JPS5830337B2 - Nannenseino Sugreta styrene cage - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a styrenic resin composition with excellent flame retardancy. A styrenic resin with excellent flame retardancy can be obtained by blending salt, mixing this mixture at a temperature where the fatty acid metal salt melts, pulverizing it, and adding the resulting flame retardant alone or together with other flame retardants. The present invention relates to a method for producing a composition.

A method of imparting flame retardancy to a thermoplastic resin by adding a halogen-containing compound or a combination of a halogen-containing compound and antimony trioxide to the thermoplastic resin as a flame retardant is already well known.

When antimony trioxide as a flame retardant is added to thermoplastic resins, the resulting resin composition often suffers from a decrease in impact resistance and lack of flame retardant effect. This is thought to be due to poor dispersion in the resin.

One possible solution to this problem of poor dispersion is to use antimony trioxide in the form of ultrafine particles, and this type of antimony trioxide is also commercially available.

However, even if antimony trioxide in the form of ultrafine particles is used, it is difficult to reduce the decrease in impact resistance, and the current objective cannot be achieved.

On the other hand, in the case of rubber-modified impact-resistant materials such as ABS resin and high-impact polystyrene, it is possible to increase the rubber content to improve the impact resistance. Conversely, the rigidity decreases and the flammability increases, so in order to make such rubber-modified impact-resistant materials flame retardant, it is necessary to increase the amount of antimony trioxide and other flame retardants. The impact resistance must be increased, which again leads to a decrease in impact resistance.

As described above, it has been extremely difficult to make rubber-modified impact-resistant materials flame-retardant without having almost any adverse effect on the impact resistance.

Under such circumstances, the present inventors have arrived at the present invention as a result of intensive studies aimed at making rubber-modified impact-resistant styrenic resin flame retardant.

An object of the present invention is to overcome the above-mentioned technical difficulties and provide a method for producing a styrenic resin composition having high impact resistance and excellent flame retardancy.

For this purpose, for 100 parts by weight of antimony dioxide,
2 to 50 parts by weight of a fatty acid metal salt is blended, this mixture is mixed at a temperature where the fatty acid metal salt melts, and the resulting mixture is crushed into styrenic resin either alone or in combination with other flame retardants. This can be easily achieved by blending.

Hereinafter, the present invention will be described in detail. The fatty acid metal salt that can be used in the present invention has a melting point of 80 to 1
A temperature range of 80°C is preferred.

The reason for this is that substances with melting points in this range are solid at room temperature during storage and mixing, and are easy to handle. When mixed at a temperature where the fatty acid metal salt melts, only the fatty acid metal salt becomes molten and covers the antimony trioxide particles, and when this returns to room temperature, antimony trioxide coated with the fatty acid metal salt is obtained. This is because it is preferable because it can be pulverized and made into fine powder if necessary.

Specific examples of such fatty acid metal salts include magnesium stearate, zinc stearate, and the like.

The shape of this particular fatty acid metal salt can be various, such as powder, flake, or bead, but among these, it is easy to crush when mixed at the temperature at which the fatty acid metal salt melts, and A material that can easily adhere uniformly to antimony oxide particles is preferred.

The amount of fatty acid metal salt added to antimony trioxide is preferably 2 to 50 parts by weight based on 100 parts by weight of antimony trioxide.

If it is less than 2 parts by weight, it will not be possible to prevent antimony trioxide from agglomerating, and if it exceeds 50 parts by weight, it may adversely affect the flame retardant effect of the molded product or reduce the impact resistance. This is because physical properties deteriorate.

Therefore, the amount within the above range is preferred, and particularly preferred is 10 to 40 parts by weight.

Note that not only one type of fatty acid metal salt but also a mixture of two or more types can be used.

The following method is used to mix, melt, and grind antimony trioxide with a fatty acid metal salt.

The above-mentioned amount of fatty acid metal salt is weighed into antimony trioxide and mixed uniformly in a conventional manner.

