JPS62143960A - Heat-resistant, flame-retardant resin composition - Google Patents

Abstract

PURPOSE:A resin composition having improved heat resistance and flame retardance without damaging characteristic physical properties of ABS resin, especially impact resistance, comprising a modified ABS resin and a specific phosphorus compound. CONSTITUTION:100pts.wt. modified ABS resin comprising (A) 97-75wt% resin component consisting of (i) 50-87wt% mixed monomer of vinyl aromatic monomer (preferably styrene) and acrylonitrile, (ii) 8-35wt% (meth)acrylic acid ester of halogen-containing phenolic derivative shown by formula I (R1 is H or CH$3; R2 is 1-4C alkyl or chloro; m is 2-5; n and l are 0-3 and l+m+n=5) and (iii) 5-30wt% mixed monomer of maleic anhydride and n- phenyl-maleimide and (B) 3-25wt% rubber component (preferably butadiene rubber) is blended with (C) 0.5-10pts.wt. phosphorus compound shown by formula II or formula III (R3 is H, 1-18C alkyl, alkylene, etc.; R4 and R5 are 1-18C alkyl, alkylene, etc.), having >=240 deg.C/760mmHg boiling point.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a flame-retardant resin composition with excellent heat resistance.

More specifically, the following general formula (I), where a: H or C is R,: C, - q alkyl group or chloro m: 2,3
,4,5 n,'e: 0,1,2,3 However, e+m+n=s is an integer of acrylic or methacrylic acid esters of halogen-containing phenol derivatives, vinyl aromatic monomers, acrylonitrile, maleic anhydride, Modified ABS resin containing n-phenylmaleimide as a resin component and general formula (1
1) Phosphorus compound (III) (with a boiling point of 240°C
The present invention relates to a flame-retardant resin composition with excellent thermal properties comprising:

88-P-8 (Iri8heP- (III) ++ Into the formula: hydroxyl group, alkyl group from C1 to Cps, alkylene group and aromatic substituent RlFt,: O, to alkyl group from C+a, alkylene Groups and aromatic substituents (prior technology) ABS resin is used for automobile parts, electric/electronic equipment parts, precision/OA equipment parts, etc. due to its excellent moldability, mechanical strength, and electrical insulation properties. In many cases, flame retardancy is required in order to use the equipment.In recent years, the above-mentioned equipment has been becoming smaller and lighter due to thinner walls, so it is necessary to improve various performances, especially heat resistance. It is well known that there is a growing demand for

In this way, ABS resins for the above applications are required to have excellent heat resistance and flame retardancy, in addition to the excellent moldability, mechanical strength, and electrical insulation properties that ABS resins inherently have. ing.

As a method for making ABS resin flame retardant, so-called flame retardants are added to ABS resin.
A method of adding and mixing with a resin, a method of copolymerizing a flame retardant compound, a method of introducing a functional group into a resinous component and reacting it with a flame retardant containing a functional group that is reactive with this in an extruder etc. Various methods are being used.

(Problems to be Solved by the Invention) However, although flame retardance is obtained in either method, there is a tendency for other physical properties to be adversely affected.

In the method of adding and mixing nonflammable or flame retardant compounds,
They always tend to reduce their main properties, impact resistance and thermal stability during molding. Furthermore, when a low molecular weight flame retardant is added and mixed, in addition to the above-mentioned problems, there is a reduction in heat distortion temperature, generation of corrosive gas during molding, and sanitary problems due to substances exuding from the resin during long-term use. The sustainability of flame retardancy is becoming an issue.

On the other hand, flame retardancy using copolymerization or reaction can prevent a decrease in heat resistance, but in reality, the only way to achieve flame retardancy by copolymerization is to copolymerize a flame retardant imparting compound and a functional monomer. In many cases, it is difficult to provide the desired physical properties to the resulting resin composition.Furthermore, flame retardants containing functional groups that are reactive with the resinous components are introduced. However, it is still difficult to control the reaction and to provide the resulting resin composition with the desired physical properties.

As mentioned above, the physical properties that ABS resin originally has, especially #
At present, it has not yet been sufficiently developed to obtain a flame-retardant, impact-resistant resin composition that has excellent heat resistance without any adverse effect on impact properties.

