JPS6019338B2 - Flame retardant thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a magnesium- or aluminum-containing inorganic compound flame retardant that, when used in a base capable of imparting sufficient flame retardancy to a resin, causes a considerable deterioration in the physical properties of the resin, such as impact strength and other properties. and synergy with certain metal compounds (excluding metal oxides).

The present invention relates to a flame-retardant thermoplastic resin composition that can impart exceptionally excellent flame retardancy without causing any negligible deterioration of the physical properties of the resin. More specifically, at least one magnesium- or aluminum-containing inorganic compound selected from the group consisting of magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, and hydrotalcite is added to 100 parts by weight of the thermoplastic resin. from about 60 to about 15 parts by weight, preferably from about 70 to about 13 parts by weight; A metal compound selected from the group consisting of the discovered inorganic compounds of V metal is used in an amount of about 0.0.
05 to about 1% by weight, preferably about 0.1 to about 5% by weight
The present invention relates to a flame-retardant thermoplastic resin composition comprising: .

It has been known that magnesium- or aluminum-containing inorganic compounds such as those described above have an effect as an inorganic retardant on thermoplastic resins.

However, due to the combination of such inorganic retardants,
In order to impart high flame retardancy such as UL94V-0 or V-1, it becomes necessary to incorporate a fairly large amount of these inorganic flame retardants, and along with this, the desirable mechanical properties inherent in thermoplastic resins, especially It is known that the impact strength deteriorates to a non-negligible extent and the suitability for ripening also decreases.
The present inventors have conducted research to overcome these deficiencies. As a result, it is possible to impart excellent flame retardancy to a thermoplastic resin with a reduced amount of the inorganic flame agent used in combination with the specific metal compound (excluding metal oxides) described in (1) above; It was also discovered that the amount of the above-mentioned metal compound used in combination in this case can be used in a small amount, thereby imparting high flame retardance to the thermoplastic resin without causing any substantial adverse effects on the physical properties of the resin. did. The reason for the mutual effect caused by the combined use of the magnesium- or aluminum-containing inorganic compound of '11 above and a small amount of the specific metal compound (excluding metal oxides) of {2-, above, is not clear, but As will be shown later with comparative examples, the inorganic flame retardant in ``1'' above is blended in an amount that can improve the UL94 to only day shift grade, and a few percent of the specific metal compound in ``2-'' is coexisting. It has been discovered that the unexpected synergistic effect of improving the UL94 to V-0 can be achieved. Furthermore, it has been discovered that the deterioration in flow characteristics during molding due to the inorganic refueling agent blending is improved and excellent moldability is also achieved, which is a completely unexpected effect. Furthermore, according to the present invention, by simply using both of the above m and Effects can be obtained. Therefore, an object of the present invention is to provide a flame-retardant thermoplastic resin composition that overcomes the disadvantage of decreased physical properties due to the use of inorganic flame retardants and can provide excellent flame retardance with a reduced amount of flame retardant used. It's about doing.

The above objects and many other objects and advantages of the present invention include:
It will become clearer from the following description that the above {1' magnesium or aluminum selected from the group consisting of magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, and hydrotalcites is used in the composition of the present invention. The inorganic compounds contained can be used alone or in combination, and have a BET specific surface area of about 20.
It is preferable to use particles that have a particle size of less than or equal to .

For example, one having a BET specific surface area of about 10 to about 20 m/m, more preferably about 1 to about 15 m/m is preferable. As the above hydrotalcites, the formula, M&-x mountain x (
OH)2(C03)x/2 ・mH20 [However, 0<
It is preferable to use the formula represented by x<0.4 h<1]. Such tamagnesium or aluminum-containing inorganic compounds are present in an amount of about 60 to about 15 parts by weight, preferably about 70 to about 12 parts by weight, based on 10 parts by weight of the thermosetting resin.
It is used in a usage amount of parts by weight. If the amount of the inorganic compound used is within the above range and is too small, it will be difficult to impart a sufficiently high flame retardant effect, and if it exceeds the above range and is too excessive,
Since there is a risk of non-negligible deterioration of physical properties, it is preferable to use the amount within the above range. In the composition of the present invention,
A small amount selected from the group consisting of inorganic acid salts of metals selected from Cu, Pb and Co in [21] and inorganic compounds of V metals selected from halogenated alkali vanadates and ammonium salts. Even if the amount of the inorganic compound (1') is reduced, a sufficiently high elutriation effect can be imparted by using one kind of metal compound in combination. The scale flame effect of UL94V-0 can be obtained even with the following amount of the inorganic compound used, and it is possible to advantageously avoid the risk of deterioration of the physical properties of the resin composition and impart a high flame retardant effect. . In this way, even if the amount of the inorganic retardant used is reduced to an amount that does not cause any risk of deterioration of the physical properties of the resin composition, the excellent retardant effect can be achieved by coexisting with a small amount of the metal compound mentioned above. This was a completely unexpected result, and it has great significance as an improvement in the field of scale combustion technology. In the composition of the present invention, the metal compound (2) used in combination with the inorganic compound (11), which is known as an inorganic flame retardant for thermoplastic resins, is not usable in any way even if it is blended with the thermoplastic resin in the above amount. The achievement of the above-mentioned improvement effect by the composition of the present invention was completely unexpected, considering that the composition does not exhibit any effective flame retardant effect and often results in a decrease in flame retardancy.

