JP5394380B2 - Flame retardant resin composition - Google Patents

Description

  The present invention relates to a flame retardant resin composition having acid resistance and a molded article formed therefrom. Specifically, the present invention relates to a resin composition containing aluminum salt hydroxide particles as a flame retardant and a phosphorus compound, carbon powder, silicone, etc. as a flame retardant aid, and a molded article formed therefrom.

As a safe non-halogen flame retardant technology for synthetic resins, flame retardant using metal hydroxides such as magnesium hydroxide particles has been proposed.
However, since magnesium hydroxide particles are alkaline, they have weakness in acid resistance, and a resin composition containing a large amount of magnesium hydroxide particles can be exposed to carbonated water or acid rain for a long time. There was a problem that basic magnesium carbonate or the like was precipitated and the surface was whitened to deteriorate the appearance of the molded product.
In order to cope with this, Patent Documents 1 to 3 propose a method of improving acid resistance by using magnesium hydroxide and aluminum hydroxide together.
Patent Documents 4 to 7 propose resin compositions containing a metal hydroxide as a flame retardant and a phosphorus compound, carbon powder, silicone or the like as a flame retardant aid.
Further, Patent Document 8 discloses a method of preventing whitening of the resin surface by carbon dioxide gas by blending a metal hydroxide, red phosphorus and carbon powder with a synthetic resin.
If aluminum hydroxide is added to a synthetic resin and kneaded or injection molded at a temperature of 170 ° C or higher, particularly 200 ° C or higher, foaming occurs due to the release of water accompanying the thermal decomposition of the structural water of aluminum hydroxide. It is.
Moreover, when red phosphorus and carbon black are used in combination with magnesium hydroxide described in Patent Document 8, the carbon dioxide resistance of the synthetic resin can be improved and surface whitening can be prevented. It is difficult to improve the properties and hydrochloric acid resistance.

Japanese Patent Laid-Open No. 10-338818 Japanese Patent No. 3115934 Japanese Patent Laid-Open No. 11-181305 JP 2002-356574 A JP 2003-105295 A JP 2006-71914 A JP 2006-143896 A Japanese Patent No. 3027790 specification

Accordingly, a first object of the present invention is to provide a resin composition excellent in flame retardancy and acid resistance. A second object of the present invention is to provide a resin composition having excellent mechanical properties, less silver streak and excellent surface appearance.
The present inventors paid attention to the acid resistance exhibited by aluminum salt hydroxide particles containing a mineral called a so-called alunite, and studied the application of this to flame retardant technology. As a result, the present invention was completed.

The aluminum salt hydroxide particles used in the present invention are essential for ensuring acid resistance, but when used alone, the effect of imparting flame retardancy to the synthetic resin is low. Phosphorus compounds, carbon powders, and silicones are generally used as flame retardant aids for metal hydroxide flame retardants, but it is difficult to impart flame retardancy to resins with these flame retardant aids alone. It is.
The inventors of the present invention use a combination of specific aluminum salt hydroxide particles and at least one selected from the group consisting of phosphorus compounds, carbon powders, and silicones to provide flame resistance and acid resistance to synthetic resins. It was found that the occurrence of silver streaks can be suppressed.

That is, the present invention includes the following inventions.
1. (I) 100 parts by weight of a synthetic resin, where the synthetic resin is polypropylene, ABS resin or polyamide resin,
(Ii) 10 to 200 parts by weight of a flame retardant represented by the following formula (1), and (iii) 0.5 to 20 parts by weight of at least one selected from the group consisting of a phosphorus compound, carbon powder and silicone. Flame retardant aid,
Containing a resin composition.

(Wherein, M is at least one cation selected from the group consisting of Na ⁺ , K ⁺ , NH ₄ ⁺ , H ₃ O ⁺ and Ca ²⁺ , M ′ is Zn ²⁺ , Ni ²⁺ , Sn ⁴⁺ , Zr ^At least one metal cation selected from the group consisting of ⁴⁺ and Ti ⁴⁺ , A represents at least one organic acid anion, B represents at least one inorganic acid anion, and a, b, m, n, x, y and z are 0.7 ≦ a ≦ 1.35, 2.7 ≦ b ≦ 3.3, 0 ≦ m ≦ 5, 4 ≦ n ≦ 7, 0 ≦ x ≦ 0.6, 1.7 ≦ y ≦ 2.4 and 0 ≦ z ≦ 0.5 are satisfied.)