(Means for solving the problem) In view of the above circumstances, the inventors of the present invention have conducted extensive studies and have found that
A modified ABS resin containing as an essential component a resin obtained by copolymerizing anhydrous derivative acrylic acid or methacrylic ester, which is effective in improving heat resistance, with a vinyl aromatic monomer and acrylonitrile, is combined with general formula (II) or (III). It has been revealed that a flame-retardant and impact-resistant resin with excellent heat resistance can be obtained by adding one or a mixture of the following phosphorus compounds, thereby achieving the present invention.

More specifically, in the process of the present invention, the present inventors prepared an acrylic acid or methacrylic acid ester of maleic anhydride and n-phenylmaleimide with a halogen-containing phenol derivative in the presence of a vinyl aromatic monomer and acrylonitrile. It has been found that a modified ABS resin whose essential component is a polymer obtained by copolymerizing the above has excellent heat resistance and flame retardancy.

However, in order to obtain flame retardancy using only the above-mentioned modified ABS resin, 12 wt% or more of halogen is required in terms of bromine content. Increasing the amount of acrylic acid or methacrylic ester of a halogen-containing phenol derivative as a resin component is not only disadvantageous in terms of cost, but also makes it difficult to control the polymerization reactivity, especially the rubber particle size during graft polymerization to the rubber component. Undesirable.

It is well known to use flame retardant aids such as antimony trioxide and phosphorus compounds to reduce the amount of halogen required for flame retardancy.

However, the addition of antimony trioxide can significantly reduce the impact resistance of ABS resin q) and may impair its original physical properties.
Also, phosphorus compounds such as triphenylphosphite□,
Addition of tris dibromopropyl phosphate etc. is A.
It is also well known that this may lower the heat distortion temperature of the BS resin or impart an undesirable hue to the molded product.

However, the inventors of the present invention discovered that the above-mentioned modified AB
When phosphorus compounds of general formula (■) or ([) are added alone or as a mixture to S@ fat, there is no adverse effect on P# impact strength and heat distortion temperature, but due to the interaction of the bromine compound and the phosphorus compound, there is a significant The present invention was achieved by clarifying that the flame retardant effect can be achieved.

The modified ABS resin which is the first component of the present invention is rubber component 3.
~25 wt% and a resin component of 97 to 75 wt%, the resin component being 50 to 87 wt% of a mixed monomer of vinyl aromatic monomer and acrylonitrile, and 8 to 87 wt% of a halogen-containing phenol derivative ester of acrylic acid or methacrylic acid. 35 wt% and 5 to 30 wt% of a mixed monomer of maleic anhydride and n-phenylmaleimide.

Styrene is most suitable as the vinyl aromatic monomer, but styrene derivatives such as α-methylstyrene, P-methylstyrene, etc. can also be used, and these may also be used in combination.

The ester of acrylic acid or methacrylic acid of a halogen-containing phenol derivative is a compound represented by the following general formula (1), and is an ester obtained by the reaction of a halogen-containing phenol derivative with acrylic acid chloride or methacrylic acid chloride. be.

In the formula, R, :H or C is F%: C, ~q alkyl group or chloro e:2. 3. 4. 5 m, n: 0. 1. 2. 3 However, e +m+
Integer n = s The content of the mixed monomer of vinyl aromatic monomer and acrylonitrile in the resin component is 50 to 8'ywt%,
The usage ratio of both vehicles is Vini IV aromatic monomer/acryloni)! The range of jzu=65.about.9515˜35 (weight ratio) is desirable.

The content of acrylic acid or methacrylic ester of the halogen-containing phenol derivative is from 8 wt% to 35 wt%, preferably from 10 Vi't% to aowt%. 8wt
If it is less than 35 wt %, it is unfavorable from the viewpoint of flammability, and if it is more than 35 wt %, it is unfavorable from the viewpoint of controlling the properties of the resin obtained and the polymerization reaction.

Further, the content of the mixed monomer of maleic anhydride and n-phenylmaleimide is from Swt% to 30wt%, preferably from Swt% to 2 owt%. If it is less than swt%, the resulting resin will have insufficient heat resistance and 30
If it exceeds wt%, it is unfavorable from the viewpoint of the properties of the resulting resin and the control of the polymerization reaction.

