JPS6050829B2 - Flame retardant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame-retardant resin composition with excellent heat resistance.

More specifically, a resin composition ( I), containing an epoxy group that can react with the functional group in (I),
ΣヱY4, τfu) 4n Ie4, 1Ln, Oyolゝ thing (■
) The present invention relates to a flame-retardant resin composition having excellent heat resistance.

Due to its excellent properties, so-called styrene-based resins are used in a wide variety of fields such as household electrical appliances, automobile parts, construction materials, and various other molded products.

However, styrenic resins, like many other synthetic polymers, are easily flammable and pose a high risk of fire.
On the other hand, in recent years, there has been a demand for synthetic polymers to be flame retardant, especially for household light electrical parts.

Furthermore, legal regulations regarding flame retardation are becoming stronger in each country from the standpoint of consumer protection. Currently, flame retardant synthetic polymers are mainly made by adding compounds containing halogens, phosphorus, etc., and flame retardants such as antimony trioxide. Although flame retardant properties can be achieved, there is a tendency to have unfavorable effects on other properties.

In particular, when low-molecular-weight flame retardants are added, the heat distortion temperature decreases, the generation of corrosive gases during J-forming, the toxicity of substances exuded from the resin during long-term use, and the persistence of flame retardancy. It is considered a problem. On the other hand, in the method of making flame retardant by copolymerization, a compound containing halogen or phosphorus is used as a flame retardant imparting compound, but it is difficult to achieve copolymerizability with other monomers and desired physical properties of the resulting resin composition. Because it is difficult to equip them, there are very few of them in actual use at present, and many of them are expensive.

In order to improve the above-mentioned drawbacks, the present inventors have made extensive studies and found that by introducing a functional group into a resinous component and combining it with a flame retardant containing a functional group that is reactive with the resinous component,
It has been found that a resin composition with excellent flame retardancy, heat resistance, and safety can be easily obtained.

That is, the present invention comprises 0 to 4% by weight of the com component and 100 to 60% of the resinous component having one or more functional groups selected from hydroxyl groups, carboxyl groups, and acid anhydrides (groups).
Resin (1) obtained from 98 to 6 parts by weight and (1)
A flame-retardant resin composition with excellent heat resistance consisting of 2 to 4 parts by weight of a halogen flame retardant containing an epoxy group, alone or in a mixture of two or more (■), which can react with the functional groups in the flame retardant. The resin component consists of a vinyl aromatic monomer and one or more vinyl monomers copolymerizable with the vinyl aromatic monomer, and is selected from a hydroxyl group, a carboxyl group, and an acid anhydride (group). The weight average molecular weight of one or more functional groups is 1000.
Contains 3% by weight or more of a copolymer having 1 to 55 functional groups or a copolymer that has been post-treated to have the above functional groups based on the total resinous component, and contains 99 to 35% by weight of a vinyl aromatic monomer. % and 1 to 65% by weight of one or more vinyl monomers copolymerizable with the vinyl monomer.

The post-treatment of the copolymer referred to in this) refers to the conversion of functional groups in the copolymer into other functional groups through treatments such as saponification! Refers to the operation to be performed. In this case, the most suitable vinyl aromatic monomer is styrene, but various substituted styrene derivatives such as α-methylstyrene, p-methylstyrene, and 0-chlorostyrene can also be used. can also be used at the same time.

There are no particular restrictions on the vinyl monomer that can be copolymerized with the vinyl aromatic monomer, but examples include acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, and 2-hydroxyethyl methacrylate. acrylic acid, methacrylic acid, maleic anhydride, vinyl acetate, 2-chlorovinyl ether, etc., and there is no problem in using two or more of them at the same time. Examples of the halogenated flame retardant having an epoxy group according to the present invention include dipromucresyl glycidyl ether and bromophenol novolak epoxy resin.

(1) The functional group in the resin (1) and the flame retardant (■
) with the functional group is not particularly restricted as long as they can react.

As the rubbery component in the present invention, those commonly used in the production of impact-resistant θ polymers may be used, such as polybutadiene rubber, butadiene-styrene rubber, ethylene-propylene rubber, acrylic rubber, Chloroprene rubber etc. can be used.

In the present invention, the resinous component is composed of a vinyl aromatic monomer and one or more vinyl monomers copolymerizable with the same, and includes a hydroxyl group, a carboxyl group, an acid anhydride (
A copolymer having one or more functional groups selected from the following with a weight average molecular weight of 10,000 or a copolymer post-treated to have the above-mentioned functional groups is used as a whole resin. A resin composition containing 3% by weight or more based on the form component, and consisting of 99 to 35% by weight of a vinyl aromatic monomer and 1 to 65% by weight of one or more vinyl monomers copolymerizable therewith. It is a thing.