During this mixing step, the fatty acid metal salt should not be melted.

As the mixing means, a commonly used mixer is used.

However, since many powders have a small specific volume, a ribbon blender or a Henschel type blender is particularly suitable.

After the above formulation is uniformly mixed, antimony trioxide is melt-coated with the fatty acid metal salt by mixing at a temperature where the fatty acid metal salt melts, and then pulverized to form particles.

This mixture can be mixed at a temperature at which the fatty acid metal salt melts by feeding the mixture into a shaker or a hammer type high-speed crusher that can be preheated to near the melting point of the fatty acid metal salt. You can.

However, if a hammer type high-speed crusher is used in this case, the subsequent crushing step can be omitted.

In addition, as a hammer type high-speed crusher, the
Equipped with a swing hammer that rotates at a high speed of 0 to 12,000 mm, the rotation of this hammer impacts the mixture of antimony trioxide and fatty acid metal salt, instantly crushing and melting the fatty acid metal salt, thereby converting the antimony dioxide into It is preferable to have a structure that allows the particle size to be adjusted to a desired size by controlling the shape of the screen to be coated or attached, the size, the number of rotations of the hammer, the number of hammers, the amount of compound supplied, etc.

Examples of such high-speed pulverizers include the Micro Pulverizer manufactured by Hosokawa Iron Works Co., Ltd., the Nick Atomizer manufactured by Fuji Paudal Co., Ltd., and the Ec Pulverizer manufactured by Fuji Paudal Co., Ltd.

Next, the styrenic resin in the present invention refers to polymers of styrene and vinyl aromatic compound monomers such as α-substituted styrene such as α-methylstyrene, vinyltoluene, and nuclear-substituted styrene such as O-chlorostyrene; Mainly vinyl aromatic compound monomers, other monomers copolymerizable with them, such as acrylonitrile, acrylic acid and methacrylic acid, vinyl compounds such as methyl or ethyl esters, vinyl pyridine, vinyl carbazone, etc. Copolymers with vinyl heterocyclic compounds, etc.: Other common diene compounds such as butadiene, 1-chlorobutadiene, 2-chlorobutadiene, isoprene, and EPD
It includes a graft polymer in which a vinyl aromatic compound monomer alone or a vinyl compound as described above is grafted onto a saturated rubber such as M, butyl rubber, and the like.

Note that the amount of antimony dioxide melt-coated with the fatty acid metal salt that should be added to the styrene resin that should impart flame retardancy depends on the type of styrene resin used, especially the amount of antimony dioxide in it. The amount of antimony dioxide is preferably 5 to 20 parts by weight per 100 parts by weight of the styrene resin as the base, although it mainly depends on the amount of the rubber component contained.

In the method of the present invention, antimony trioxide surface-treated with a fatty acid metal salt is blended into the styrene resin that serves as the base as described above, but it is also possible to use this blend in combination with other flame retardants. .

Flame retardants that can be used in this case include halogen-containing polymers such as chlorinated polyethylene, chlorinated paraffins, halogenated aliphatic compounds such as tetrabromobutane and hexabromocyclododecane, pentafromotoluene, hexabromobenzene, One type or a mixture of two or more types of halogenated phosphorus-containing compounds such as tetrabromobisphenol A can be used.

To obtain the composition of the present invention, antimony trioxide, the surface of which is fused and coated with the fatty acid metal salt obtained by the above method, is blended alone or together with the above flame retardant into the above styrene resin.

This compound is mixed in a commonly used mixer such as a conical blender, drum tumbler 1 or Henschel mixer, then kneaded in an extruder or Banbury mixer and pelletized to obtain a flame-retardant resin composition. You can get it.

At this time, other additives such as antioxidants, ultraviolet absorbers, blowing agents, fillers, other compatible resins (polyvinyl chloride, , chlorinated polyethylene, etc.), pigments, dyes, etc., can of course be added to the scales.

The composition obtained by the method of the present invention contains antimony dioxide that has been surface-treated with a fatty acid metal salt, and has extremely good dispersion in a styrenic resin.