Further, there is no particular restriction on the ratio of maleic anhydride to n-phenylmaleimide.

Next, as the rubber component, a butadiene rubber is suitable, which is generally used in the production of impact-resistant resins, but it is not particularly limited. The amount of rubber in the modified ABS resin is from 3 wt% to 25 wt%. 3wt
If it is less than 2 swt%, the impact resistance will be insufficient, and if it is more than 2 swt%, defects will occur in physical properties other than impact resistance.

The modified ABS resin in the present invention can be produced by mixing the reactive compounds constituting the resin component in a predetermined ratio and graft polymerizing the mixture in the presence of a rubber component, or by adding the resin component in the presence or absence of rubber. A method can be adopted in which a resin obtained by mixing and copolymerizing the constituent reactive compounds is mixed with an ordinary ABS resin at a predetermined ratio.

The phosphorus compound which is the second and third component of the present invention is a phosphine compound represented by the following general formula (■), (([1) (n) (nu) in which H or CI to C1, is an alkyl group, alkylene group, or aromatic substituent, and 8 and 8 are an alkyl group, alkylene group, or aromatic substituent of CI to C1°.

The boiling point of the phosphorus compound represented by the above general formula (II) and general formula Qll) is determined because the molding temperature of the modified ABS resin to which it is added is around 230°C and to maintain the heat resistance of the resin after molding. The temperature must be 240°C or higher/760ffHg.

The amount of the phosphorus compound of general formula (n) and general formula (Ill) to be added is preferably in the range of C5 to towt%. o,
If it is less than swt%, no significant flame retardant effect can be expected, and if it is more than towt%, the heat distortion temperature will be slightly lowered, which is not preferable.

Phosphorus compound of general formula (ff) (boiling point 240°C or higher/76
For example, diphenylphosph
fin, trill founfi
Aluminum, triphenylphosphine, tritrilylphosphine, trisethylphenylphosphine, trinuchlorophenylphosphine, etc.

Phosphorus compound of general formula (II[) (boiling point 2'40℃ or higher 7
760mH9) includes, for example, triethylphosphine oxide, tripropylphosphthryl phosphine oxide, triethyl phenylphosphine oxide, trischlorphenylphosphine oxide, etc.

In addition to the above-mentioned three components, various additives such as commonly used heat stabilizers, antioxidants, lubricants, and colorants can be added at the same time as necessary.

Next, the mixing method does not require any special means, and conventional mixing equipment such as an extruder, a Panbury mixer, etc. can be used.

The present invention will be described in detail with reference to Examples below.

The flame resistance in the Examples and Comparative Examples was measured by a method based on Subject No. 94 established by the American Underwriters Laboratory (hereinafter abbreviated as UL Standard No. 94). The shape of the test piece is 1 inch thick, 1 inch wide, and 6 inches long.

(Example 1) A 10e autoclave equipped with a stirrer, a reflux condenser, a nitrogen inlet, and an addition nozzle was charged with 2346 g of styrene, and styrene-butadiene rubber cut into small pieces (
153 g of Tuffden 2000A (manufactured by Asahi Kasei ■) was added and stirred for 4 hours under a nitrogen stream to completely dissolve the rubber. Next, in this solution, 351 g of acrylonitrile, 2,4.6
-) Lipromov, enyl methacrylate 255 g,
26.5 g of maleic anhydride, 26.5 g of n-phenylmaleimide, and 10.5 g of lauroyl peroxide as a polymerization initiator. sq, toluene 750 as polymerization solvent
q and stirred at room temperature for 30 minutes, then heated to 75°C and stirred for 5 minutes.
Polymerized for hours. At this time, after the internal temperature rose to 75℃,
Every minute, maleic anhydride 78,59 and n-phenylmaleimide 78,59 were post-added in powder form from the inlet nozzle according to the divided addition schedule shown in Table 1.