The copolymer having the above-mentioned functional group includes the above-mentioned acrylic acid, methacrylic acid, maleic anhydride, and 2-hydroxyethyl methacrylate as all or a part of the vinyl monomer copolymerizable with the vinyl aromatic monomer. It can be obtained by using a monomer having a functional group selected from a hydroxyl group, a carboxyl group, and an acid anhydride (group), and copolymerizing this with a vinyl aromatic monomer by a commonly known method. Alternatively, it can be obtained by converting a copolymer of a vinyl aromatic monomer and, for example, a (meth)acrylic acid ester into the above functional group by subjecting it to a post-treatment such as hydrolysis. The amount of the copolymer having a functional group in this) corresponds to the amount of the functional group it has and the type and amount of the functional group-containing flame retardant, but if it is not used in an amount of 3% by weight or more based on the resinous component, However, a resin composition with excellent heat resistance and safety, which is the object of the present invention, cannot be obtained. Furthermore, the functional group in the copolymer having a functional group has a weight average molecular weight of 10,000
Even if the ratio is less than 1 per 0, the desired heat resistance and safety cannot be imparted to the flame retardant resin composition. Furthermore, if the resin has too many functional groups, the physical properties of the flame-retardant resin composition may be deteriorated. Next, these resinous components include, in addition to the copolymer having the above-mentioned functional group, each homopolymer of the vinyl aromatic monomer (a) or the vinyl monomer (b) copolymerizable therewith. Combination or two or more types (a)
Alternatively, it is a resin composition containing a copolymer of (a) and (b) other than the copolymer of (b) and a copolymer having a functional group.

There are no particular restrictions on the polymerization method of these resin compositions, and radical polymerization, cationic polymerization, anionic polymerization, etc. are used.
sell. Next, in the method of mixing a resinous component and a rubbery component, monomers (a) and/or (b) are homopolymerized in the presence of a rubbery component, similar to the synthesis of so-called high impact polystyrene and ABS resin. Alternatively, there may be a graft polymerization method in which copolymerization is carried out, a blending method in which a resinous component and a rubbery component are mechanically mixed, etc., and these methods are not particularly limited.

On the other hand, the halogen flame retardant used in the present invention has an epoxy group, and has a functional group in the resin (1). It is a compound with reactivity of If the amount is more than 1 part by weight, the amount used will be excessive, and the physical properties of the resin, especially the thermal stability, will be deteriorated.

The flame retardant resin composition of the present invention comprises the halogen flame retardant (
■) can be added at any time during the production of resin (1), or the obtained resin (1) and halogen flame retardant (
It can also be easily produced by mixing (2) with a conventional mixing device such as a hot roll, a panburi mixer, or an extruder.

In addition, when reacting the resinous component with the functional group in the halogen flame retardant, tetra n-butylammonium bromide,
There is no particular problem in adding a reaction accelerator such as 2-ethyl-4-imidazole or boron trifluoride to the extent that the physical properties of the flame-retardant resin composition are not impaired. Also, resin (1
There is no problem in using inorganic flame retardants such as halogen-based flame retardants, phosphorus-based flame retardants, and antimony trioxide in combination, which do not react with the functional groups in ).

The present invention will be described in detail with reference to Examples below. The flame retardance in Examples, Reference Examples to Comparative Examples was measured based on Subject No. 94 established by the Underwriters Laboratory of the United States. .

The dimensions of the test piece are 118 inches thick, 112 inches wide, and 6 inches long. Also, all parts in the example sentences refer to parts by weight. Reference example 1 acrylonitrile
28 parts styrene
72〃Styrene●Butadiene rubber (Tuffden, 2000
A manufactured by Asahi Kasei Gyo Co., Ltd.) 15〃Benzoyl peroxide 0.15〃Dicumyl peroxide
0.08 tertiary dodecyl mercaptan
0.35 The above composition was charged into a closed reaction vessel equipped with a stirring device, and the rubber component was completely dissolved, and the temperature was raised to 77C.
Bulk polymerization was carried out for half an hour.