Therefore, compared to conventionally known flame-retardant styrenic resin compositions containing antimony dioxide that are not treated with fatty acid metal salts, the flame-retardant effect can be maintained at the same level or higher even when the amount of antimony trioxide added is reduced. It is possible to significantly improve the deterioration of impact resistance, and its industrial utility value is extremely large.

Next, the present invention will be specifically explained with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

The test method adopted in the following examples is as follows.

・Izotsu impact strength (notched) test: JIS-
6871 - Flammability test: UL-94 method, subject 94/746
(dated February 1, 1974).

This standard was developed by the U.S. Underwriters Laboratory.
・Ink (underwriterslaborato
ries I nc,), during the vertical combustion test, the burning drippings do not ignite the dry surgical cotton, but the time to emit a flame and burn is less than 10 seconds (
94V-0, less than 30 seconds (within 5 seconds on average, and less than 30 seconds of red-hot combustion time without emitting a flame)
94V-1, which burns red hot for less than 25 seconds on average and burns red hot without producing a flame for less than 60 seconds. It burns for less than 30 seconds (on average less than 25 seconds, and the time to burn red hot without emitting a flame is less than 60 seconds), and the flame is in front of the 40 inch standard line during the horizontal combustion test. 94V-2, and during the horizontal combustion test, the burning rate in the 30 inch section disappears within 1.5 inch/- or before the 4.0 inch standard line, but does not meet the criteria of the vertical test. The thing is called 94HB.

Example 1 (1) Treatment of antimony trioxide Antimony trioxide (manufactured by Sumitomo Metals KK, average particle size approximately 1 μm)
)900? and magnesium stearate (Nitto Kasei KK)
100f (manufactured by Manufacturer), respectively, put them in a beaker and mix them, then preheat this to 100°C.
The mixture was placed in a 1-capacity shaker (manufactured by Ishikawa Factory Co., Ltd.), and stirring was continued for 30 minutes at 32 rpm while maintaining the temperature at 100°C.

At this mixing stage, the magnesium stearate was melted and softened, and the antimony trioxide fine powder was uniformly dispersed therein.

After stirring, this mixture was taken out from the shaker, cooled to room temperature, and the solidified mixture was crushed using a mortar.

What was obtained was a white powder in which the surface of antimony trioxide was coated with magnesium stearate.

This is called flame retardant I.

(2) Add 10 parts by weight of the flame retardant I obtained by the treatment described in (1) above to a resin whose main component is acrylonitrile-polychloroprene-styrene terpolymer (hereinafter referred to as
This was blended into 90 parts by weight of Copolymer A*1), kneaded in a Banbury mixer, and then test pieces were prepared, and the impact resistance and flame retardance of the test pieces were evaluated.

The results are shown in Table 1.

Note *1 Copolymer A is the following “crumb”, JA B S
Resin” and 5AN-C (manufactured by Mitsubishi Monsanto Chemical Co., Ltd., As
resin).

(b) Production of "crumb" Polychloroprene latex (manufactured by DuPont, NPR-3570) was placed in a 51-capacity autoclave equipped with a stirrer, reflux condenser, thermometer, auxiliary agent addition device, and emulsifier addition port.
, solids content 47%) to 1240? , Dowfax (Dow Chemical Company, sodium salt of alkyldiphenyloxide sulfonate) 581, tilpinoline 3.22
, 15562 liters of deionized water was charged.

Nitrogen gas was introduced into the autoclave while the contents of the autoclave were stirred at 200 rpm, and after sufficient nitrogen substitution, heating was started under a nitrogen atmosphere to bring the contents of the autoclave to 85°C.

While keeping warm at this temperature, a monomer mixture consisting of styrene 5212 acrylonitrile 2451 t-dodecyl mercaptan 3.22 4% aqueous solution of hydrium persulfate 204 The mixture was charged and a polymerization reaction was performed.

