flame-retardant resin composition in which the amount of flame retardant including flame retardant aid can be reduced.

[0005]

[Means and effects for solving the problems] The flame-retardant resin composition according to the present invention is characterized by containing the following components A, B, and C. A: Polyolefin resin 70-96wt
%B: Flame retardant containing the following a and b 20~
3wt%

[Chemical formula 1] b: Brominated polystyrene C: Antimony oxide 10-1w
t% However, A+B+C=100wt%

[0006] The polyolefin resin (A) used in the present invention is not particularly limited and can be appropriately selected depending on the intended use. For example, PP, HD
Examples include PE, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and the like. Also, mixtures of these may be used. If the content of the polyolefin resin is less than 70 wt%, the physical properties, especially elongation, will be significantly lowered, and if it exceeds 96 wt%, the flame retardancy will be significantly lowered.

In the flame retardant (B), specific examples of the halogenated phthalimide derivative represented by Chemical Formula 1 include the following compounds. For example, methylene bis (tetrabromophthalic acid imide), ethylene bis (tetrabromophthalic acid imide), propylene bis (tetrabromophthalic acid imide), butylene bis (tetrabromophthalic acid imide), benzidine bis (tetrabromophthalic acid imide), Methylenebis(tetrachlorophthalimide),
There are ethylene bis (tetrachlorophthalic acid imide), propylene bis (tetrachlorophthalic acid imide), butylene bis (tetrachlorophthalic acid imide), etc. Among these, ethylene bis (tetrabromophthalic acid imide) is particularly
is preferred. The degree of polymerization and bromine content of the brominated polystyrene in the flame retardant (B) are not particularly limited;
Those having three or more bromines per styrene unit are preferred.

[0008] If the content of the flame retardant (B) containing these a and b is less than 3 wt%, the flame retardancy decreases, and even if it is added in excess of 20 wt%, an improvement in flame retardancy is observed. This will increase costs. In addition, a in the flame retardant (B),
The content ratio of b is set to a/b=30 to 70/70 to 30 (weight ratio), but if it is out of this range, sufficient flame retardance will not be obtained. The antimony oxide (C) acts as a flame retardant aid, and specific examples thereof include diantimony trioxide (Sb2O3), diantimony tetroxide (Sb2O4), diantimony pentoxide (Sb2
O5) etc. Among these, diantimony trioxide is particularly preferred. If the content of antimony oxide (C) is less than 1 wt%, the flame retardancy will be lowered, and if it exceeds 10 wt%, the physical properties, especially the tensile elongation rate, will be significantly lowered. The content ratio of the flame retardant (B) and antimony oxide (C) is B/C = 2 to 4/1 (weight ratio),
Outside this range, sufficient flame retardancy cannot be obtained.

The flame retardant resin composition of the present invention contains the above-mentioned A
, B, and C, various additives and fillers may be added. For example, additives include those commonly added to resin molded products, such as antioxidants, lubricants, ultraviolet absorbers, stabilizers, and pigments, and these can be used as appropriate. Further, as the filler, talc, calcium carbonate, precipitated barium sulfate, etc. can be used as appropriate. In addition, the mixing and kneading methods of raw materials when producing the flame-retardant resin composition of the present invention are arbitrary. For example, in addition to the methods described in the examples below, polyolefin resin (A), flame retardant (B)
, antimony oxide (C) are mixed and kneaded to prepare a masterbatch, and a polyolefin resin (A) is blended therein in an amount of 5 to 15 times the amount of the masterbatch to finally produce the resin according to the present invention. A composition may also be manufactured.

0010

Examples Examples 1 to 5 First, the following raw materials were mixed in the proportions shown in Table 1 to obtain resin pellets comprising the flame retardant resin compositions according to each example. The kneader used here is a Warner type PCM 45 mm twin-screw kneader manufactured by Ikegai Tekko Co., Ltd. The rotation speed of the screw is 150 rpm, and the cylinder temperature during molding is 230°C and 250°C from the hopper side to the die side.
, 230℃, 220℃, 220℃, (Dice) 220℃
distribution. The density and melt index (MI) of the resin composition according to each example are shown in Table 1. Note that this MI is 190°C for HDPE resin.
, measured under the condition of load 2160g, and HDPE/PP
The system and PP resin were measured under the conditions of 230° C. and a load of 2160 g. In addition, in the table, polyolefin resin, flame retardant, and flame retardant aid are shown in wt% in the blending amount of each raw material,
The parts by weight of the dispersant and antioxidant are based on the total of the above three parts being 100 parts by weight.

Polyolefin resin...HDPE (MI=0.25)
Halogenated phthalic acid imide derivative of chemical formula 1...the following chemical compound 2
Cytex BT-93 (trade name, manufactured by Ethyl Corporation, substance name: 1,2-bis(tetrabromophthalimide)ethane) shown in

[Chemical formula 2] Brominated polystyrene...Pyrocheck 68PB shown in Chemical formula 3 below [trade name, manufactured by Nissan Ferro Organic Chemical Co., Ltd.]