2. 2. The resin composition according to item 1, wherein the phosphorus compound is at least one selected from the group consisting of red phosphorus, phosphate ester, condensed phosphate ester and polyphosphate.
3. 2. The resin composition according to item 1, wherein the carbon powder is at least one selected from the group consisting of carbon black, activated carbon and graphite.
4). 2. The resin composition according to item 1, wherein the silicone is at least one selected from the group consisting of silicone resins, silicone greases, and silicone rubbers.
5. The flame retardant represented by the formula (1) is at least one surface treatment agent selected from the group consisting of higher fatty acids, titanate coupling agents, silane coupling agents, aluminate coupling agents, and alcohol phosphate esters. 2. The resin composition according to item 1 being treated.
6 . A molded article formed from the resin composition according to any one of items 1 to 5 .

  The resin composition and molded product thereof of the present invention are excellent in flame retardancy and acid resistance. The resin composition of the present invention is excellent in mechanical properties, has few silver streaks, and is excellent in surface appearance.

It is the SEM photograph which image | photographed the disk shaped aluminum salt hydroxide particle | grains (flame retardant C) of the synthesis example 1 of an Example by 20,000 time. It is a graph in connection with a sulfuric acid resistance test among the acid resistance tests of Example 13. It is a graph in connection with the nitric acid resistance test among the acid resistance tests of Example 13. It is a graph in connection with a hydrochloric acid resistance test among Example 13 acid resistance tests.

(Flame retardants)
The flame retardant used in the present invention is aluminum salt hydroxide particles represented by the following formula (1).

In the formula, M represents at least one cation selected from the group consisting of Na ⁺ , K ⁺ , NH ₄ ⁺ , H ₃ O ⁺ and Ca ²⁺ .
M ′ represents at least one metal cation selected from the group consisting of Zn ²⁺ , Ni ²⁺ , Sn ⁴⁺ , Zr ⁴⁺ and Ti ⁴⁺ .
A represents at least one organic acid anion. The organic acid anion is preferably at least one selected from oxalate ion, citrate ion, malate ion, tartrate ion, glycerate ion, gallate ion and lactate ion.
B represents at least one inorganic acid anion. The inorganic acid anion is preferably at least one selected from the group consisting of SO ₄ ²⁻ , PO ₄ ³⁻ , NO ₃ ⁻ , SiO ₃ ²⁻ , SiO ₄ ⁴⁻ and HSi ₂ O ₅ ⁻ . SO ₄ ²⁻ is most preferable in that the particle diameter is uniform.

a satisfies 0.7 ≦ a ≦ 1.35, preferably 0.9 ≦ a ≦ 1.2.
b satisfies 2.7 ≦ b ≦ 3.3, preferably 2.8 ≦ b ≦ 3.2.
m satisfies 0 ≦ m ≦ 5, preferably 0 ≦ m ≦ 2.
n satisfies 4 ≦ n ≦ 7, preferably 5 ≦ n ≦ 6.5.
x satisfies 0 ≦ x ≦ 0.6, preferably 0 ≦ x ≦ 0.3.
y satisfies 1.7 ≦ y ≦ 2.4, preferably 1.8 ≦ y ≦ 2.2.
z satisfies 0 ≦ z ≦ 0.5, preferably 0 ≦ z ≦ 0.4.
Furthermore, a, b, m, n, x, y, and z are 3.6 ≦ a + b ≦ 4.4, 0 ≦ m ≦ 2, 0 ≦ x ≦ 0.3, 7.5 ≦ y + n ≦ 8.5. Is preferably satisfied.