As this metal compound, a metal compound selected from the group {2} above is used. These metal compounds can be used alone or in combination. Examples of such metal compounds of group (1) include inorganic acid salts such as hydrochlorides, sulfates, nitrates, perchlorates, phosphates, carbonates, etc. of metals selected from C, Pb, and Co. and halides such as chlorides, as well as inorganic compounds of V metal selected from alkali vanadate salts and ammonium vanadate salts. Specific examples of these metal inorganic compounds include sulfuric acid steel, lead nitrate, sodium meta- or orthovanadate, cobalt sulfate, cobalt chloride,
Examples include cobalt bromide, copper perchlorate, lead iodide, cobalt phosphate, basic carbonate steel, cobalt carbonate, and lead thiocyanate. These metal compounds (21) are preferably used in powder form, and more preferably in fine powder form with an average particle size of about 1 French or less.

The amount used may be small, and it is used in an amount of about 0.05 to about 1% by weight in terms of metal, based on the non-compound containing magnesium or aluminum in '1'. Preferably, it is used in an amount of about 0.05 to about 5% by weight. If the combined amount of this metal compound is too small outside the above range, it will be difficult to achieve the above-mentioned mutual effect, and if the amount is too excessive, not only will further improvement not be expected.
On the contrary, it may cause a decrease in effectiveness, so it is better to select and use the amount within the above range as appropriate. Furthermore, in the present invention, the Cu
, Pb, V, and Co, these metals or oxides of these metals may be used in combination, and within the range of the amount of the metal compound used, a portion thereof may be used. can be replaced with the above metal or metal oxide. The presence of the metal compound '2} in a dispersed manner near the surface of the inorganic compound particles {1-} above helps to achieve a particularly excellent synergistic effect.

In order to achieve such dispersion, it is preferable to premix the inorganic compound of '11 above and the metal compound of (2) above beforehand. After such premixing, mixing with the thermoplastic resin is carried out, for example, in an aqueous medium, as described in '11 above.
The magnesium- or aluminum-containing inorganic compound and the metal compound powder of '2-' are mixed uniformly in a water or alcohol medium or under sufficient sludge conditions, dried, and then mixed with a thermoplastic resin. This can be done by melt-kneading. Furthermore, in the present invention, the particles of the above-mentioned magnesium- or aluminum-containing inorganic compound and/or the above-mentioned {2} metal compound can be surface-treated with an anionic surfactant, which often yields favorable results.

In such surface treatment, it is preferable to treat the surface with an anionic surfactant in an amount of about 1 to about 1% by weight based on the weight of the inorganic compound in [11] and/or the metal compound in t2 above. . For example, the above magnesium- or aluminum-containing inorganic compounds and/or the above metal compound powder (①) are added to an aqueous solution of an anionic surfactant such as sodium stearate under sufficient conditions, or vice versa. An aqueous solution of sodium stearate is added to the suspension of these powders to chemically adsorb the anionic surfactant onto the surface of these solid powders. As described above, surface treatment improves dispersibility and improves fluidity, which is effective in improving workability. The anionic surfactant used is of the formula RCOOM (wherein,
R represents a C3-C4o alkyl group, M represents an alkali metal atom) Higher fatty acid alkali salt: Alkyl sulfate represented by formula ROS03M (wherein R and M have the same meanings as above): Formula RS03M Alkyl sulfonic acid represented by the formula (wherein R and M have the same meanings as above): Alkylaryl sulfone ROCO represented by the formula R-a-S03M (wherein R and M have the same meanings as above)
CH2 salt: and the formula l (wherein R and R
There are sulfosuccinic acid ester salts represented by OCOCHS03M (M is the same as above).

