JPS591307B2 - Nannenseiji Yushisoseibutsu - 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) obtained from a resinous component containing a vinyl monomer having an epoxy group as an essential component, alone or in a mixture with a rubber component, and a hydroxyl group, a phenolic hydroxyl group, a carboxyl group, or an acid anhydride. The present invention relates to a flame-retardant resin composition with excellent heat resistance, which is composed of a halogen-based flame retardant containing halogen-based flame retardants alone or in a mixture of two or more.

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, like many other synthetic polymers, styrenic resins 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 rogens, phosphorus, etc., and flame retardants such as antimony trioxide. Although the desired flame retardance can be obtained, there is a tendency for other physical properties to be adversely affected.

In particular, when a low molecular weight flame retardant is added and mixed, there are problems such as a decrease in heat distortion temperature, generation of corrosive gas during molding, toxicity of substances exuded from the resin during long-term use, and sustainability of flame retardancy. It is said that On the other hand, in the method of making flame retardant by copolymerization, compounds containing halogen or phosphorus are used as flame retardant imparting compounds, but they do not have the ability to copolymerize with other monomers or the desired physical properties of the resulting resin composition. Because they are difficult to equip, there are still only a few of them in actual use, 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, in the present invention, the rubber component is 0.
98 to 60 parts by weight of a resin obtained from 100 to 60 parts by weight of a resinous component containing as an essential component a vinyl monomer containing an epoxy group and a hydroxyl group, a phenolic hydroxyl group, a carboxyl group, or an acid anhydride. Single or mixture of two or more halogenated flame retardants (11) 2-40
A flame-retardant resin composition with excellent heat resistance consisting of parts by weight,
It is characterized in that its resinous component consists of.

Here, the vinyl monomer having an epoxy group includes glycidyl methacrylate, glycidyl acrylate, glycidyl vinyl ether, etc., and there is no problem even if two or more of them are used in combination.

The halogen flame retardants having a hydroxyl group according to the present invention include 2,2-bis(3',5'-dibromo-4'β-oxyethoxyphenyl)propane and 2,2-bis(bromomethyl)-1 - 3-propanediol, etc., and the halogenated flame retardant having a phenolic hydroxyl group includes tetraprombisphenol A1, tetraprombisphenol S, tripromphenol, and the like. Furthermore, the halogen-based flame retardants having a carboxyl group include tribromobenzoic acid and tribromoacetic acid, and the halogen-based flame retardants having an acid anhydride include tetrabromo-phthalic anhydride and chlorendic anhydride. As the rubber component in the present invention, those commonly used in the production of impact-resistant polymers may be used, such as polyptadiene rubber, butadiene/styrene rubber, ethylene/propylene rubber,
Acrylic rubber, chloroprene rubber, etc. can be used.

Next, as the vinyl aromatic monomer, styrene is most suitable, but various substituted styrene derivatives such as α-methylstyrene and p-methylstyrene can also be used, and mixtures of these and styrene can also be used. be able to. Furthermore, as the vinyl cyanide monomer, acrylonitrile is most suitable, but memecrylonitrile and the like can also be used. In the present invention, the resinous components are as follows, and the amount of the vinyl monomer containing an epoxy group (a) used depends on the type of functional group-containing flame retardant required to make the resin flame retardant,
Corresponding to the amount of
It is not necessary to use more than % by weight, and it is rather disadvantageous in terms of the physical properties of the resin composition and also in terms of cost.

As described above, in the present invention, resinous components modified to contain epoxy groups are used. Among the above monomers, (a) and ( copolymers of (a), (5) and (c), such as copolymers of b), modified acrylonitrile styrene (AS) resins, rubbery components such as modified acrylonitrile fluoride styrene (ABS) resins; to (a)
, Cb) and (c) are graft copolymerized.

Furthermore, these single resins can be used as (b) resins such as polystyrene.
A copolymer of (b) and (c) such as AS resin, a graft copolymer of (b) with a rubbery component such as high impact polystyrene, or a rubbery component such as ABS resin. It can be used as the resinous component of the present invention by blending it with the graft copolymers (b) and (c). Particularly preferred resinous components include modified AS resins and blends thereof with AS resins or ABS resins, modified ABS resins and blends thereof with AS resins or ABS resins, and modified polystyrenes and high-impact polystyrenes or A specific example is a blend with polystyrene. There are no particular restrictions on these polymerization methods and blending methods, and conventional methods may be used.
On the other hand, the halogen-based flame retardant used in the present invention is a compound containing a functional group that is reactive with an epoxy group, and the amount used varies depending on the degree of flame retardation aimed at. In the flame retardant resin composition of the invention, if it is less than 2 parts by weight, the purpose of flame retardation cannot be achieved, and if it is more than 40 parts by weight,
If the amount used is excessive, the physical properties of the resin, especially the thermal stability, etc. will be deteriorated.