The average secondary particle diameter of the flame retardant is preferably 0.2 to 6 μm, more preferably 0.5 to 4 μm, and still more preferably 0.5 to 2 μm. The flame retardant is preferably close to monodisperse. The BET specific surface area of the flame retardant is preferably 1 to 50 m ² / g, more preferably 1 to 20 m ² / g, and still more preferably ^{2 to 20} m ² / g.
The aluminum salt hydroxide particles of formula (1) are synthesized by the method described in page 21 line 19 to page 26 line 6 of the pamphlet of WO 2005/085168 and the method described in the examples. Can do. That is, in the aluminum salt hydroxide particles of the formula (1), for example, when the inorganic acid ion of B is a sulfate ion, aluminum sulfate, the sulfate of M ′ in the formula (1), the sulfate of M, the organic acid and / or or organic acid salts, for example, in a mixed solution of oxalic acid _{(H 2 C 2 O 4)} , can be produced by heating the reaction by adding an alkali hydroxide aqueous solution containing the M. If necessary, the water-containing powder of the organic acid anion-containing aluminum salt hydroxide particles can be obtained by filtering, washing and drying the produced organic acid anion-containing aluminum salt hydroxide particles.

In particular, in the case of z = 0 in formula (1), that is, aluminum salt hydroxide particles not containing an organic acid anion, from page 19 line 1 to page 23 line 15 of WO 2006/109847 pamphlet. It can be synthesized by the methods described and the methods described in the examples. That is, the alunite-type compound particles are made of a salt of an ion selected from the group consisting of Na ⁺ , K ⁺ , NH ₄ ⁺ and H ₃ O ^{+ in} a salt of Al ³⁺ ion that is water-soluble in a pH range of 1-7. It can be obtained by adding the solution so that the alkali equivalent ratio is 0.6 to 1.1, preferably 0.7 to 1.0, particularly preferably 0.8 to 0.9, and heating the mixture. it can.
As a commercially available product, Almicron 210 (registered trademark / manufactured by Kyowa Chemical Industry Co., Ltd.) or the like can be used.
The shape of the aluminum salt hydroxide particles varies depending on the type of the cation M, the metal cation M ′ and the organic acid anion A in the formula (1). The shape is known to exhibit a spherical shape, a meteorite shape (disc shape), a cubic shape, a hexagonal plate shape, a disc shape, a rice grain shape, and the like, but the effects of the present invention are manifested regardless of the shape.

(surface treatment)
The flame retardant used in the present invention can be blended into the resin as it is, but can be used after being treated with a surface treatment agent. Examples of such a surface treatment agent include at least one selected from the group consisting of higher fatty acids, titanate coupling agents, silane coupling agents, aluminate coupling agents, and alcohol phosphate esters. These surface treatments are performed using a surface treatment agent of 10% by weight or less, preferably 5% by weight or less based on the flame retardant.
In the present invention, the surface of the flame retardant is acid-resistant coated with at least one selected from the group consisting of a silicon compound, a boron compound and an aluminum compound, and additionally the higher fatty acids, titanate coupling agent, and silane coupling as necessary. By treating with at least one surface treatment agent selected from the group consisting of an agent, an aluminate coupling agent, and an alcohol phosphate ester, an even higher acid resistant resin composition can be obtained. These acid resistant coatings are coated at 2% by weight or less based on the aluminum hydroxide particles.

(Flame retardant aid)
As the phosphorus compound used as a flame retardant aid in the present invention, at least one selected from the group consisting of red phosphorus, phosphate ester, condensed phosphate ester and polyphosphate can be used.
As the carbon powder used in the present invention, at least one selected from the group consisting of carbon black, activated carbon and graphite can be used.
Examples of the silicone used in the present invention include compounds containing organopolysiloxane as a main component. That is, as the silicone, at least one selected from the group consisting of silicone resin, silicone grease, and silicone rubber can be used.

(Synthetic resin)
Synthetic resins used in the present invention is polypropylene, ABS resin or polyamide resin. Examples of the polyamide resin include nylon 6, nylon 66, nylon 12, nylon 46, nylon 11, and the like.