Specific examples of such surfactants include sodium stearate, potassium stearate, sodium oleate, potassium oleate, sodium palmitate, potassium palmitate, sodium laurate, potassium laurate, potassium behenate, Examples include sodium laurylbenzenesulfonate, potassium octadecyl sulfate, sodium laurylsulfonate, and disodium 2-sulfoethyl Q-sulfostearate.

In the composition of the present invention, about 60 to about 150 parts by weight of at least one of the above-mentioned magnesium- or aluminum-containing inorganic compounds and the above-mentioned metal compound are added to 100 parts by weight of the thermoplastic resin. The content is about 0.05 to about 1% by weight based on the compound.

Examples of thermoplastic resins used in such compositions include polymers or copolymers of ethylene, propylene, butene-1, and other Q-olefins; one or more of such Q-olefins; Copolymers with conjugated or non-conjugated genes: polystyrene or styrenic copolymers such as ABS resins; polyesters or copolyesters: polycarbonate resins. In particular, in order to improve the flame retardancy of non-polar to weakly polar resins, it is preferable to use the inorganic compound (01) and the metal compound (2) of the present invention in combination. There are no particular restrictions on the method of blending these thermoplastic resins and the above additives, and any means that can uniformly mix these additives into the resin, such as extrusion,
It can be carried out using means such as roll mixing and at any temperature below that which causes thermal degradation of the resin. The thermoplastic flame retardant composition of the present invention may further contain other conventional additives.

Examples of such other additives include fillers such as asbestos, glass fiber, talc, silica/lastonite, calcium silicate, aluminum silicate, calcium carbonate; carbon black, phthalocyanine,
Quinacridone, indoline, azo pigment, titanium oxide,
Colorants such as cadmium pigments, yellow lead, and Bengara: G-t
- Antioxidants such as butyl-p-cresol, distearylthiodipropionate, dilaurylthiodipropionate, lubricants such as calcium stearate, zinc stearate, butyl stearate, ethylene bisstearamide; 2-hydroxy- Examples include ultraviolet absorbers such as 4-octoxybenzophenone, 2(2'-hydroxy-5-methylphenyl)penzotriazole, and ethyl-2-cyano-3,3-diphenyl acrylate. The amount of these other additives can be selected as appropriate, for example, about 10 to about 10 parts by weight of fillers, about 0.1 to about 10 parts by weight based on 10 parts by weight of thermoplastic resin.
about 0.1 to about 1 part by weight of antioxidants, about 0.1 to about 5 parts by weight of lubricants, about 0.1 to about 1 part by weight of ultraviolet light absorption. For example, the amount of compounding agents can be exemplified. Examples 1 to 4 and Comparative Examples 1 to 2 Ta Approximately 5% of the sulfuric acid steel CuS04/Group 20 was added to the water in the amount shown in Table 1 below (expressed as weight percent relative to magnesium hydroxide in terms of Cu metal). ) and further, BE
Magnesium hydroxide with a specific surface area of 15% is added to the first
Add the amounts shown in the table (expressed as parts by weight of Mg(OH)2 to parts by weight of polypropylene 010) and mix thoroughly.

Next, 30 g of sodium oleate, an anionic surfactant, is added, and about 3 powders are further mixed and reacted for surface treatment, followed by filtering, washing with water, and drying. This dried product was mixed with 100 parts by weight of polytapropylene in the amount shown in Table 1 in terms of Mg(OH)2, and melt-cross-wire molded. The results of the flammability test on the molded articles are shown in Table 1. For comparison, in addition to omitting the use of sulfuric acid steel, 0 is
About 101 parts by weight of the total amount in Example 1 (about 101 parts by weight of the total amount in Example 1) of magnesium hydroxide, which was treated in the same manner as in the above example, was converted into Mg(OH)2 to 10 parts by weight of polypropylene.
Comparative Example 1) and 15 parts by weight of the conventional amount (Comparative Example 2),
Table 1 shows the results of each blend, as well as the results of a control example in which no flame retardant was added.