[
Chemical 3]

Antimony oxide...Diantimony trioxide (Sb2O
3) Dispersant... Cadenax GS90 [Product name, Lion (
Co., Ltd., substance name: Glycerin Monostearate] and Rheostat T-60 [Product name, Lion Co., Ltd., substance name: Sorbitan Monostearate] Antioxidant...Mark 2112 [Product name, Adeca Argus ( manufactured by Asahi Denka Co., Ltd., substance name: tris(2,4 di-t-butylphenyl) phosphite] and mark AO-60 [trade name, manufactured by Asahi Denka Co., Ltd., substance name: tetrakis-[methylene-
3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane

0013
Next, test pieces made of the resin compositions of each example were prepared and subjected to a tensile test, a bending test, and an IZOD test.
An impact test was conducted on each. The tensile test is AST
Tensile strength, tensile modulus, and tensile elongation were measured in accordance with MD638. The bending test is
Bending strength and flexural modulus were measured in accordance with ASTM D790. The Izod impact test
In accordance with TMD256, measurements were made for those with and without a notch. The results are shown in Table 1. In the table, NB in the Izod impact test column means non-break (not destroyed).

Next, using the resin pellets of each example, a plate (3.2 mm x 80 m
m x 80 mm) and film (thickness 20-50 μm, 5
0 mm x 50 mm). The injection molding machine used for producing the plate was FS150 manufactured by Nissei Jushi Kogyo Co., Ltd.
(product name). The cylinder temperature during molding is 190℃, 200℃, 210℃, (
Dice) had a distribution of 200°C. The molding machine used for film production was a 50t compression molding machine manufactured by Toho Kikai Kogyo Co., Ltd., and the heater temperature was 200°C. In addition, two types of test pieces (3.2 mm x 12.7 mm x 12
7mm and 1.6mm x 12.7mm x 127mm
) was created. The injection molding machine used was FS50 (trade name) manufactured by Nissei Jushi Kogyo Co., Ltd. The cylinder temperature during molding is 190℃ and 20℃ from the hopper side to the die side.
It had a distribution of 0°C, 210°C, and (dice) 200°C.

Next, the dispersion state of the flame retardant was determined using these plates and films, and a combustion test was conducted using the two types of test pieces. The results are shown in Table 1 below.
Shown below. These dispersion determination methods and combustion test methods are as follows. Dispersion Judgment Method (1) Dispersion judgment using an injection plate was performed by counting how many white spots (agglomerates due to poor dispersion of the flame retardant) with a diameter of 0.1 to 0.5 mm were observed on the plate. (2) Dispersion determination using a press film was performed by counting the number of white spots present in the film as in the case of the plate. In these dispersion evaluations, 0 to 5 white points were evaluated as ◯, 6 to 30 white points as △, and 31 or more white points as ×. Combustion test method This combustion test method is based on the U.S. UL (Underwrite)
rs Laboratories Inc. ) The test was conducted based on the UL94 vertical test (V). Its flammability ranges from poor to good: HB,
Evaluation is divided into four stages: V-2, V-1, and V-0. Note that the thinner the test piece is, the more easily it burns, so the conditions become stricter.

[Table 1]

Comparative Examples 1 to 4 In the same manner as in the above Examples, various physical property tests were conducted on the resin compositions of each Comparative Example, and flame retardant dispersion determination and combustion tests were also conducted. The results are shown in Table 2 below. however,
As shown in Table 2, the raw materials and blending ratios used were different for each comparative example. That is, in Comparative Example 1, only a halogenated phthalimide derivative was used among the flame retardants, and in Comparative Example 2, only brominated polystyrene was used. Also,
In Comparative Examples 3 and 4, the amount of at least one of the polyolefin resin, flame retardant, and antimony oxide was outside the range according to the present invention.

[Table 2]

Discussion of Examples and Comparative Examples According to Examples 1 to 5 above, the test pieces made of the flame-retardant resin compositions of each example showed the results of the tensile test, bending test, and Izod impact test, respectively. It has good physical properties. In addition, in the dispersion evaluation of the flame retardant, the plates and films made of the resin compositions according to each example showed almost no white spots indicating aggregates due to poor dispersion of the flame retardant, indicating that the flame retardant was present in the plate or in the film. It can be seen that the particles are well dispersed. Because the flame retardant was well dispersed in the plate or film, the two types of test pieces made of the resin compositions according to each example showed flame retardant properties, as shown by the results of the combustion test. have.