(Content)
Content of a flame retardant is 10-200 weight part with respect to 100 weight part of synthetic resins, Preferably it is 10-160 weight part, More preferably, it is 10-100 weight part. By setting the content of the flame retardant in this range, a resin composition excellent in terms of acid resistance, mechanical properties, surface appearance and silver streak resistance can be obtained.
The content of the flame retardant aid is 0.5 to 20 parts by weight, preferably 1 to 20 parts by weight, more preferably 2 to 18 parts by weight with respect to 100 parts by weight of the synthetic resin. If the total content of the flame retardant aid is less than 0.5 parts by weight, the flame retardant effect is small, and if it exceeds 20 parts by weight, the mechanical strength is not improved and it is uneconomical.
The total amount of the flame retardant and the flame retardant aid is preferably 10 to 100 parts by weight with respect to 100 parts by weight of the synthetic resin. When the total amount of the flame retardant and the flame retardant auxiliary is within this range, the resin composition is excellent in flame retardancy and acid resistance.

(Other ingredients)
Various additives, reinforcing agents, fillers, polymer alloy compatibilizers and the like that are usually added can be added to the resin composition of the present invention as long as the object of the present invention is not impaired.
As the polymer alloy compatibilizer, maleic anhydride modified styrene-ethylene-butylene resin, maleic anhydride modified styrene-ethylene-butadiene resin, maleic anhydride modified polyethylene, maleic anhydride modified EPR, maleic anhydride modified polypropylene, carboxyl modified Examples include polyethylene and epoxy-modified polystyrene / PMMA.

(Manufacture of resin composition)
The resin composition of the present invention can be produced by mixing a synthetic resin, a flame retardant, and a flame retardant aid. For example, each component and other additives can be mixed in advance, and then melt kneaded and produced by an open roll, a single or twin screw kneading extruder, a Banbury mixer, and the like. In particular, from the viewpoint of preventing the occurrence of silver streak, the kneading extruder is preferably a vent type.
The flame retardant used in the present invention is more effective in terms of preventing the occurrence of silver streak if it is previously dried at 100 to 320 ° C. before blending with the synthetic resin and a hopper dryer is used when kneading with the synthetic resin. .

(Molding)
There is no special provision for the molding method of the resin composition. Examples of the molding method include injection molding, extrusion molding, and press molding. In particular, the molding machine is preferably a vent type in terms of preventing silver streak.
By molding the resin composition of the present invention at a temperature of 320 ° C. or lower, a molded product having excellent flame retardancy, acid resistance, mechanical properties, and surface appearance and having less silver streak and foaming can be obtained. If the molding temperature is 320 ° C. or lower, even if the molding temperature is 170 ° C. or higher and even 200 ° C. or higher, no silver streak occurs and no foaming occurs.

(Method to improve flame retardancy and acid resistance)
The present invention is a method for improving the flame retardancy and acid resistance of a synthetic resin, comprising: (i) 100 parts by weight of a synthetic resin;
(Ii) 10 to 200 parts by weight of a flame retardant represented by the following formula (1), and (iii) 0.5 to 20 parts by weight of at least one selected from the group consisting of a phosphorus compound, carbon powder and silicone. Flame retardant aid,
The method characterized by including is included.

(Wherein, M is at least one cation selected from the group consisting of Na ⁺ , K ⁺ , NH ₄ ⁺ , H ₃ O ⁺ and Ca ²⁺ , M ′ is Zn ²⁺ , Ni ²⁺ , Sn ⁴⁺ , Zr ^At least one metal cation selected from the group consisting of ⁴⁺ and Ti ⁴⁺ , A represents at least one organic acid anion, B represents at least one inorganic acid anion, and a, b, m, n, x, y and z are 0.7 ≦ a ≦ 1.35, 2.7 ≦ b ≦ 3.3, 0 ≦ m ≦ 5, 4 ≦ n ≦ 7, 0 ≦ x ≦ 0.6, 1.7 ≦ y ≦ 2.4 and 0 ≦ z ≦ 0.5 are satisfied.)

  Hereinafter, the present invention will be described in detail based on examples. The specific surface area, average secondary particle diameter, and silver streak measurement method by the BET method in each example will be described below.

(1) Component analysis Na: measured by atomic absorption.
Ca, Al, Ni, Zn and Sn: measured by chelate analysis.
NH ₄ , Ti: measured by a colorimetric method.
SO ₄ , Zr: measured by gravimetric method.
_{H 2 C 2 O 4, H} 3 C 6 H 5 O 7, H 2 C 4 H 4 O 6: was measured by oxidation-reduction method.
H ₂ O: measured by weight loss after drying at 120 ° C. for 1 hour.
Stearic acid: measured by ether extraction.