After 1 and 2 hours had passed after starting the continuous addition of the above monomers, 5% of a 10% aqueous solution of sodium lauryl sulfate was added.
8.5f each was charged into the autoclave.

After completing the continuous addition of the above monomer mixture, styrene 50
A styrene solution consisting of Y and 4.12% of azobisisobutyronitrile was continuously blended into an autoclave over a period of 15 minutes in such a proportion that the amount charged was % and the polybutadiene was 2.5% by weight.

Example 2 (1) Treatment of antimony trioxide 800 y of antimony dioxide and 200 y of magnesium stearate were each weighed and treated in the same manner as described in Example 1 (1), so that the surface of antimony trioxide became stearin. A white powder coated with magnesium acid was obtained.

This is called a flame retardant■.

(2) 11.3 parts by weight of the flame retardant ■ obtained by the treatment described in (1) above was blended with 88.7 parts by weight of copolymer A similar to that used in Example 1 (2), and Banbury mixer
After kneading, a test piece was prepared, and the impact resistance and flame retardance of this test piece were evaluated.

The results are shown in Table 1.

Example 3 (1) Treatment of antimony trioxide 70 oz of antimony dioxide and 300 y of magnesium stearate were each weighed and treated in the same manner as described in Example 1 (1), so that the surface of antimony trioxide became stearin. A white powder coated with magnesium acid was obtained.

This is called a flame retardant■.

(2) 112.9 parts by weight of the flame retardant 11 obtained by the treatment described in (1) above was blended with 87.1 parts by weight of the same copolymer A used in Example 1 (2), and a Banbury mixer was added. - After kneading, a test piece was prepared, and the impact resistance and flame retardance of this test piece were evaluated.

The results are shown in Table 1.

Example 4 (1) Treatment of antimony trioxide 45 kg of antimony trioxide and 5 kg of magnesium stearate were each weighed, and both were mixed in a 2501 capacity glue pump blender at room temperature at 6° rpm for 30 minutes. The obtained mixture was put into the hopper of a nick atomizer (manufactured by Fuji Powder Co., Ltd.) and heated to 85% at room temperature.
Operation was started at 0° rpm.

After starting, cooling water was poured to prevent the temperature of the machine from rising too high.

The compound put into the hopper is fed into the grinding chamber by a screw feeder within about an hour, and is subjected to an impact force between a high-speed rotating hammer and a lining plate to remove the magnesium stearate in the compound. This melted and coated the surface of the antimony dioxide fine powder, and while this state passed through a screen, it became a white powder with the desired particle size.

This is called a flame retardant■.

(23 Parts by weight of the flame retardant IVIO obtained by the treatment described in (1) above were blended with 90 parts by weight of the same copolymer A as used in Example 1 (2), and the mixture was kneaded in a Banbury mixer. A test piece was prepared, and the impact resistance and flame retardance of this test piece were evaluated.

The results are shown in Table 1.

Example 5 (1) Treatment of antimony trioxide 40 kg of antimony trioxide and 10 kg of magnesium stearate were each weighed and treated in the same manner as described in Example 4 (1) to remove the A white powder was obtained in which the surface of antimony trioxide fine powder was melted and coated with magnesium stearate.

This is called a flame retardant ■. (2) 11.3 parts by weight of the flame retardant V1 obtained by the treatment described in 81 above was added to Example 1 (2).
The mixture was blended with 88.7 parts by weight of copolymer A similar to that used in , and kneaded in a Banbury mixer to prepare a test piece, and the impact resistance and flame retardance of this test piece were evaluated.

The results are shown in Table 1.

Example 6 (1) Treatment of antimony trioxide Same as the method described in Example 4 (1) (flame retardant ■) (2
) Flame retardant ■ 4 parts by weight dibutyltin maleate stabilizer 4.
5 parts by weight and 30 parts by weight of Vinyryoku KR-600 (manufactured by Mitsubishi Monsanto Kasei KK, polyvinyl chloride trade name) and 30 parts by weight of Tufflex 610A (manufactured by Mitsubishi Monsanto Kasei KK, ABS
Resin (trade name) was added to 100 parts by weight and kneaded in a Banbury mixer to prepare test pieces, and the test pieces were evaluated for impact resistance and flame retardancy.