On the other hand, according to Comparative Example 1, only a halogenated phthalic acid imide derivative was used among the flame retardants, and brominated polystyrene was not added. Both the plate and the film had many conspicuous white spots, indicating that the flame retardant was not well dispersed in the plate or film. Furthermore, the tensile elongation rate is low. According to Comparative Example 2, of the flame retardants, only brominated polystyrene was used and no halogenated phthalimide derivative was added, so the plate and film made of the resin composition according to this comparative example were white. The dots are noticeable, indicating that the flame retardant is not well dispersed in the plate or film. According to Comparative Example 3,
Since the blending amount of the polyolefin resin was higher than the range according to the present invention, and the blending amount of the flame retardant and antimony oxide was lower than the range according to the present invention, the flame retardance was poor. According to Comparative Example 4, the blending amount of the polyolefin resin was lower than the range according to the present invention, and the blending amount of antimony oxide was higher than the range according to the present invention, so the dispersion judgment and flame retardancy were good. However, there were problems with tensile elongation and Izod impact strength.

Examples 6 to 13 Flame-retardant resin compositions according to each example were produced in the same manner as in Examples 1 to 5 above, and these resin compositions were subjected to physical property tests similar to those in the above Examples. , flame retardant dispersion determination and combustion test were conducted. The results are shown in Tables 3 and 4 below. however,
As shown in Tables 3 and 4, the raw materials and blending ratios used were different for each example. That is, in these Examples, PP and HDPE were used as the polyolefin resins.

Comparative Examples 5 to 7 Flame-retardant resin compositions according to each comparative example were produced in the same manner as in Examples 6 to 13 above, and these resin compositions were subjected to physical property tests similar to those in the above Examples. , flame retardant dispersion determination and combustion test were conducted. The results are shown in Table 4 below. However, as shown in Table 4, the raw materials and blending ratios used were different for each comparative example. That is, in Comparative Example 5, among the flame retardants,
Only halogenated phthalimide derivatives were used, and in Comparative Example 6, only brominated polystyrene was used. Furthermore, in Comparative Example 7, the amount of at least one of the polyolefin resin, flame retardant, and antimony oxide was outside the range according to the present invention.

[Table 3]

[Table 4]

Discussion of Examples and Comparative Examples According to Examples 6 to 13 above, the test pieces made of the flame-retardant resin compositions of each example showed the results of the tensile test, bending test, and Izod impact test, respectively. It has good physical properties. In addition, in the plates and films made of the resin compositions according to each example, almost no white spots were observed in the flame retardant dispersion evaluation, indicating that the flame retardants were well dispersed in the plates or films. . Because the flame retardant was well dispersed in the plate or film, the two types of test pieces made of the resin compositions according to each example showed flame retardant properties, as shown by the results of the combustion test. have.

On the other hand, according to Comparative Example 5, only a halogenated phthalic acid imide derivative was used among the flame retardants, and no brominated polystyrene was added, so that the resin composition according to this comparative example The resulting plate and film each had many conspicuous white spots, indicating that the flame retardant was not well dispersed in the plate or film, and the flame retardancy was also poor. According to Comparative Example 6, among the flame retardants, only brominated polystyrene was used and no halogenated phthalimide derivative was added, so the plate and film made of the resin composition according to this comparative example were white. The dots are conspicuous, indicating that the flame retardant is not well dispersed in the plate or film, and the flame retardancy is also poor. According to Comparative Example 7, the blending amount of the polyolefin resin and antimony oxide is lower than the range according to the present invention, and the blending amount of the flame retardant is higher than the range according to the present invention, so the dispersion judgment and flame retardancy are good. However, there were problems with tensile elongation and impact properties.

Examples 14 and 15 Flame-retardant resin compositions according to each example were produced in the same manner as in Examples 1 to 5 above, and the same physical property tests as in the above Examples were conducted using these resin compositions. , flame retardant dispersion determination and combustion test were conducted. The results are shown in Table 5 below. However, Table 5
As shown in , the raw materials used and the blending ratios were different for each example. That is, in these Examples, PP was used as the polyolefin resin.

Comparative Examples 8 to 10 Flame-retardant resin compositions according to each comparative example were produced in the same manner as in Examples 14 and 15 above, and the same physical property tests as in the above Examples were conducted using these resin compositions. , flame retardant dispersion determination and combustion test were conducted. The results are shown in Table 5 below. however,
As shown in Table 5, the raw materials and blending ratios used were different for each comparative example. That is, in Comparative Example 8, only a halogenated phthalimide derivative was used among the flame retardants, and in Comparative Example 9, only brominated polystyrene was used. Also,
In Comparative Example 10, the amount of at least one of the polyolefin resin, flame retardant, and antimony oxide was outside the range according to the present invention.