(2) Specific surface area by BET method It measured with 12 sample fully automatic surface measuring apparatus Multisorb-12 of Yuasa Ionics Co., Ltd.

(3) Average secondary particle size and particle size distribution sharpness Apparatus: Microtrac MT3300 (manufactured by Leed & Norrup Instruments Company) Method: 700 mg of sample powder was added to 70 ml of 0.2 wt% sodium hexametaphosphate aqueous solution, and ultrasonic waves (manufactured by NISSEI, After dispersion for 3 minutes at MODEL US-300, current 300 μA), 2-4 ml of the dispersion was taken while stirring with a stirrer and added to the sample chamber of the particle size distribution analyzer containing 250 ml of deaerated water. The analyzer is turned on and the suspension is circulated for 3 minutes, and then the particle size distribution is measured.A total of two measurements are made, and the mv obtained for each measurement is taken as the average particle size of the sample.
As an evaluation method of particle size uniformity and monodispersity, the particle diameter is plotted on the horizontal axis, the cumulative frequency is plotted on the vertical axis, and the particle size from the smallest particle size to the cumulative frequency of 25% with respect to the total number of particles. The particle diameter at which D ₂₅ , 75% is D _75, and the ratio D ₇₅ / D _{25 of} these ratios, that is, the particle size distribution sharpness, represents the spread of the particle size distribution.

(4) Acid resistance test The following elution test of aluminum or magnesium was used as the acid resistance test. A 1/8 inch thick UL94 vertical test piece was cut in half length and immersed in 200 ml of 3.6 N sulfuric acid, hydrochloric acid or nitric acid solution with sulfuric acid resistance at 50 ° C. Hydrochloric acid resistance and nitric acid resistance were evaluated by leaving at 95 ° C. for 7 days. The aluminum or magnesium content of the aqueous solution was evaluated by ICP analysis. The smaller the aluminum or magnesium content of the aqueous solution, the better the acid resistance because the elution amount of aluminum or magnesium from the test piece is smaller.

(5) Flame retardancy Measured by UL94 vertical test and UL94HB method.

(6) Tensile strength at yield point Measured according to JIS K7113. However, polypropylene was measured at a test speed of 50 mm / min, and ABS and nylon 6 were measured at a test speed of 5 mm / min.

(7) Silver streak on the surface of the molded product A disk having a thickness of 2.1 mm and a diameter of 50 mm was injection-molded at 230 ° C. using an injection molding machine with a vent. The degree of silver streak generated in this disk was visually ranked in the following grades 1-4. Grade 3 or higher is the degree of occurrence of silver streak that causes no problem in appearance, and is preferably grade 2 or higher.
1st grade: No silver streak 2nd grade: Slightly silver streak near the gate 3rd grade: Slight silver streak 4th grade: Significant silver streak on the entire surface

Synthesis Example 1 (Synthesis of flame retardant C)
160 mol of aluminum sulfate and 0.2 mol of sodium sulfate were dissolved in 700 L of ion exchange water, 0.1 mol of oxalic acid (H ₂ C ₂ O ₄ ) was added thereto, and the mixture was stirred in a 1 m ³ reaction vessel. Further, 633 mol of sodium hydroxide was added to the mixed solution while stirring, and hydrothermal treatment was performed at 170 ° C. for 3 hours. The cooled reaction solution was filtered, washed with water, dried and pulverized at 120 ° C. for 24 hours, and as a result, discoid (meteorite) aluminum salt hydroxide particles (hereinafter referred to as flame retardant C) shown in FIG. 1 were obtained. It was.

Synthesis examples 2 and 3 (synthesis of flame retardants A and B)
2 kg of the obtained flame retardant C was suspended in 20 L of ion exchange water to prepare a slurry. 60 g of sodium stearate was added to the slurry of flame retardant C, stirred at 80 ° C. for 1 hour, filtered, washed with water, dried and pulverized at 120 ° C. for 10 hours, flame retardant A surface-treated with sodium stearate And B were obtained (sodium stearate was 2% by weight and 3% by weight, respectively).