The flame retardant resin composition of the present invention comprises the halogen flame retardant (
I[) can be added at any time during the production of resin (1), or the resulting resin (1) and halogenated flame retardant (
11) in a conventional mixing device, such as a hot roll, a Banbury mixer, or an extruder.

In addition, when the resin component reacts with the functional group in the rogen-based flame retardant, a reaction accelerator such as tetra-n-butylammonium bromide, 2-ethyl-4-imidazole, or boron trifluoride is used. There is no particular problem in adding it within a range that does not impair the physical properties of the flame-retardant resin composition.

Further, there is no particular problem in using halogen-based flame retardants, phosphorus-based flame retardants, and inorganic flame retardants such as antimony trioxide in combination, which do not react with epoxy groups.

The details of the present invention will be described below with reference to Examples, and the flammability in the Examples, Reference Examples, and Comparative Examples was measured based on Subdivision No. 94 established by the Underlimaze Laboratory of the United States.

The dimensions of the test piece are 1/8 inch thick, 1/2 inch wide, and 6 inches long. All parts in the example sentences refer to parts by weight. Reference Example 1 The above composition was charged into a closed reaction vessel equipped with a stirring device, and the temperature was raised to 72°C until the rubber component was completely dissolved, and bulk polymerization was carried out for 3 and a half hours.

Furthermore, an aqueous dispersant solution prepared in advance by mixing 100 parts of water, 4 parts of magnesium hydroxide, and 0.002 parts of sodium lauryl sulfate was added, and the mixture was stirred and suspended. 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 pressed in a hydraulic press (200°C/10 minutes, gauge pressure 100 kg).
/Cd) was press-molded and cut into test pieces, and the flammability was measured, and it burned well. The above composition was charged into a closed reactor equipped with a stirring device containing an aqueous dispersant solution prepared by mixing 100 parts of water with 4 parts of magnesium hydroxide and 0.002 parts of sodium lauryl sulfate. ,
Suspended well.

Thereafter, suspension polymerization was carried out at 70°C for 10 hours. 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 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.

Further, an aqueous dispersant solution prepared in advance by mixing 100 parts of water, 4 parts of magnesium hydroxide, and 0.002 parts of sodium lauryl sulfate was added, and the mixture was stirred and suspended. 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 D. Furthermore, this resin D
The flammability of the material was measured in the same manner as in Reference Example 1, and it burned well. Reference Example 5 In the same manner as in Reference Example 4, polymerization was carried out at a polymerization temperature of 70° C. for 15 hours, and a polymer was obtained after drying.

When this obtained polymer was measured by gel permeation chromatogram (GPC), its weight average molecular weight was 47,000, and glycidyl methacrylate was
It contained 8.6%. This will be referred to as resin E. The flammability of this resin E was measured in the same manner as in Reference Example 1, and it burned well. Reference Example 6 The above composition was placed in a reaction vessel equipped with a stirrer to form a suspension, and the temperature was raised to 120°C.

After polymerization was carried out at 120° C. for 10 hours, the obtained polymer was washed and dried.

This is referred to as resin F. The flammability of this resin F was measured in the same manner as in Reference Example 1, and it burned well. Example 1 56 parts of the resin A obtained in Reference Example 1, 22 parts of the resin C obtained in Reference Example 3, and 22 parts of tetrabromofunolic anhydride were melt-blended at 200°C for 5 minutes using a Brabender plastogram, and then press-molded (200°C). °C/10 minutes, 100
k9/Cr! l), a specified test piece was prepared by cutting, and the physical properties were measured by a conventional method, and the tensile strength was 4551.
<g/Cd tensile elongation at break 9%, heat distortion temperature (load 18.
6 kg/Cd) The flammability was V-0 at 80°C.

Comparative Example 1 When the physical properties were measured in the same manner as in Example 1 except that Resin B was used instead of Resin C in Example 1, the flammability was V-
Moreover, the heat distortion temperature (load: 18.6 kg/Cd) was as low as 70°C, and the flame retardance and heat resistance were inferior to Example 3.