[Table 5]

Discussion of Examples and Comparative Examples According to Examples 14 and 15 above, the test pieces made of the flame-retardant resin compositions of each example showed the results of the tensile test, bending test, and Izod impact test, respectively. It has good physical properties. In addition, the plates and films made of the resin compositions according to each example were evaluated for dispersion of flame retardants.
Almost no white spots were observed, indicating that the flame retardant was well dispersed in the plate or film. Because the flame retardant was well dispersed in the plate or film, the two types of test pieces made of the resin compositions according to each example showed flame retardant properties, as shown by the results of the combustion test. have.

On the other hand, according to Comparative Example 8, only a halogenated phthalic acid imide derivative was used among the flame retardants, and brominated polystyrene was not added. Both the plate and the film had many conspicuous white spots, indicating that the flame retardant was not well dispersed in the plate or film. In addition, the impact properties were also poor. According to Comparative Example 9, of the flame retardants, only brominated polystyrene was used and no halogenated phthalimide derivative was added, so the plate and film made of the resin composition according to this comparative example were white. The dots are noticeable, indicating that the flame retardant is not well dispersed in the plate or film. It also has low impact strength and tensile elongation. According to Comparative Example 10, the blending amount of the polyolefin resin is higher than the range according to the present invention, and the blending amount of the flame retardant is lower than the range according to the present invention, so even if the flame retardant is well dispersed, the There was a problem with flammability.

Example 16 A flame retardant resin composition according to Example 16 was produced in the same manner as in Examples 1 to 5 above, and this resin composition was used to perform physical property tests and flame retardant tests in the same manner as in the above Examples. Dispersion determination and combustion tests were conducted. The results are shown in Table 6 below. However, as shown in Table 6, in this example, the raw materials used and the blending ratio were different. That is, in this example, PP and HDPE were used as polyolefin resins, and talc was also used as a filler. In addition, in this Table 6, the amount of talc is expressed in wt%. In addition, in this table, the total of polyolefin resin, flame retardant, flame retardant aid, and talc is
% by weight, and other additives are shown in parts by weight when the total of the above four additives is 100 parts by weight.

Comparative Examples 11 and 12 Flame-retardant resin compositions according to each comparative example were produced in the same manner as in Example 16 above, and these resin compositions were subjected to the same physical property tests and resistance tests as in the above Example. A fuel dispersion determination and a combustion test were conducted. The results are shown in Table 6 below. However, as shown in Table 6, the raw materials and blending ratios used were different for each comparative example. That is, in Comparative Example 11, only the halogenated phthalimide derivative was used among the flame retardants, and in Comparative Example 9, only the halogenated phthalimide derivative was used.
In this case, only brominated polystyrene was used.

[Table 6]

Discussion of Examples and Comparative Examples According to Example 16 above, the test piece made of the flame-retardant resin composition of this example had the following properties as shown in the results of the tensile test, bending test, and Izod impact test, respectively. It has good physical properties. In addition, the plate and film made of the resin composition according to this example were used to determine the dispersion of flame retardant.
Almost no white spots were observed, indicating that the flame retardant was well dispersed in the plate or film. Because the flame retardant was well dispersed in the plate or film, the two types of test pieces made of the resin composition according to this example showed flame retardant properties, as shown by the results of the combustion test. have.

On the other hand, according to Comparative Example 11, only a halogenated phthalic acid imide derivative was used among the flame retardants, and brominated polystyrene was not added. The plate and film consist of
Many white spots were noticeable in each case, indicating that the flame retardant was not well dispersed in the plate or film. According to Comparative Example 12, among the flame retardants, only brominated polystyrene was used and no halogenated phthalimide derivative was added, so the plate and film made of the resin composition according to this comparative example were white. The dots are noticeable, indicating that the flame retardant is not well dispersed in the plate or film. In addition, in these comparative examples, in addition to problems with tensile elongation and impact properties, in flame retardancy tests, when the test piece is thick, it has good flame retardancy, but when it becomes thin, it has poor flame retardancy. has become defective.

[0031]

[Effects of the Invention] The flame retardant resin composition according to the present invention has excellent flame retardancy because the flame retardant is well dispersed. In addition, while having excellent physical properties, the amount of flame retardants including flame retardant aids added can be reduced, and it is also excellent in economic efficiency.

Claims (3)

[Claims] 1. A flame-retardant resin composition containing the following components A, B, and C. A: Polyolefin resin 70-96wt
%B: Flame retardant containing the following a and b 20~
3wt% [Formula 1] b: Brominated polystyrene C: Antimony oxide
10~1wt% However, A+B+C=100wt% [Claim 2] The content ratio of a and b of the flame retardant (B) is:
The flame-retardant resin composition according to claim 1, characterized in that a/b=30-70/70-30 (weight ratio). [Claim 3] Flame retardant (B) and antimony oxide (C
) The flame-retardant resin composition according to claim 1 or 2, characterized in that the content ratio of B/C is 2 to 4/1 (weight ratio).