Synthesis Example 4 (Synthesis of flame retardant D)
194 ml (0.2 mol) of aqueous aluminum sulfate solution, 28.4 g (0.2 mol) of sodium sulfate and 6.3 g (0.03 mol) of citric acid are mixed, diluted to 600 ml with ion-exchanged water, and the crystalline substance is dissolved while stirring. I let you. To this solution, 7.35 g (0.03 mol) of nickel sulfate was added and dissolved. Further, 235 ml (0.8 mol) of sodium hydroxide solution was added to the above mixture in 6 minutes at room temperature. After stirring at room temperature for 1 hour, hydrothermal treatment is performed at 170 ° C. for 2 hours, and the reaction solution after hydrothermal treatment is filtered, washed with water and dried (105 ° C., 15 hours) to form spherical aluminum salt hydroxide particles (flame retardant) D) was obtained.

Synthesis Example 5 (Synthesis of flame retardant E)
At room temperature, 99.43 g sodium sulfate, 26.27 g tartaric acid (H ₂ C ₄ H ₄ O ₆ ), aluminum sulfate solution 660 ml (0.7 mol) and zinc sulfate 14.38 g (0.05 mol) were ion exchanged. Add water to 1.7 L, and dissolve by stirring at room temperature. To this mixed solution, 853 ml (2.87 mol) of sodium hydroxide solution was added and stirred for 10 hours, followed by hydrothermal treatment at 170 ° C. for 2 hours. The reaction solution after the hydrothermal treatment was filtered and washed with water, and dried at 105 ° C. for 15 hours to obtain aluminum salt hydroxide particles (flame retardant E).

Synthesis Example 6 (Synthesis of flame retardant F)
Flame retardant F was prepared by adding flame retardant A to a saturated calcium hydroxide aqueous solution and replacing Na ions with Ca ions while stirring at 60 ° C. for 1 hour.

Synthesis Example 7 (Synthesis of flame retardant G)
Mix 0.08 mol of titanium sulfate (64 g of 30% solution), 28.4 g of sodium sulfate, 63.03 g of oxalic acid, and 1.9 L (2 mol) of aluminum sulfate solution to 8.0 L with ion-exchanged water and stir. did. All dissolved at 45 ° C. The mixture was further stirred for 1 hour and hydrothermally treated at 100 ° C. for 1 hour. The reaction solution after the hydrothermal treatment was filtered, washed with water, and dried (105 ° C., 15 hours) to obtain aluminum salt hydroxide particles.

Synthesis Example 8 (Synthesis of flame retardant H)
Zirconium oxychloride 0.03 mol (ZrCl ₂ O.8H ₂ O: 9.67 g), 28.4 g of sodium sulfate, 63.03 g of oxalic acid, and 1.9 L (2 mol) of an aluminum sulfate solution were mixed to obtain ion-exchanged water. To 8.0 L and stirred. The whole was dissolved at 45 ° C., further stirred for 1 hour, and hydrothermally treated at 100 ° C. for 1 hour. The reaction solution after hydrothermal treatment was filtered, washed with water, and dried (105 ° C., 15 hours) to obtain aluminum salt hydroxide particles (flame retardant H).

Synthesis Example 9 (Synthesis of flame retardant I)
Flame retardant I was synthesized in the same manner as flame retardant D by using tin sulfate instead of nickel sulfate.

Synthesis Example 10 (Synthesis of flame retardant J)
0.1 mol of aluminum sulfate was dissolved in 500 ml of water, this solution and 208 ml (0.125 mol) of an aluminum hydroxide suspension were mixed, and 0.05 mol of oxalic acid was added. After sufficiently stirring, hydrothermal treatment was performed at 170 ° C. for 5 hours. The cooled liquid was washed with filtered water and dried at 95 ° C. for 15 hours to obtain aluminum salt hydroxide particles (flame retardant J).

