JPS62257949A - Flame-retardant styrenic resin composition - Google Patents

Abstract

PURPOSE:The titled composition useful as electrical parts, etc., having improved molding and processing properties, mechanical strength, transparency, etc., obtained by blending an aromatic vinyl copolymer with a brominated aromatic compound having a specific melting point and a phosphorus compound having a specified melting point in a specific ratio. CONSTITUTION:(A) 70-96wt% resin consisting of A1: 60-90wt% aromatic vinyl monomer (e.g. styrene, etc.) and A2: 40-10wt% vinyl cyanide monomer (e.g. acrylonitrile, etc.) is blended with (B) 1-25pts.wt. one or more brominated aromatic compounds (e.g. tetrabromobisphenol A, etc.) having 90-210 deg.C melting point and (C) 1-15pts.wt. compound shown by formula I or formula II (X is H, Br, etc.; Y is -CH2, etc.; Z is group shown by formula III, etc.) in such a way that total amounts of the components A-C are 100pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a flame-retardant nutyrene resin acid compound having excellent transparency and integrity and good moldability.

[Conventional technology]

Due to its excellent properties, so-called styrene resins are used in a wide variety of fields, including household electrical appliances, electronic equipment, OA equipment, various parts for automobiles, construction materials, toys, and various other molded products. Especially acrylonitrium
M-styrene copolymer resin (hereinafter referred to as As resin) takes advantage of its excellent transparency and is used in lighting materials, displays, electronics, etc. [Widely used in gastrointestinal parts, etc.] However, styrenic resin itself is easily flammable, so its uses may be limited.

On the other hand, in recent years, there has been a strong demand for flame retardant plastic materials, especially for household light electrical parts and furniture, and legal regulations regarding flame retardancy have also been strengthened in various countries from the standpoint of consumer protection.

There are many proposals to make plastic flame retardant, but most of them involve (1) copolymerizing flame retardant monomers into the resin itself, or (2) adding flame retardants. be.

In the former method (1), the flame-retardant monomer is mainly composed of halogen compounds and phosphorus compounds, and when the copolymer resin obtained by this method is molded at a high molding temperature, heat is generated. There are many problems with stability.

In the latter method (2), when a styrene resin is used as the base, flame retardant additives include, for example, a method using an organic bromine compound (Japanese Patent Application Laid-open No. 80159/1983), a method using a phosphate compound and Bisphenol/L'A
(Japanese Unexamined Patent Publication No. 49-52247), a method using vinyl chloride polymer (Japanese Unexamined Patent Application Publication No. 54-54), a method using decaglomodiphenyl μ ether (Unexamined Japanese Patent Application No. 54-1982), 50060), a method using red phosphorus (Japanese Unexamined Patent Publication No. 59-24752), and the like. However, when using these methods, the resin becomes opaque or translucent, and even if a transparent resin can be obtained, the coloring is significant and the moldability and physical properties are significantly reduced.
At present, styrenic resins with excellent optical properties and flame retardancy have not been obtained.

[Problem that the invention seeks to solve]

In a flame retardant agent containing halogen or phosphorus, simply having a high halogen or phosphorus content does not necessarily mean that the flame retardant property is high, and the flame retardant properties of the resin composition as a final product are not necessarily high. The amount of halogen or phosphorus in
More does not necessarily mean greater effect. Furthermore, even if the type and number of atoms forming f4/ in a compound are the same, if the structure is different! The flame retardant effect is also different, and it is generally extremely difficult to predict the flame retardant effect. The imparting of nonflammability is a comprehensive combination of complex factors.
Therefore, it is possible to expect an unexpected flame retardant effect by using a combination of several different mood-imparting agents or by combining certain additives.

In addition, when handling transparent resin, the coloring of the resin has a large impact on the product value, but the degree of coloring is also
Similar to the case of flame retardant additives, or even more complex factors are thought to be intertwined, and combinations of additives often produce unexpected effects.