The results are shown in Table 1.

Example 7 (1) Treatment of antimony trioxide Same as the method described in Example 4 (1) (flame retardant ■) (2
) Flame retardant ■ 5 parts by weight, 4.5 parts by weight of diptyltin maleate and vinylic KR in the same manner as described in Example 6 (2).
-Tuflex 610A100 with 60030 parts by weight
After mixing in parts by weight and kneading in a Panbury mixer, a test piece was prepared, and the impact resistance and flame retardance of this test piece were evaluated.

The results are shown in Table 1. Example 8 (1) Treatment of antimony trioxide Same method as described in Example 4 (1) (flame retardant ■).

(2) Flame retardant (1) 6 parts by weight of Tuflex 610 was added to 4.5 parts by weight of dibutyltin maleate and 6 parts by weight of Vinica KR-60030 in the same manner as described in Example 6 (2).
After blending with 100 parts by weight of A and kneading in a Banbury mixer, test pieces were prepared, and the impact resistance and flame retardance of the test pieces were evaluated.

The results are shown in Table 1. Example 9 (1) Treatment of antimony trioxide Same method as described in Example 5 (1) (flame retardant ■).

(2) Parts by weight of flame retardant V5 were added to Tuflex 610A10 along with 4.5 parts by weight dibutyltin maleate and Vinyl KR60030 parts by weight, as described in Example 6(2).
After blending to 0 parts by weight and kneading with a Banbury mixer,
A test piece was prepared, and the impact resistance and flame retardance of this test piece were evaluated.

The Q results are shown in Table 1. Example 10 (1) Treatment of antimony dioxide Same method as described in Example 4 (1) (flame retardant ■).

(2) 3.4 parts by weight of M fuel IV was mixed with hexabromobenzene (manufactured by Nippo Chemical KK, FRB (trade name)) and Tuflex 410A (manufactured by Mitsubishi Monsanto Kasei KK, ABS).
After adding the mixture to a resin (trade name) and kneading it in a Banbury mixer, a test piece was prepared, and the impact resistance and flame retardance of this test piece were evaluated.

The results are shown in Table 1. Example 11 (1) Treatment of antimony dioxide Same method as described in Example 4 (1) (flame retardant ■).

(2) Add 4.5 parts by weight of flame retardant ■ to 15 parts by weight of flame retardant tetrabromobisphenol A (manufactured by Kijin Kasei KK, FG2000 (trade name)) and Dialex H'l'-59 (
After adding L to 100 parts by weight of impact-resistant polystyrene (trade name, manufactured by Mitsubishi Monsanto Kasei KK) and kneading it in a Banbury mixer, test pieces were prepared, and the impact resistance and flame retardance of the test pieces were evaluated.

The results are shown in Table 1.

Example 12 (1) Treatment of antimony dioxide Same method as described in Example 4 (1) (flame retardant ■).

(2) Flame retardant IV5. Parts by weight of O were added to 100 parts by weight of Dialex HT-59 along with 15 parts by weight of tetrabromobisphenol A in the same manner as described in Example 11 (2), and after kneading in a Banbury mixer, a test piece was prepared. The impact resistance and flame retardance of the test pieces were evaluated.

The results are shown in Table 1.

Next, for comparison with the resin compositions according to the present invention described in Examples 1 to 12, a composition in which untreated antimony trioxide was blended with copolymer A, ABS resin, and high-impact polystyrene was prepared. Examples of similar evaluation tests for products are shown below.

Comparative Example 1 9 parts by weight of untreated antimony trioxide were blended with 91 parts by weight of the same copolymer A used in Example 1 and kneaded in a Banbury mixer to prepare a test piece. and flame retardancy were evaluated.