Synthesis Example 11 (Synthesis of flame retardant K)
0.2 mol of aluminum sulfate and 0.2 mol of ammonium sulfate were dissolved in 600 ml of pure water, and 0.025 mol of oxalic acid was added. While stirring, 89 ml of a 25% aqueous ammonium hydroxide solution was added to the mixed solution, followed by heat treatment at 100 ° C. for 1 hour. The cooled liquid was washed with filtered water and dried at 95 ° C. for 15 hours to obtain aluminum salt hydroxide particles (flame retardant K).
Table 1 shows the characteristics of each flame retardant.
In addition, the commercially available magnesium hydroxide flame retardant L (average secondary particle size 1 μm, BET specific surface area 5 m ² / g, 3% sodium stearate treated with 2.4% stearic acid adsorption amount) used in the comparative example The characteristics are also shown in Table 1.

Examples 1-9, Comparative Examples 1-5, Blank Anti-oxidant 1 (registered trademark: IRGANOX1010 / Ciba Specialty Chemicals Co., Ltd.) 0.5 weight per 100 parts by weight of impact-resistant polypropylene (PP) for injection molding Parts, antioxidant 2 (DLTDP; trade name: DLTP / produced by Yoshitomi Pharmaceutical Co., Ltd.) 0.5 parts by weight and flame retardants A to K obtained in Synthesis Examples 1 to 11, commercially available magnesium hydroxide flame retardant L Were added in amounts shown in Tables 2 and 3 and kneaded at 200 ° C. using a vented twin screw extruder to produce pellets of the resin composition.
The flame retardant used was predried at 200 ° C. before blending.
As a flame retardant aid, red phosphorus (registered trademark: Nova Excel F5 / manufactured by Rin Chemical Industry Co., Ltd.), carbon black (oil furnace method FEF) and silicone resin powder (registered trademark: Dow Corning 4-7081 / Toray Dow Corning) The amount shown in Tables 2 and 3 was added.
The obtained pellets were dried with hot air at 120 ° C. for 5 hours and then injection molded at 230 ° C. using an injection molding machine with a vent to prepare test pieces. In Comparative Example 3, test pieces were prepared using an apparatus without venting for kneading and injection molding. Tables 2 and 3 show the evaluation results of the test piece characteristics.

Examples 10-11, Comparative Example 6
Examples 1 to 9 except that an injection molding grade ABS resin was used instead of polypropylene, the kneading temperature was changed to 230 ° C, and the drying conditions of the pellets were changed to 70 ° C and vacuum drying for 16 hours. A test piece was produced in the same manner. Table 4 shows the evaluation results of the test piece characteristics.

Example 12, Comparative Example 7
Examples 1 to 9 except that injection-grade nylon 6 was used instead of polypropylene, the kneading temperature was changed to 230 ° C., and the drying conditions of the compound pellets were changed to vacuum drying at 70 ° C. for 16 hours. A test piece was prepared in the same manner as described above. However, antioxidant 3 (registered trademark: IRGANOX 1098 / manufactured by Ciba Specialty Chemicals) was used as an antioxidant. Table 4 shows the evaluation results of the test piece characteristics.

Example 13 (acid resistance test)
Of the test pieces produced in the above resin composition production examples, in Example 1, the compounding amount of the flame retardant A is 45 parts by weight, 50 parts by weight, 95 parts by weight, 100 parts by weight with respect to 100 parts by weight of the resin. , 150 parts by weight, 200 parts by weight, and 250 parts by weight. For comparison, in Comparative Example 4, the blending amount of the flame retardant L is 45 parts by weight, 50 parts by weight, 95 parts by weight, 100 parts by weight, 150 parts by weight, 200 parts by weight, 250 parts by weight with respect to 100 parts by weight of the resin. Test pieces were prepared as parts by weight. These test pieces were subjected to sulfuric acid resistance, nitric acid resistance, and hydrochloric acid resistance tests. The results are shown in FIGS. 2 to 4 with the flame retardant blending amount (PHR) on the horizontal axis and the elution amount (ppm) on the vertical axis. The sulfuric acid resistance is also shown in Tables 2 and 3.
As can be seen from Tables 2 and 3 and FIGS. 2 to 4, the molded product produced with the resin composition of the present invention is superior in acid resistance compared to the molded product produced with a conventional resin composition containing magnesium hydroxide. Yes.