Example 2 53 parts of the resin A obtained in Reference Example 1, 22 parts of the resin C obtained in Reference Example 3, and 25 parts of tetraprombisphenol A were melt-blended in the same manner as in Example 1, and then a test piece was prepared and the physical properties were determined. When measured, the tensile strength was 470kg/Cr!
IL, tensile elongation at break 7%, heat distortion temperature (load 18.6k
9/CrA) The flammability was VO at 86°C.

Comparative Example 2 The physical properties were measured in the same manner as in Example 1 except that Resin B was used instead of Resin C in Example 2, and the flammability was V-
0, but the heat distortion temperature (load 18.6 kg/
Cd) is as low as 64° C., and the heat resistance is inferior to that of Example 2.

Example 3 After melt blending the resin B6O part obtained in Reference Example 2, the resin C2O part obtained in Reference Example 3, and the tetraprombisphenol A2O part in the same manner as in Example 1, a test piece was prepared and the physical properties were evaluated. When measured, the tensile strength was 440k9/Cd,
Tensile elongation at break 6%, heat distortion temperature (load 18.6 kg/C
rli) Flammability was V2 at 81°C.

Comparative Example 3 When the physical properties were measured in the same manner as in Example 1 except that Resin B was used instead of Resin C in Example 3, the flammability was -2 as in Example 3, but the heat distortion temperature was (Load 18.

6k9/Cd) was as low as 71°C.

Example 4 89 parts of resin B obtained in Reference Example 2 and Reference Example 3
5 parts of the resin C obtained in step 1 and 6 parts of tetraprombisphenol A were blended in a simple blender, and then an extruder (2
A test piece was prepared using an injection molding machine (cylinder temperature: 220°C), and its physical properties were measured. The tensile strength was 620kg/Cd, the tensile elongation at break was 8%, and the heat distortion temperature (load: 18.6kg). /Cd) At 78℃, the flammability is -
It was 2.

Example 5 56 parts of the resin D obtained in Reference Example 4, 22 parts of the resin E obtained in Reference Example 5, and 22 parts of tetrabromo phthalic anhydride were melt-blended using a Brabender plastogram, then press-molded, and the physical properties were determined by a conventional method. When measured, the tensile strength was 452 kg/Cd, the tensile elongation at break was 7%, the heat distortion temperature was 74°C, and the flammability was V-0.

Comparative Example 4 The physical properties were measured in the same manner as in Example 5 except that Resin D was used instead of Resin E in Example 5, and the flammability was -2.
Moreover, the heat distortion temperature was as low as 62° C., and the flame retardance and heat resistance were inferior to that of Example 5.

Example 6 56 parts of Resin D obtained in Reference Example 4, 22 parts of Resin E obtained in Reference Example 5, and 22 parts of Tetraprombisphenol A were melt-blended in the same manner as in Example 1, and then a test piece was prepared and the physical properties were determined. When measured, the tensile strength was 440k9/Cd,
The tensile elongation at break was 6%, the heat distortion temperature was 78°C, and the flammability was -0.

Comparative Example 5 The physical properties were measured in the same manner as in Example 6 except that Resin F was used instead of Resin E in Example 6, and the flammability was V-2.
Moreover, the heat distortion temperature was as low as 59° C., and the flame retardancy and heat resistance were inferior to that of Example 6.

The molding conditions and measurement conditions in the Examples and Comparative Examples are as follows.

O Molding conditions (a) Brabender plastogram (c) Extrusion (d) Injection molding (a) Flammability UL standard subdivision No. 94 test piece (b) Tensile strength and tensile elongation at break (c) Heat distortion temperature

Claims (1)

[Claims] 1 100 to 60% resinous component consisting of 1 to 30% by weight of an epoxy group-containing vinyl monomer, 99 to 35% by weight of a vinyl aromatic monomer, and 0 to 35% by weight of a vinyl cyanide monomer
98 to 60 parts by weight of a resin or resin mixture (I) obtained from 0 to 40 parts by weight of a rubbery component and a halogenated flame retardant containing a hydroxyl group, a phenolic hydroxyl group, a carboxyl group, or an acid anhydride, alone or A mixture of two or more types (I
I) A flame retardant resin composition comprising 2 to 40 parts by weight.