[Means for solving problems]

As a result of intensive study in view of the current situation as described above, the inventor of the present invention found that
It has excellent moldability and mechanical strength by blending an aromatic vinyl copolymer, a brominated aromatic compound with a melting point in a specific range, and a phosphorus compound with a melting point in a specific range, respectively, in specific ranges. The present invention was accomplished by discovering that a flame-retardant styrenic resin composition with less coloration and excellent transparency can be obtained.

That is, the gist of the present invention is that the aromatic vinyl μ monomer 6
0-90% by weight and vinyl cyanide monomer 40-10
Resin C1170 to 96 parts by weight consisting of heavy #,
1 to 25 parts by weight of at least one kind of brominated aromatic compound [■] having a melting point of 90 to 210°C and the following formula cA),! Take [F]) Compound [II
Consisting of 1 to 15 parts by weight of at least one of [I], [■]
This is a flame-retardant styrenic resin composition in which the total amount of ~[III] is 100 parts by weight.

(However, X is H, Bri or C1, Y is -CH2CH2
-1-(CHz)3-1-CH, -C(CH3)2-C
H, -1-CH, -C(CH2Cl), CH2- or -CH2-C(CH2Br)2 CH2-12
The resin [I] used in the present invention contains 60 to 90% by weight, preferably 60 to 86% by weight of aromatic vinyl μ monomer and 40 to 10% by weight, preferably 35 to 10% by weight of cyanide vinyl μ monomer. %. When the aromatic vinylμ monomer exceeds 90 fkcs, compound CIII
It is not preferable that not only the flame retardant synergistic effect due to the blending of 'l is lost, but also the transparency of the resin composition finally obtained is impaired. Moreover, if the cyanide vinyl monomer exceeds 40% by weight, coloring will become significant, which is not preferable.

Examples of the aromatic vinyl monomer include derivatives of various substituted styrenes such as styrene, α-methylμstyrene, and p-methylstyrene, which can be used alone or in combination.

In addition, as vinyl cyanide monomers, acrylonitrium μ,
Examples include methacrylonitrile p and the like, and these can be used alone or in combination.

Note that up to 30% by weight of the aromatic vinyl μ monomer can be replaced with other copolymerizable monomers. Examples of monomers that can be copolymerized include methyl methacrylate, ethyl methacrylate, butymethacrylate! Methyl acrylate, ethyl acrylate, buty acrylate, etc.; Saturated acid esters; acid anhydrides such as maleic anhydride; N-cyclo-xylmaleimide, N-
Examples include maleimides such as phenylmaleimide, N-(o-chlorophenylmaleimide), N-nee F-/remaleimide, and the like, and these can be used alone or in combination.

Resin [I] in 100 parts by weight of the resin composition of the present invention
The blending ratio is 70 to 96 parts by weight, preferably 75 to 95 parts by weight.
Parts by weight. If it is less than 70 parts by weight, the mechanical strength will decrease relatively significantly, which is not preferable. Moreover, if it exceeds 96 parts by weight, the flame retardance will be poor, which is not preferable.

The brominated aromatic compound [■] used in the present invention has a melting point in the range of 90 to 210°C, preferably 100 to 190°C.
It is preferable to obtain the flame-retardant resin composition having excellent optical properties and mechanical properties according to the present invention. If a compound with a melting point of less than 90° C. is used, the heat resistance of the resulting resin composition will not only deteriorate, but also problems are likely to occur during production. For example, it may be difficult to blend or vent during extrusion. Furthermore, there is also the disadvantage that the flame retardant tends to bleed, which is undesirable. On the other hand, if a compound with a melting point exceeding 210°C is used, the compatibility with the resin [■] used in the present invention may decrease, and the resulting resin composition may have spots or the flame retardant effect may decrease, which is not preferable. .

The proportion of the brominated aromatic compound [■] in 100 parts by weight of the resin composition of the present invention is 1 to 25 parts by weight, preferably 1 to 20 parts by weight. Compound C below 1 electric value part
There is a tendency for the synergistic effect with III) to decrease, resulting in a decrease in flame retardancy, and also in molding fluidity. Moreover, if it exceeds 25 parts by weight, the mechanical strength of the resulting resin composition will decrease, which is not preferable.