After polymerization, transfer the highly viscous polymerization solution to an aluminum foil box.
First stage in vacuum dried product: 100℃X 10 TOrrX
The mixture was devolatilized under reduced pressure for 3 hours and second stage: 160° C. for 3'rorrxs hours to obtain milky white yellow lumpy resin 16109. The produced resin was fractionated with an acetate, and the m'f& viscosity (solvent, methyl ethyl ketone measurement temperature: 30° C.) of the soluble portion after centrifugation was measured, and it was found that [η) = 0.66.

Table 1 Schedule for the divisional addition of maleic anhydride and n-phenylmaleimide The obtained resin was analyzed as follows: Styrene: 63 parts by weight Acrylonitrile: 11 parts by weight 2, 4.6-1-Lipromophenyl methacrylate 12 Maleic anhydride: 7 n- It had a composition of 7 parts phenylmaleimide and 10 parts styrene-butadiene rubber. After uniformly mixing 100 parts by weight of this resin and 3 parts by weight of triphenylphosphine in a ribbon blender, an extruder (cylinder temperature 230°C)
), predetermined test pieces were prepared using an injection molding machine (cylinder temperature: 230°C, gauge pressure: 801°C), and flame resistance, heat distortion temperature, and Izod strength were measured. The results are shown in Table 2, and the composition showed excellent heat resistance, flame retardancy, and impact resistance.

(Comparative Example 1) The resin obtained in Example 1 was extruded and
Test pieces were prepared by injection molding and evaluated in the same manner as in Example 1. The results are shown in Table-2. Although this resin exhibited a heat distortion temperature slightly lower than that of Example 1, its flame resistance was 94% B.

(Comparative Example 2) Styrene 64 parts by weight
mouth ni tril
242, 4.6-) Ripromophenyl methacrylate
1 2 Styrene-butadiene rubber 1°benzoyl peroxide o415 dicumyl peroxide 0.1 The above composition was charged into a closed reactor equipped with a stirring device,
After the rubber component was completely dissolved, the temperature was raised to 70 iC and bulk polymerization was carried out for 4 hours while stirring.

Furthermore, in advance, 200 parts by weight of water, 10 parts by weight of magnesium hydroxide,
An aqueous dispersant prepared by mixing 5 parts by weight of sodium lauryl sulfate α0 was added and stirred to suspend. Thereafter, the temperature was raised to 120°C and suspension polymerization was carried out for 5 hours. Next, the reaction product was cooled to room temperature, the dispersant was decomposed with hydrochloric acid, and the resulting polymer particles were washed with water and dried.

100 parts by weight of the resin thus obtained and tripheny/L'
A 3N portion of 7-year-old sphine was mixed, extruded, and injection molded in the same manner as in Example 1 to prepare a test piece, and evaluated in the same manner as in Example 2. The results are shown in Table 1. This composition exhibits flame resistance and impact resistance equivalent to the composition of Example 1, but
Since the resin component does not contain n-phenylmaleimide, the heat distortion temperature is poor.

Table-2 Example 1 Comparative Example 1 Comparative Example 2 Br content in the composition 7. OW t
% 7.1wt% 6.4Wtf) Triphenylpho 17wt% O2, 7wt% Sphine content in the composition Flame resistance (UL Standard No. 94) 94V-2'
94HB 94'V-2 Eye shift impact strength. Lee/fji'm o, 7. I, °°´掬“°°70 °
°'''゛0 (Example 2) 231゜q of styrene was placed in the apparatus described in Example 1, and 115 g of styrene-butadiene rubber was dissolved in the same manner as in Example 1. 369 g, 2,4.6-) 276 g of rifromophenyl methacrylate, 319 g of Macan V47 acid anhydride
After adding 14 g of Un-phenylmaleimide to form a homogeneous solution, 10.8 g of lauroyl peroxide and 7509 toluene were added, and after stirring at room temperature for 30 minutes, the temperature was raised to 75° C. and polymerized for 5 hours. At this time, after the internal temperature reached 75°C, 72.2 g of maleic anhydride and 32.19 g of n-phenylmaleimide were added in portions every 20 minutes using the method shown in Example 1, so that the resin composition was uniform. I tried to be. After the polymerization was completed, 1250 g of a pale white-yellow resin was obtained by the post-treatment method described in Example 1. Also, this was it.