The results are shown in Table 1. Comparative Example 2 In place of the flame retardant I used on the same side in Example 1, 9 parts by weight of untreated antimony trioxide was used together with 1 part by weight of magnesium stearate, and the mixture was kneaded and tested in the same manner as in Example 1. A test piece was prepared, and the impact resistance and flame retardance of this test piece were evaluated.

The results are shown in Table 1.

Comparative Example 3 Instead of the flame retardant ■ used on the same side in Example 1, colloidal antimony trioxide (Nyacol, USA) was used.
manufactured by Inc., average particle diameter of about 15 mμ, 5b203
Using 10 parts by weight (content 90% by weight), a test piece was prepared by kneading in exactly the same manner as in Example 1, and the impact resistance and flame retardance of this test piece were evaluated.

The results are shown in Table 1. Comparative Example 4 A test piece was prepared by kneading in exactly the same manner as in Example 6, except that 4 parts by weight of untreated antimony dioxide was used in place of the flame retardant ■ used on the same side in Example 6. Impact resistance and flame retardancy were evaluated.

The results are shown in Table 1.

Comparative Example 5 In Example 7, 5 parts by weight of untreated antimony trioxide was used in place of the flame retardant ■ used in the same example, and a test piece was prepared by kneading in the same manner as in Example 7. The pieces were evaluated for impact resistance and flame retardancy.

The results are shown in Table 1.

Comparative Example 6 In Example 8, 6 parts by weight of untreated antimony trioxide was used in place of the flame retardant ■ used in the same example, and a test piece was prepared by kneading in the same manner as in Example 8. The impact resistance and flame retardance of the test pieces were evaluated.

The results are shown in Table 1.

Comparative Example 7 In Example 10, 3 parts by weight of untreated antimony trioxide was used in place of the flame retardant (■) used in the same example, and a test piece was prepared by kneading in the same manner as in Example 10, except that 3 parts by weight of untreated antimony trioxide was used.
This test piece was evaluated for impact resistance and flame retardancy.

The results are shown in Table 1.

Comparative Example 8 In Example 10, 5 parts by weight of untreated aftimone dioxide was used in place of the flame retardant (■) used in the same example, and a test piece was prepared by kneading in the same manner as in Example 10, except that
This test piece was evaluated for impact resistance and flame retardancy.

The results are shown in Table 1.

Comparative Example 9 In Example 11, 5 parts by weight of untreated antimony trioxide was used in place of the flame retardant (■) used in the same example, and a test piece was prepared by kneading in the same manner as in Example 11, except that 5 parts by weight of untreated antimony trioxide was used.
This test piece was evaluated for impact resistance and flame retardancy.

The results are shown in Table 1.

From Examples 1 to 5 and Comparative Examples 1 to 3 in Table 1, the resin compositions containing antimony trioxide whose surface was coated with magnesium stearate were mixed with untreated antimony dioxide, or with magnesium stearate, or with magnesium stearate. It is clear that the composition exhibits superior impact strength and flame retardant effect compared to any combination of colloidal antimony trioxide.

Also, in Examples 6 to 9 and Comparative Examples 4 to 6 in Table 1, the resin compositions containing magnesium stearate-coated antimony trioxide obtained according to the method of the present invention were different from the resin compositions containing untreated antimony trioxide. It is clear that the impact strength and flame retardant effect are superior to those obtained by using the same method.

Furthermore, comparisons between Example 10 and Comparative Example 7.8 and Example 11.12 and Comparative Example 9 in Table 1 also show that the resin composition obtained by the method of the present invention has excellent impact resistance. It is clear that it exhibits strength and flame retardant effects.

Claims (1)

[Claims] 1 2 to 50 parts by weight of a fatty acid metal salt is blended with 100 parts by weight of antimony trioxide, and this mixture is mixed at a temperature where the fatty acid metal salt melts, and then pulverized. 1. A method for producing a styrenic resin composition with excellent flame retardancy, which comprises blending a combination of and another flame retardant into a styrene resin.