Brominated aromatic compounds (Specific examples of 10 include tetrabromobispheno-/'A, brominated biphenyl oxide, and derivatives thereof, and these are preferred. These are preferred alone or in combination. used.

Furthermore, the compound [] represented by the above formula or (B) used in the present invention is polymethymu methacrylic V-
It is known that transparent resins may be obtained by blending with other materials.

However, when these are used alone, there are problems such as coloring, increased water absorption, and poor fluidity during molding.

In the present invention, by combining this compound CIII with the brominated aromatic compound [■] and blending it into the resin (1), the synergistic effect results in molding with low water absorption, excellent transparency, and heat resistance, with little coloring. A major feature is that a flame-retardant carbon-based resin composition with good properties can be obtained.

The compound [Tl11] represented by the above formula or [F] in the present invention has a melting point in the range of 90 to 210°C, preferably in the range of 100 to 195°C.

When using a compound with a melting point of less than 90°C or a compound with a melting point of more than 210°C, it is not preferable for the same reason as in the case of the brominated aromatic compound (n).

Compound [r] in 100 parts by weight of the resin composition of the present invention
The blending ratio of lI) is 1 to 15 parts by weight.

If it is less than 1 part by weight, it is difficult to obtain a flame retardant effect;
If the amount exceeds 5 parts by weight, water absorption increases and coloration becomes significant, which is not preferable.

Further, it is known that this compound (III) has a flame retardant effect when blended with methacrylic resin, but the brominated aromatic compound ( When used in combination with compound (m), flame retardancy can be achieved with a much smaller amount than when using 1 kg of methacrylic resin, and compound (m) has poor compatibility with styrenic resins. It is surprising that although it is cloudy, has poor optical properties, and has poor flame retardant effect, when it is blended with resin [1], a product with excellent optical properties and flame retardancy can be obtained. . Furthermore, chemical compound CIII] is mQWC
I:], it is possible to obtain a resin composition with lower hygroscopicity, lower water absorption, and superior dimensional stability than when blended with methacrylic resin.

The resin composition of the present invention may contain a mold release agent, other flame retardants, stabilizers, colorants, ultraviolet absorbers, light dispersing agents, etc., as long as the gist of the present invention is not impaired. In particular, when using a stabilizer, add a phosphite stabilizer to the porcelain composition 1.
It is preferable to use the flame retardant in an amount of 105 to 3 parts by weight per 00 parts by weight because it can exhibit the tlI power effect with the flame retardant and can also reduce coloring. If it is used in an amount exceeding 3 parts by weight, the mechanical properties will deteriorate, which is not preferable. If a large amount of stabilizer with a magnetic point of less than 40°C is blended, the surface of the resulting resin composition will become sticky, and if the stabilizer has a magnetic point of more than 200°C, the compatibility will be poor and the transparency of the resulting resin composition will be reduced. This is not desirable.

Some preferred stabilizers are illustrated below, but are not limited thereto.

Pentaerythritol water-added bispheno-triphenylphosphite polymer (existing chemical substance 7-190)
0, mp98℃, manufactured by Johoku Kagaku Kogyo Co., Ltd., product name, TP
H-3800), tris(2,4-di-t-butylphenyl) phosphite (mp170-190°C, manufactured by Adeka Argus Chemical Co., Ltd., trade name mark 2112)
, water-added bispheno-/l/A phosphite polymer (mp70-80°C, manufactured by Johoku Chemical Co., Ltd., trade name HBP), bispheno-1vA pentaerythritol phosphite (mp70°C, manufactured by Johoku Chemical Co., Ltd. jEll)
, trade name JPP-3-00), allyl diphonupite (mpi 10-120°C, manufactured by Ajika Argus Chemical Co., Ltd., trade name markPEP-2), distearyl pentaerythrityl siphosphite (mp 40-50°C, existing chemical Substance 5-1081. Manufactured by Johoku Kagaku Kogyo Co., Ltd., trade name, rpp-zooo; Ajika Argus Chemical Co., Ltd., Oku, trade name, mark PEP-8).