Further, an aqueous dispersant solution prepared in advance by mixing 1 (1) part of water, 4 parts of magnesium hydroxide, and 0.0 part of sodium lauryl sulfate was added and stirred to suspend. then 12
The temperature was raised to 0°C, and suspension polymerization was carried out for 5 hours. The obtained particles were washed with water and then dried. This is called resin A. This resin A was heated under a hydraulic press (200'C/10 minutes, cage pressure 100k).
9/d) and then cut to make a test piece.The test piece was measured for flammability, and found that it burned well. Reference example 2 Acrylonitrile 28 parts styrene
72〃Lauroyl peroxide
0.32 tertiary dodecyl mercaptan 0.2
7. Contains an aqueous dispersant solution prepared by mixing the above composition in advance with 4 parts of magnesium hydroxide and 0.0 part of sodium lauryl sulfate per 1 part of water.

The mixture was charged into a closed reactor equipped with a stirring device and thoroughly suspended. Thereafter, one direction suspension polymerization was carried out at 70'C. ．． The obtained particles were washed with water and then dried. This will be referred to as resin B. The flammability of this resin B was measured in the same manner as in Reference Example 1, and it burned well. Reference example 3 Styrene 1 (4) parts) Polybutadiene rubber (Diene NF-35AS manufactured by Asahi Kasei Industries, Ltd.) W part dibenzoyl peroxide
0.2〃Dicumyl peroxide 0.
07 Tertiary Decyl Mercaptan 0.05 The above composition was charged into a closed reaction vessel equipped with a stirring device, and after the rubber component was completely dissolved, the temperature was raised to 85° C. and bulk polymerization was carried out for 3 hours.

Furthermore, an aqueous dispersant solution prepared in advance by mixing 100 parts of water, 4 parts of magnesium hydroxide, and 0.0 part of sodium lauryl sulfate was added and stirred to suspend. Thereafter, the temperature was raised to 120°C, and suspension polymerization was carried out for 10 hours. The obtained polymer particles were washed with water and then dried. This will be referred to as resin C. Furthermore, this resin C
The flammability of the material was measured in the same manner as in Reference Example 1, and it burned well. Reference example 4 Styrene 1 (1) part Ditamyl peroxide 0.1 part Tertiary decyl mercaptan 0.5 part Magnesium hydroxide
4 parts Sodium lauryl sulfate 0.00
? 1 tap of water Pour the above composition into a reaction vessel equipped with a stirrer and make a suspension for 12 hours.
The temperature was raised to 0 can C.

After polymerization was carried out at 120° C. for 1 hour, the obtained polymer was washed and dried.

This will be referred to as resin D. The flammability of this resin D was measured in the same manner as in Reference Example 1, and it burned well. Reference example 5 Acrylonitrile 2z styrene
58〃Methacrylic acid
20〃α,α-Azobisisobutyronitrile 0.5〃In a reactor equipped with a stirring device and a reflux device,
Add the above composition and 1 (1) part of benzene and stir until the temperature reaches 70°C. This temperature was then maintained for 6 hours to effect polymerization.

The obtained benzene solution of the polymer was applied to a rotary evaporator to remove benzene and residual monomers, and then vacuum-dried. The obtained polymer had a weight average molecular weight of 68,000 as measured by gel permeation chromatogram (GPO) and contained 18.5% methacrylic acid. (21 carboxyl groups per weight average molecular weight 10,000) This is referred to as resin E. Furthermore, this resin E
The flammability of the material was measured in the same manner as in Reference Example 1, and it burned well. Reference example 6 Acrylonitrile 25 styrene
58〃2-hydroxyethyl methacrylate 20〃α,α-azobisisobutyronitrile 0.5〃Benzene 1
00 Polymerization and drying were performed under the same conditions as in Reference Example 3 to obtain a polymer.

The obtained polymer had a weight average molecular weight of 55,000 as measured by gel permeation chromatogram (GPC).
and 2-hydroxyethyl methacrylate is 19.
It contained 8%. (One hydroxyl group per weight average molecular weight of 10,000) This is designated as resin F. The flammability of this Resin F was measured in the same manner as in Reference Example 1, and it burned well.
Reference Example 7 100 parts of benzene was placed in a reactor equipped with a stirring device, a reflux device, and a monomer dropping device, and the temperature was raised to 70°C.

