ADDITIVE MIXTURES FOR PLASTICS, LASER-MARKABLE POLYMER COMPOSITIONS COMPRISING THEM AND THE USE THEREOF

Abstract

The invention relates to additive mixtures for plastics containing phosphinic acid of the formula (I) as component A,

##STR00001##

wherein R.sub.1 and R.sub.2 mean ethyl, M is Al, Fe, TiO.sub.p or Zn, m means 2 to <4, preferably 2 or 3, and p=(4m)/2 is a compound selected from the group of Al, Fe, TiO.sub.p or Zn salts of ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid and/or dihexylphosphinic acid as component B, phosphonic acid salt of formula (II) as component C,

##STR00002##

wherein R.sub.3 means ethyl, Met is Al, Fe, TiO.sub.q or Zn, n means 2 to 3, and q=(4n)/2, and antimony, tin and/or indium as component D. Polymer compositions containing said additive mixtures are characterized by exceptional flame protection and by very good laser markability or laser weldability.

Claims

1. An additive mixture for plastics, comprising phosphinic salt of the formula (I) as component A ##STR00006## in which R.sub.1 and R.sub.2 are ethyl, M is Al, Fe, TiO.sub.p or Zn, m is 2 to 3, preferably 2 or 3, and
p=(4m)/2; compound selected from the group of the Al, Fe, TiO.sub.p and Zn salts of ethylbutylphosphinic acid, of dibutylphosphinic acid, of ethylhexylphosphinic acid, of butylhexylphosphinic acid and/or of dihexylphosphinic acid as component B; phosphonic salt of the formula II as component C ##STR00007## in which R.sub.3 is ethyl, Met is Al, Fe, TiO.sub.q or Zn, n is 2 to 3, preferably 2 or 3, and
q=(4n)/2; and antimony, tin and/or indium as component D.

2. The additive mixture as claimed in claim 1, wherein M and Met are Al, m and n are 3, and component B is an aluminum salt.

3. The additive mixture as claimed in claim 1, wherein the proportion of component A is 5% to 85% by weight, the proportion of component B is 0.01% to 10% by weight, the proportion of component C is 0.01% to 10% by weight, and the proportion of component D is 0.0001% to 3% by weight, where the percentages are based on the total amount of the additive mixture.

4. The additive mixture as claimed in claim 3, wherein the proportion of component A is 10% to 60% by weight, the proportion of component B is 0.1 A to 2.5% by weight, the proportion of component C is 0.1 A to 2.5% by weight, and the proportion of component D is 0.1% to 2% by weight, where the percentages are based on the total amount of the additive mixture.

5. The additive mixture as claimed in claim 1, which comprises, as component D, 0.0001% to 2.6% by weight of antimony, preferably 0.17% to 1.7% by weight of antimony, and/or 0.0001% to 1.5% by weight of tin, preferably 0.1% to 1% by weight of tin and/or 0.0001% to 1.5% by weight of indium, preferably 0.1% to 1% by weight of indium.

6. The additive mixture as claimed in claim 1, wherein component D is antimony- or fluorine-doped tin oxide, indium tin oxide and/or antimony oxide.

7. The additive mixture as claimed in claim 1, wherein component D is selected from the group consisting of antimony-doped tin oxide, fluoride-doped tin oxide and indium tin oxide, the content of dopants in the tin oxide is 1-15 mol %, preferably 3-10 mol %, and the content of tin in the indium tin oxide is 5-15 mol %.

8. The additive mixture as claimed in claim 1, wherein component D is antimony-doped tin oxide containing 0.0001-2.6% by weight of antimony and/or 0.0001-1.5% by weight of tin, or component D is indium tin oxide containing 0.0001-1.5% by weight of indium and/or 0.0001-1.5% by weight of tin, or component D is tin dioxide/diantimony trioxide-coated mica containing 15-30% by weight of tin and 0.3-2% by weight of antimony, or component D is antimony oxide.

9. The additive mixture as claimed in claim 1, which comprises a colorant E.

10. The additive mixture as claimed in claim 1, which comprises an inorganic phosphonate as component F.

11. The additive mixture as claimed in claim 10, wherein the inorganic phosphonate is a compound of the formula III ##STR00008## in which Me is Fe, TiO.sub.r, Zn or especially Al, o is 2 to 3, preferably 2 or 3, and
r=(4o)/2, where the compound of the formula (III) is present in an amount of 0.01% to 50% by weight, especially in an amount of 0.02% to 25% by weight, based on the total amount of the additive mixture.

12. The additive mixture as claimed in claim 1, which comprises a melamine polyphosphate having an average degree of condensation of 2 to 200 as component I.

13. The additive mixture as claimed in claim 1, wherein components A, B and C and optionally F and I are in particulate form, where the median particle size (d.sub.50) is 1 to 100 m.