Table 1 [Note] 1...Mg(OH) per 100 parts by weight
) as weight sound &2... Mg (OH
)% by weight relative to 2.

Example 5 and Comparative Example 3 Approximately 5 lead nitrate Pb (N03
) 2 in terms of Pb, the hydrotalcite compound Mgo. 7N
oQ(OH)2(C03)M50.5 spot 201k9 is also added, and the flies are thoroughly mixed.

The temperature of this mixed system was raised to about 70°C, 150ml of an aqueous solution of 50ml of sodium stearate was added, and the mixture was thoroughly mixed for about 3 ships to dissolve the sodium stearate. It was chemically adsorbed onto the surface of hydrotalcite compounds. This surface-treated product is heated in a furnace, washed with hot water, and dried. The results of the same flammability test as shown in Table 1 for a composition in which this dry product was blended with high-density polyethylene in the amounts shown in Table 2 below were as shown in Table 2 below. .
For comparison, the results of the same procedure except for omitting the use of lead nitrate but using a dried product obtained in the same manner (Comparative Example 3) and the results of a control example in which no flame retardant was added are shown together. It's listed. Example 6 and Comparative Example 4 In Example 5, basic magnesium carbonate was used instead of the hydrotalcite compound, and cobalt chloride CoC12/Hoso 20 was used instead of lead nitrate, in the amounts shown in Table 2 below. The rest was carried out in the same manner as in Example 5, and the results shown in Table 2 were obtained.

For comparison, results were obtained in the same manner as in Comparative Example 3, except that the use of cobalt chloride was omitted (Comparative Example 4).
) are shown together. Example 7 and Comparative Example 5 Approximately 5 liters of sodium metavanadate NaV03 and 40 liters of sodium stearate were dissolved in the water, and the temperature of the yarn was raised to approximately 70 degrees Celsius, and then the BET ratio table was heated. Magnesium hydroxide lk9 was added to the mixture in an amount of 10 times the area and thoroughly mixed, followed by filtering in an oven, washing with water, and drying.

Table 2 shows the results of the same combustion tests shown in Table 1 for compositions in which the dry matter was blended with polystyrene in the amounts shown in Table 2 below. In addition, for zero comparison, the results obtained in the same manner using a dried product obtained in the same manner except that the use of sodium metavanadate was omitted (Comparative Example 5) and the results of a control example in which no retardant was added are also included. It is listed in. Example 8 and Comparative Example 6 Example 7 was prepared by performing the same operation except that sodium orthovanadate Na3V04 was used as a flame retardant aid for 15 days in terms of metal.

This was blended into ethylene-propylene copolymer resin in the amounts shown in Table 2, and the results are shown in Table 2 below. In addition, 0 for comparison
Therefore, the results are shown together for the case where the use of sodium orthovanadate was omitted (Comparative Example 6) and the case where the brood retardant was not added (Control Example). Example 9 and Comparative Example 7 About 5 lead nitrate Pb(N03)2 and copaltate sulfate COS0 were added to the water.
Aluminum hydroxide lk9 having a BET specific surface area of 5 was added to the system in which 20 on the 4th and 7th days were added and dissolved on a metal equivalent basis for 5 days each, and the mixture was thoroughly mixed.

This was dehydrated and dried. Table 02 shows the results of blending this into low density polyethylene in the amounts shown in Table 2. For comparison, the results are also shown when the use of lead nitrate and cobalt sulfate was omitted (Comparative Example 7) and when no flame retardant was added (Control Example). Female boat ball sea bream place.

Toki school Akebono S* corpse register appearance Chikan Spirits enshrinement Black eel cape" Tsukuda Pass 〇ya Yutaka key ■ Word≦ navy blue

Claims (1)

[Scope of Claims] 1. For 100 parts by weight of the thermoplastic resin, (1) a magnesium- or aluminum-containing inorganic compound selected from the group consisting of magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, and hydrotalcites; about 60 to about 15 of at least one type of fuel
0 parts by weight, and (2) a metal selected from the group consisting of inorganic acid salts of metals selected from Cu, Pb and Co, and inorganic compounds of V metals selected from halides and alkali vanadate salts and ammonium salts. A flame-retardant thermoplastic resin composition, characterized in that the compound is contained in an amount of about 0.05 to about 10% by weight, based on the magnesium- or aluminum-containing inorganic compound flame retardant, on a metal basis.