While maintaining this temperature, 200 parts of benzene and 5 parts of styrene were added using two monomer dropping devices while stirring. and a solution of 0.5 part of α,α-azobisisobutyronitrile and 4 parts of maleic anhydride in 2 (1) parts of benzene. A solution containing the above was continuously added to the reactor over a period of 2 hours to carry out polymerization. Thereafter, the temperature was maintained at 70°C for an additional 2 hours. The resulting benzene-insoluble polymer was separated, washed with hot benzene, and then dried in vacuum. The resulting polymer had a weight average molecular weight of 22,000 as determined by gel permeation chromatogram (GPC) and contained 54% maleic anhydride. (55 acid anhydrides per weight average molecular weight 10,000)
This will be referred to as resin G. The flammability of this resin G is shown in Reference Example 1.
When measured in the same manner as above, it burned well. Example 1 47 parts of resin A obtained in Reference Example 1 and resin E2 obtained in Reference Example 5. Brominated phenol novolac epoxy resin (trade name BRENl manufactured by Nippon Kayaku Co., Ltd. Brome content 36.5% by weight, epoxy equivalent) 285) 33 parts were melt-blended for 5 minutes at 200°C using a Brabender plastogram, and then breath molded (200C/10 minutes, 100k9/Cf).
l), a predetermined test piece was prepared by cutting, and the physical properties were measured using conventional methods.The tensile strength was 420k9/d1, the tensile elongation at break was 6%, and the heat distortion temperature (load 18.6kg/Clt).
) The flammability was -1 at 75°C.

Comparative Example 1 Physical properties were measured in the same manner as in Example 1 except that resin B was used instead of resin E in Example 1, and the flammability was V-2.
Furthermore, the heat distortion temperature was as low as 67° C., and the flame retardancy and heat resistance were inferior to that of Example 1.

Example 2 47 parts of resin A obtained in Reference Example 1, a part of resin F obtained in Reference Example 6, and 33 parts of brominated phenol novolak epoxy resin (trade name BREN, manufactured by Nippon Kayaku Co., Ltd.) were analyzed by Brabender plastogram. After melt blending, it was press molded and its physical properties were measured using a conventional method, and the tensile strength was 446.
The k9/d1 tensile elongation at break was J8%, the heat distortion temperature was 76°C, and the flammability was -1.

Comparative Example 2 Physical properties were measured in the same manner as in Example 2 except that Resin B was used instead of Resin F. The flammability was V-2, and the heat distortion temperature was as low as 66°C. Compared to Example 2, flame retardancy and heat resistance are inferior.

Example 3 Resin C5 obtained in Reference Example 3? 5 parts of the resin Gl obtained in Reference Example 7 and 33 parts of a bromated phenol novolac epoxy resin (trade name: BREN manufactured by Nippon Kayaku Co., Ltd.) were melt-blended in the same manner as in Example 1, and then a test piece was prepared and the physical properties were determined. Measured tensile strength: 410 kg/c, surface tensile elongation: 7%,
The heat distortion temperature was 76°C and the flammability was V-2.

Comparative Example 3 The physical properties were measured in the same manner as in Example 3 except that Resin D was used instead of Resin G, and the flammability was -
Although it was the same as Example 2, the heat distortion temperature was as low as 69°C and the heat resistance was inferior to that of Example 3.The molding conditions and u constant conditions in the Examples and Comparative Examples were as follows.

) Molding conditions (a) Brapenter ◆ Blastogram Mixer temperature 200℃ Rotor rotation speed 50r'Pm Kneading time
5 minutes (b) Breath molding Breath temperature: 200°C Breathing time: 5 minutes preheating, pressurized 1 powder (when pressurized) Gauge pressure: 100k9/CrfL (C) Extrusion Cylinder temperature: 2200C Screw rotation speed
50r'Pm(d) Injection molding Cylinder temperature 2200C gauge pressure
70kg/d Mold temperature
50'C) Measurement temperature (a) Flammability UL standard Subject No. 94 Test piece Length 118 inches, Width 1-2 inches, Length 6 inches (b) Tensile strength and tensile elongation at break Breath molding completely cut One test piece JISK injection molded product ASTM D638 Measurement conditions Temperature 20°C Humidity 65% (C) Heat distortion temperature ASTM D-648 Measuring load 18.56 kg/d

Claims (1)

[Claims] 1 Consisting of a vinyl aromatic monomer and one or more vinyl monomers copolymerizable with it, one or two selected from hydroxyl groups, carboxyl groups, and acid anhydrides (groups).
The number of functional groups is 1 to 1 per 10,000 weight average molecular weight.
A copolymer having 55 or a copolymer post-treated to have the above-mentioned functional groups is contained in an amount of 3% by weight or more based on the total resinous component, and together with 99 to 35% by weight of a vinyl aromatic monomer. One or more polymerizable vinyl monomers 1-65
Resin (I) 98 obtained from 100 to 60% by weight of a resinous component consisting of 100% to 60% by weight and 0 to 40% by weight of a rubbery component
~60 parts by weight of a flame retardant resin composition consisting of 2 to 40 parts by weight of a halogen flame retardant alone or a mixture of two or more (II) containing an epoxy group capable of reacting with a functional group in the resin (I) thing.