Various methods can be adopted to add the brominated aromatic compound [■] and the compound CllTl to the copolymer [I], but since the melting points of each component are limited to relatively close ranges, tumbler Alternatively, the method of mixing in a Henschel mixer and uniformly mixing in an extruder is the simplest method and also has excellent productivity. Heat roll or Banbury mixer
etc. can also be used. In addition, brominated aromatic compounds (I
The desired resin composition can also be obtained by dissolving II and/or the compound [■] and performing bulk or suspension polymerization.

〔Effect of the invention〕

The resin composition of the present invention has excellent flame retardancy, optical properties, and mechanical properties, so it can be used in electronic and electrical parts, OA equipment parts,
It is useful for applications such as automobile parts, building materials, signboards, and V-ging materials.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples. In addition, "part" and "chi" in an example indicate "heavy duty part" and "weight%."

r4j! Physical property evaluation in Examples was measured based on the following method.

(1) Tensile strength, elongation ASTM-D-638 (2) Izot impact strength ASTM-D-256 (mild notch) (3) Heat distortion resistance Heat distortion temperature (HDT), (℃) AS'rM-D-648 (4) Total light transmittance, haze value ASTM-D-1005 (two plate thicknesses) (5) Melt index ASTM-D-1238 230℃, load 10kg, xay (6) R original viscosity 30℃, 0.5p /dt methyl ethyl ketone solution was determined using a Cannon-Fenske 5o:# viscosity tube.

(7) AN (acrylonitrile/
I/) was determined using a unit ratio elemental analyzer.

(8) Color tone and transparency of injection molded plate Visual inspection and Y, I, ffl were determined according to ASTM-D-192.
5.

(9) Weather resistance accelerated exposure test for 120 hours at a temperature of 6 with a Suga Co., Ltd.
The experiment was carried out under the conditions of 0°C, carbon arc lamp, and 12 minutes of rain per hour.

(To) Combustion test The test was carried out using the vertical method in accordance with the US UL standard 5ubject 94.

The thickness of the specimen was evaluated as 1.5+w or 311111.

01) Compound Composition Analysis Phosphorus: Measured according to a conventional method using a modified absorbance method using molybdenum blue and an absorbance method using chlorine and bromine dirodane mercury.

(1) Types of resin [I] Cl-1) to [1 to 3]: Polymerization was carried out continuously under the conditions shown in Table 1 using a complete mixing type polymerization machine with a capacity of 5 tons. .

The obtained polymerization reaction product had a solid content of 45 to 55%, and was continuously treated in a volatile matter separation and removal device maintained at a temperature of about 230°C under conditions of about 50 ta Hg abs. A desired A8 resin pellet was obtained.

Table 1 Cl-4) to CT-63: The following commercially available As resin for injection molding was used.

The AN ratio in the resin was as follows.

CI-a]: Estyrene As-30 (trade name) manufactured by Nippon Steel Chemical Industry Co., Ltd. (AN ratio 28%) (r-51: Tairi/L' 789 (trade name) manufactured by Asahi Kasei Corporation (AN ratio 28 inches) C[-6]: Cepian N-010 (trade name) Daicel Corporation N (AN ratio 27 inches) Also, polystyrene resin and methacrylate # as comparative examples
For grease resistance, the following was used.

Cl-7) (for comparative example): G-10 (trade name, Boristine V resin general grade) manufactured by Nippon Steel Chemical Co., Ltd. Cl-8) (for comparative example) Niacrivet VH (trade name, methacrylic resin) IIYI) Manufactured by Sanbin Rayon Co., Ltd. (2) Type of Brominated Aromatic Compound (II) The following commercial product was used as it was.