As a result of analysis, the obtained resin had a composition of 62 parts by weight of styrene, 10 parts by weight of acrylonitrile, 15 parts by weight of ribromophenyl methacrylate, 15 parts by weight of maleic anhydride, 9 parts by weight of n-phenylmaleimide, and 10 parts by weight of styrene-butadiene rubber. 100 parts by weight of the above resin and 1 part by weight of triphenylphosphine were mixed, extruded, and injection molded in the same manner as in Example 1 to prepare a test piece, and the same evaluation as in Example 1 was performed. This composition exhibited excellent heat resistance, flame retardancy, and impact resistance as shown in Table 3.

(Comparative Example 3) The resin obtained in Example 2 was extruded and
Test pieces were prepared by injection molding and evaluated in the same manner as in Example 1. The results are shown in Table-3. The flame resistance of this resin was 94HB, which was the same as that of Comparative Example 1.

≠ and ← Table-3 Example 2 Comparative Example 3 Br content in composition 8.1wt%
8.2 Wt% alcohol resistance (UL standard No. 94)
94■-294HB (Example 3) Using the apparatus described in Example 1, styrene 2145Q was mixed with stirring under a nitrogen stream.
3 0 6 g2, 4; 6-)
! 504 g of J-glomophenyl methacrylate, 17.39 g of maleic anhydride, 27.7 g of n-phenylmaleimide, 10.8 g of lauroyl peroxide, and 750 g of toluene were added, and after stirring at room temperature for 30 minutes, the temperature was raised to 75°C and polymerized for 5 hours. At this time, maleic anhydride 33.59 and n-
53.57 ml of phenylmaleimide was added in portions every 20 minutes as described in Example 1. After the polymerization was completed, unreacted monomers were devolatilized under reduced pressure to recover 1020 g of a pale yellow and transparent resin. The acetone soluble content [η] of this resin (molten KMEK, measurement temperature 30°C) is 0.6
It was 8.

As a result of analysis, the obtained resin had the following composition: styrene, 511 heavy acrylonitrile, 72,4,6-tribromophenyl methacrylate, 28 maleic anhydride, 5 n-phenylmaleimide, and 8.

60 parts by weight of the thus obtained resin and AB manufactured by Japan Synthetic Rubber
S resin (product name DP-61'l) 4 o heavy f A part and U
2 parts by weight of +-liphenylphosphine oxide was mixed, extruded, and injection molded in the same manner as in Example 1 to prepare a test piece, and the same evaluation as in Example 1 was performed.

This composition exhibited excellent heat resistance and flammability as shown in Table 4.

(Comparative Example 4) 60 parts by weight of the resin obtained in Example 3 and Nippon Synthetic Rubber A
Example 1 40 parts by weight of BS resin (trade name DP-611)
Test pieces were prepared by mixing, extruding, and injection molding in the same manner as in Example 1, and the same evaluation as in Example 1 was conducted. Table 4 shows the results.
As shown in the figure, the flame resistance of this composition was 94HB.

Table-4 Example 3 Comparative example 4

Claims (1)

[Scope of Claims] (a) Mixed monomer of vinyl aromatic monomer and acrylonitrile 50 to 87 wt% (b) 8 to 35 wt% of acrylic acid or methacrylic acid ester of a halogen-containing phenol derivative represented by the following general formula (I) % ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) In the formula, R_1: H or CH_3 R_2: C_1 to C_4 alkyl group or chlor m:
2, 3, 4, 5 n,: l: 0, 1, 2, 3, where l + m + n = 5 integer (c) Mixed monomer of maleic anhydride and n-phenylmaleimide at 5 to 30 wt% [(a) + (b) + (c) = 100 wt%], the resin component is 97 to 75 wt% and the rubber component is 3 to 25 wt%.
100 parts by weight of a modified ABS resin consisting of general formula (II)
Or (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) R_3: H, alkyl group of C_1 to C_1_0, alkylene group, and aromatic substituent R_4, R_5 : C_1 to C_1_8 alkyl group,
It is represented by an alkylene group and an aromatic substituent, and has a boiling point of 240°C or higher/760mmHg
A heat-resistant and flame-retardant resin composition comprising 0.5 to 10 parts by weight of either or both of the above phosphorus compounds.