14. A polymer composition comprising thermoplastic and/or thermoset polymers and an additive mixture as claimed in claim 1.

15. The polymer composition as claimed in claim 14, which comprises thermoplastic polymers as component G, especially polyam ides or polyesters.

16. The polymer composition as claimed in claim 14, wherein the proportion of component G is 25% to 95% by weight, that of component A is 1% to 35% by weight, that of component B is 0.01% to 3% by weight, that of component C is 0.001% to 1% by weight, that of component D is 0.005% to 2% by weight, that of component E is 0% to 25% by weight and that of component F is 0% to 10% by weight, where the percentages are based on the total amount of the polymer composition.

17. The polymer composition as claimed in claim 14, which has a comparative tracking index measured by International Electrotechnical Commission Standard IEC-60112/3 of not less than 500 volts.

18. The polymer composition as claimed in claim 14, which attains a V-0 assessment according to UL94, especially measured on moldings of thickness 3.2 mm to 0.4 mm.

19. The polymer composition as claimed in claim 14, which has a glow wire flammability index according to IEC-60695-2-12 of not less than 960 C., especially measured on moldings of thickness 0.75-3 mm.

20. The polymer composition as claimed in claim 14, which has a glow wire ignition temperature (GWIT) according to IEC-60695-2-13 of at least 775 C.

21. The polymer composition as claimed in claim 14, which comprises further additives as component H, where the further additives are selected from the group consisting of antioxidants, UV stabilizers, gamma ray stabilizers, hydrolysis stabilizers, costabilizers for antioxidants, antistats, emulsifiers, nucleating agents, plasticizers, processing auxiliaries, impact modifiers, dyes or pigments other than components D and E, fillers, reinforcers and/or further flame retardants other than components A, B, C, F and I.

22. The polymer composition as claimed in claim 14, which comprises glass fibers.

23. The use of the polymer compositions as claim 14 as molding compounds, semifinished products or finished products in the electrics, electronics and motor vehicle industry, in packaging in the foods sector or in the games and toys sector, as label motifs, in medical technology or as plastic marks for individual identification of animals.

24. The use of the polymer compositions as claimed in claim 23, which are used for production of parts of circuit boards, housings, films, conduits, switches, distributors, relays, resistors, capacitors, coils, lamps, diodes, LEDs, transistors, connectors, regulators, storage elements and sensors, in the form of components of large surface area, especially of housing parts for electrical enclosures and in the form of components of complicated configuration with demanding geometry.

Description

EXAMPLES 1-11 and COMPARATIVE EXAMPLES C1-C5 with PA 6,6

[0266] The results of the experiments with PA 6,6 molding compounds are listed in the examples adduced in the table which follows. All amounts are reported as % by weight and are based on the polyamide molding compound including the additives and reinforcers.

TABLE-US-00001 TABLE 1 PA 6,6 GF 30 Test results (1-11 inventive; C1-C5 comparisons) Example No. 1a 1b 1c 1d 1e 2 3 4 5 6 7 G: Nylon-6,6 52.4 60.5 46.5 60.5 60.5 60.5 60.5 60.5 60.5 60.5 60.5 H: glass fibers 30 30 30 30 30 30 30 30 30 30 30 A + B + C: FM 3 8 12 16 8 8 A + B + C: FM 4 8 8 A + B + C: FM 5 8 8 A + B + C: FM 6 8 8 A + B: FM 2 A: FM 1 F: FM 7 I: FM 8 9 5 4 D: L1 0.1 1 3 1 1 1 D: L2 1 1 1 D: L3 1 1 1 1 E: FP 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.51 0.5 0.5 UL 94 0.4 mm/ V-0/28 V-0/28 V-0/29 V-0/29 V-0/28 V-0/24 V-0/23 V-0/42 V-0/43 V-0/28 V-0/29 time [sec.] GWFI [ C.] 960 960 960 960 960 960 960 960 960 960 960 GWIT [ C.] 800 800 800 800 800 800 800 800 800 800 800 CTI [volts] 600 600 600 600 600 600 600 600 600 600 600 Laser markability 1 1 1 1 1 1 1 1 1 1 1 Example No. 8 8a 9 10 11 C1 C2 C3 C4 C5 G: Nylon-6,6 51.48 50.5 60.5 61 61 60.5 60.5 60.5 60.5 56.5 H: glass fibers 30 30 30 30 30 30 30 30 30 30 A + B + C: FM 3 A + B + C: FM 4 12 15 6 8 8 A + B + C: FM 5 A + B + C: FM 6 A + B: FM 2 8 8 12 A: FM 1 8 8 F: FM 7 0.02 3 2 I: FM 8 5 D: L1 1 1 1 1 1 1 D: L2 1 1 D: L3 1 1 1 E: FP 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 UL 94 0.4 mm/ V-0/18 V-0/16 V-0/16 V-0/26 V-0/25 V-0/49 V-0/51 V-0/46 V-0/44 V-0/38 time [sec.] GWFI [ C.] 960 960 960 960 960 960 960 960 960 960 GWIT [ C.] 825 825 825 800 800 725 725 750 750 775 CTI [volts] 600 600 600 600 600 500 500 500 500 550 Laser markability 1 1 1 2 2 1 1 1 1 1