CI[-1)tetrabromobispheno-/L/A:
'mp, 178-181℃, Fire Guard 200
0 (product name), Cl-2 manufactured by Konjin Kasei Co., Ltd.]: Er'-'j'3 Brmp, 1
15-118°C, APR-1011 (trade name), Asahi Glass Co., Ltd. [:ll-3:]: mp, 90-105°C, Fireguard 311]1
17 (product name), Konjin Kasei Co., Ltd. PA [:n-41 octapromodiphenyl μ oxide: mp, 127-16 QClFR-j208 (product name), Promin Compounds Limited Cll-5)
(Ratio 11'll) Pentabromodiphenyl oxide: Liquid, DE-71 (trade name), manufactured by Great Lakes Chemical Company [ll-6] (Comparative example) Hexabromobenzene: mp,
320℃, AP'R-1001 (product name), Asahi Glass (
Co., Ltd. [ll-7] (comparative example): mp, 230-250°C, F'G-70110 (trade name), Konjin Kasei Co., Ltd. (n-8): mp, 200-201°C, RB-303 (product name),
Manufactured by Kenhyo Kagaku Kogyo Co., Ltd.: 3) Type of compound (m) The following (m-11 to [:lll-4]) were produced according to the description in US Patent No. 4.45a045.

[■ -1: (III-2): (III-31: CL[-43 (comparative example): (III-53 (comparative example):) Lihueni μ phosphate (manufactured by Oiri Kagaku, trade name TPP) These compounds [■-
Table 2 shows the analysis results regarding the melting points and contents of phosphorus and halogen atoms for samples 1] to [■-5].

Table 2 Analysis Results of Compound [III] Examples 1 to 3 and Comparative Examples 1 to 2 Each component was blended in the proportions shown in Table 3, mixed in a tumbler, and then Extruder (PCM-30
) to calculate the cylinder temperature shown in Table 3 as - and approximately 1
It was extruded into pellets at a vent pressure of 0 tm Hg abs.

This pellet was injection molded into various test pieces using a V-17-65 automatic screw injection molding machine manufactured by Nippon Steel Corporation at a cylinder temperature and a mold temperature of 60 DEG C. as shown in Table 5 and evaluated. The results are shown in Table 4.

As is clear from the above results, the material according to the present invention had excellent flame retardancy, optical and mechanical properties, and good molding flow characteristics.

On the other hand, the one using styrene resin as a paste had poor transparency (Comparative Example 1), and the one using methacrylic resin as a paste had poor flame retardancy (Comparative Example 2).

Examples 6-7 and Comparative Examples 3-6 85 parts of [:l-1) as resin [I], 10 parts each of those shown in Table 5 as brominated aromatic compound CIO, compound (1'I Various physical properties were determined in exactly the same manner as in Example 1 by blending 5 parts each of those shown in Table 5 as [), 12 parts of JPP-2000 as a stabilizer, and α1 part of stearic acid monoglyceride as a mold release agent. evaluated. These results are shown in Table 5.

Examples 7 to 10 and Comparative Examples 7 to 9 Test pieces were molded in the same manner as in Example 1 except that the formulations were as shown in Table 6, and the evaluation results shown in Table 6 were obtained.

The additive Tinuvin P is a UV absorber manufactured by Ciba Geigy.

Products other than those related to the present invention have a high water absorption rate (
Comparative Example 7, Comparative Example 9) or significant discoloration and poor weather resistance (Comparative Example 7, Comparative Example 8).

Claims (1)

[Scope of Claims] 1) A resin composed of 60 to 90% by weight of aromatic vinyl monomer and 40 to 10% by weight of vinyl cyanide monomer [
I] 70 to 96 parts by weight, 1 to 25 parts by weight of at least one kind of brominated aromatic compound [II] having a melting point of 90 to 210°C and a melting point of 90 to 2 represented by the following formula (A) or (B)
A flame-retardant styrenic resin composition comprising 1 to 15 parts by weight of at least one type of compound [III] at 10[deg.] C., wherein the total of [I] to [III] is 100 parts by weight. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(B) (However, X is H, Br or Cl, Y is -CH_2CH
_2-, -(CH_2)_3-, -CH_2-C(CH
_3)_2-CH_2-, -CH_2-C(CH_2C
l)_2CH_2 or -CH_2-C(CH_2Br
)_2CH_2-, Z indicates ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ) 2) The flame-retardant resin composition according to claim 1, wherein the brominated aromatic compound [II] is at least one selected from the group consisting of tetrapromobisphenol A, brominated biphenyl oxide, and derivatives thereof. thing.