According to each test result shown in Tables 2-4,
(1) Resin composition not containing the flame retardant and flame retardant aid of Table 2 (Reference Example 1), resin composition containing only 200 parts by weight of flame retardant (Comparative Example 1), and flame retardant aid only The resin composition blended with 15 parts by weight (Comparative Example 2) did not pass the UL94 vertical V-2 test (1/16 inch) and the UL94HB test (1/8 inch).
(2) As can be seen from the results of Example 1 in Table 2, the polypropylene resin composition containing 15 parts of the flame retardant aid is UL94 vertical V-2 test and UL94HB test even if only 35 parts by weight of the flame retardant is added. To pass,
(3) As can be seen by comparing the results of Example 2 in Table 2 and Comparative Example 4 in Table 3, 45 mg of magnesium hydroxide, which is a conventionally known flame retardant, is added under the same conditions in which 15 parts by weight of the flame retardant aid is blended. Even when blended by weight, the polypropylene resin composition did not pass the UL94 vertical V-2 test at 1/16 inch thickness, but the polypropylene resin composition of the present invention was flame retardant before reaching the V-2 level. Has improved,
(4) As can be seen from Tables 2 and 3 and FIGS. 2 to 4, the polypropylene resin composition of the present invention has significantly improved acid resistance as compared with the conventional polypropylene resin composition.
(5) As can be seen by comparing the elongations of Examples 2 and 3 in Table 2 and Comparative Examples 4 and 5 in Table 3, the polypropylene resin composition of the present invention under the same conditions in which 15 parts by weight of a flame retardant aid is blended Shows a greater elongation than a polypropylene resin composition containing magnesium hydroxide, a conventionally known flame retardant,
(6) From Table 4, the method of the present invention brings about the same effect as the polypropylene resin composition for the nylon 6 composition and the ABS resin composition.
(7) In all the examples, silver streak was second grade or not recognized, but when kneading and injection molding were performed with an apparatus without a vent, silver streak occurred on the surface of the finished molded product. Recognize.
As described above, it can be seen that the resin composition and the molded article of the present invention are excellent in acid resistance and satisfy the mechanical characteristics, surface appearance and silver streak at the same time.

The molded product of the present invention can be used for automobile parts, battery peripheral parts, cables and the like.

Claims (6)

(I) 100 parts by weight of a synthetic resin, where the synthetic resin is polypropylene, ABS resin or polyamide resin,
(Ii) 10 to 200 parts by weight of a flame retardant represented by the following formula (1), and (iii) 0.5 to 20 parts by weight of at least one selected from the group consisting of a phosphorus compound, carbon powder and silicone. Flame retardant aid,
Containing a resin composition.
(Wherein, M is at least one cation selected from the group consisting of Na ⁺ , K ⁺ , NH ₄ ⁺ , H ₃ O ⁺ and Ca ²⁺ , M ′ is Zn ²⁺ , Ni ²⁺ , Sn ⁴⁺ , Zr ^At least one metal cation selected from the group consisting of ⁴⁺ and Ti ⁴⁺ , A represents at least one organic acid anion, B represents at least one inorganic acid anion, and a, b, m, n, x, y and z are 0.7 ≦ a ≦ 1.35, 2.7 ≦ b ≦ 3.3, 0 ≦ m ≦ 5, 4 ≦ n ≦ 7, 0 ≦ x ≦ 0.6, 1.7 ≦ y ≦ 2.4 and 0 ≦ z ≦ 0.5 are satisfied.)   The resin composition according to claim 1, wherein the phosphorus compound is at least one selected from the group consisting of red phosphorus, phosphate ester, condensed phosphate ester and polyphosphate.   The resin composition according to claim 1, wherein the carbon powder is at least one selected from the group consisting of carbon black, activated carbon, and graphite.   The resin composition according to claim 1, wherein the silicone is at least one selected from the group consisting of a silicone resin, a silicone grease, and a silicone rubber.   The flame retardant represented by the formula (1) is at least one surface treatment agent selected from the group consisting of higher fatty acids, titanate coupling agents, silane coupling agents, aluminate coupling agents, and alcohol phosphate esters. The resin composition of Claim 1 currently processed. The molded product formed from the resin composition as described in any one of Claims 1-5 .