[0267] The inventive polyamide compositions of examples 1 to 11 attain the UL 94 V-0 fire class at 0.4 mm and simultaneously CTI 600 volts, GWFI 960 C. and GWIT 800 0/825 C. These polyamide compositions have very good laser markability; however, the omission of the dye E in examples 10 and 11 leads to slight defects in the laser marking. The addition of component F in examples 8 and 9 leads to another improvement in flame retardancy, expressed by a reduced afterflame time and an improvement in the GWIT.

[0268] The omission of components B and C in comparative examples C1 and C2 resulted not only in a prolonged afterflame time compared to examples 1-11 but also in reduced CTI and GWIT values.

[0269] The omission of component C in comparative examples C3 and C4 resulted not only in a prolonged afterflame time compared to examples 1-11 but also likewise in reduced CTI and GWIT values.

[0270] In comparative example C5, increasing the concentration of components A and B resulted in an extension of the afterflame time compared to comparative example C4. However, this polyamide composition still showed reduced GWIT and CTI values compared to examples 1 to 11.

EXAMPLES 12-22 and COMPARATIVE EXAMPLES C6-010 with PBT

[0271] The results of the experiments with PBT molding compounds are listed in the examples adduced in the table which follows. All amounts are reported as % by weight and are based on the polyester molding compound including the additives and reinforcers.

TABLE-US-00002 TABLE 2 PBT GF 30 Test results (12-22 inventive; C6-C10 comparisons) Example No. 12a 12b 12c 13 14 15 16 17 18 G: PBT 56.5 56.5 56.5 56.5 56.5 56.5 56.5 56.5 56.5 H: glass fibers 30 30 30 30 30 30 30 30 30 A + B + C: FM 3 12 12 12 A + B + C: FM 4 12 12 A + B + C: FM 5 12 12 A + B + C: FM 6 12 12 A + B: FM 2 A: FM 1 D: L1 1 1 1 1 D: L2 1 D: L3 1 1 1 1 E: FP 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 F: FM7 UL 94 0.4 mm/ V-0/28 V-0/29 V-0/23 V-0/25 V-027 V-0/47 V-0/49 V-031 V-0/33 time [sec.] GWFI [ C.] 960 960 960 960 960 960 960 960 960 GWIT [ C.] 775 775 775 775 775 775 775 775 775 CTI [volts] 600 600 600 600 600 600 600 600 600 Laser markability 1 1 1 1 1 1 1 1 1 Example No. 19 20 21 22 C6 C7 C8 C9 C10 G: PBT 56.5 56.5 57 57 56.5 56.5 56.5 56.5 56.5 H: glass fibers 30 30 30 30 30 30 30 30 30 A + B + C: FM 3 A + B + C: FM 4 10 10 12 12 A + B + C: FM 5 A + B + C: FM 6 A + B: FM 2 12 12 18 A: FM 1 12 12 D: L1 1 1 1 1 1 D: L2 D: L3 1 1 1 E: FP 0.5 0.5 1 0.5 0.5 0.5 F: FM7 2 2 UL 94 0.4 mm/ V-0/14 V-0/18 V-026 V-0/25 V-0/54 V-0/52 V-0/48 V-0/47 V-0/43 time [sec.] GWFI [ C.] 960 960 960 960 960 960 960 960 960 GWIT [ C.] 800 800 775 775 725 725 725 725 750 CTI [volts] 600 600 600 600 500 500 500 500 550 Laser markability 1 1 2 2 1 1 1 1 1

[0272] The inventive polyester compositions of examples 12 to 22 attain the UL 94 V-0 fire class at 0.4 mm and simultaneously CTI 600 volts, GWFI 960 C. and GWIT 775 0/800 C. These polyester compositions have very good laser markability; however, the omission of the dye E in examples 21 and 22 leads to slight defects in the laser marking. The addition of component F in examples 19 and 20 leads to another improvement in flame retardancy, expressed by a reduced afterflame time and an improvement in the GWIT.

[0273] The omission of components B and C in comparative examples C6 and C7 resulted not only in a prolonged afterflame time compared to examples 12-22 but also in reduced CTI and GWIT values.

[0274] The omission of component C in comparative examples C8 and C9 resulted not only in a prolonged afterflame time compared to examples 12-22 but also likewise in reduced CTI and GWIT values.

[0275] In comparative example 010, increasing the concentration of components A and B resulted in an extension of the afterflame time compared to comparative example C9. However, this polyester composition still showed reduced GWIT and CTI values compared to examples 12 to 22.