Surface treatment of particles and their use

Abstract

The invention relates to polymer compositions containing inorganic or organic particles which either have been surface-treated before the production of the compositions or are dispersed by special polyether-modified siloxanes through the production of the compositions.

Claims

1. A polymer composition, comprising: a) a solid particle, b) at least one polymer selected from the group consisting of a thermoplast and a duromer, c) 0.05 to 10 wt. % based on the total weight of the composition of a compound of formula (I), ##STR00004## where R identically or differently is R.sup.1 methyl, or hydroxy, R.sup.1 identically or differently is a polyether residue of formula (III)
—Z—(O—C.sub.mH.sub.2m-(n-1)).sub.o—[O-((AO).sub.r—R.sup.3]].sub.n  (III) where Z is a branched alkylene residue or an unbranched alkylene residue with 2 to 4 carbon atoms, m is from 2 to 4, n is from 1 to 3, o is from 0 or 1, AO is independently an oxyalkylene residue selected from the group consisting of an oxypropylene residue, an oxybutylene residue, and a combination of oxypropylene residue and oxybutylene residue, each of which optionally includes an oxyetheylene residue, R.sup.3 is hydrogen, and with the proviso that in R.sup.1 a sum of carbon and oxygen atoms is at least 70, with the proviso that r has a value that, taken together with m and n, provides said group R.sup.1 with a total number of carbon atoms and oxygens atoms of at least 70, a is from 20 to 200, b is from 1 to 50, with the proviso that if none of residues R is equal to R.sup.1, b is at least 3, and d) optionally further components.

2. The polymer composition according to claim 1, wherein R.sup.1 identically or differently is a —(CH.sub.2).sub.p—O-EO.sub.x—PO.sub.y—BO.sub.z—R.sup.3, with the proviso that in R.sup.1 the sum of carbon and oxygen atoms is at least 70, and EO is oxyethylene, PO is oxypropylene, BO is oxybutylene, x is from 0 to 20, y is from 5 to 100, z is from 0 to 20, p is from 2 to 4, and R.sup.3 is as defined in claim 1.

3. The polymer composition according to claim 1, wherein a numerical ratio of a to b is from 8:1 to 18:1.

4. The polymer composition according to claim 2, wherein x is between 0.05 and 1.2 times a sum of y and z.

5. The polymer composition according to claim 1, wherein the solid particle is a colouring pigment particle.

6. The polymer composition according to claim 1, wherein has been treated with the at least one compound of the formula (I) before mixing with component b), and the solid particle excludes a titanium dioxide particle, a barium sulphate particle, a zinc sulphide particle, and a lithopone particle.

7. The polymer composition according to claim 6, which comprises 0.01 to 3 wt. % of the at least one compound of the formula (I) based on a particle mass as part of the polymer composition.

8. The polymer composition according to claim 1, wherein the solid particle is an aluminum trihydrate (ATH) particle or a magnesium hydroxide (MDH) particle.

9. The polymer composition according to claim 1, which exhibit a decrease in water absorption of 25% compared to a polymer composition which does not contain the compound of the formula (I).

10. The polymer composition according to claim 1, which has an MFI which lies at least 10% above an MFI which was determined with the same composition which comprises the same solid particle in non-surface-treated form.

11. A method for retarding a flame, comprising contacting the polymer composition according to claim 1 with the flame, wherein the polymer composition comprises an aluminum trihydrate (ATH) particle or a magnesium hydroxide (MDH) particle.

12. The polymer composition according to claim 8, which is better by at least one UL 94 fire class, compared to a polymer composition which does not contain the at least one compound of the formula (I).

13. A process for treating a surface of a primary particle, comprising contacting the primary particle with at least one compound of formula (I) ##STR00005## where R identically or differently is R.sup.1, methyl or hydroxy, R.sup.1 identically or differently is a polyether residue of the formula (III)
—Z—(O—C.sub.mH.sub.2m-(n-1)).sub.o—[O-((AO).sub.r—R.sup.3]].sub.n  (III) where Z is a branched alkylene residue or an unbranched alkylene residue with 2 to 4 carbon atoms, m is from 2 to 4, n is from 1 to 3, o is from 0 or 1, AO is independently an oxyalkylene residue selected from the group consisting of an oxypropylene residue, an oxybutylene residue, and a combination of oxypropylene residue and oxybutylene residue, each of which optionally includes an oxyethylene residue, R.sup.3 is hydrogen, and with the proviso that in R.sup.1 a sum of carbon and oxygen atoms is at least 70, with the proviso that r has a value that, taken together with m and n, provides said group R.sup.1 with a total number of carbon atoms and oxygens atoms of at least 70, a is from 20 to 200, b is from 1 to 50, with the proviso that if none of the residues R is equal to R.sup.1, b is at least 3, wherein 0.01 to 2 wt. % of the at least one compound of the formula (I) is contacted with the primary particle, based on a mass of the primary particle to be treated, and the primary particle excludes a titanium dioxide particle, a barium sulphate particle, a zinc sulphide particle, and a lithopone particle.

14. A polymer composition, comprising: a) a solid particle, b) at least one polymer, which is a thermoplast selected from the group consisting of polyethylene, polypropylene, polyamide, polystyrene, and blends thereof, or a duromer, which is a silicone resin or a urea resin, c) at least one compound of formula (I), ##STR00006## where R identically or differently is R.sup.1, methyl, or hydroxy, R.sup.1 identically or differently is a polyether residue of formula (III)
—Z—(O—C.sub.mH.sub.2m-(n-1)).sub.o—[O-((AO).sub.r—R.sup.3]].sub.n  (III) where Z is a branched alkylene residue or an unbranched alkylene residue with 2 to 4 carbon atoms, m is from 2 to 4, n is from 1 to 3, o is from 0 or 1, AO is independently an oxyalkylene residue selected from the group consisting of an oxypropylene residue, an oxybutylene residue, and a combination of oxypropylene and oxybutylene, each of which optionally includes an oxyetheylene residue, R.sup.3 is hydrogen, and with the proviso that in R.sup.1 a sum of carbon and oxygen atoms is at least 70, with the proviso that r has a value that, taken together with m and n, provides said group R.sup.1 with a total number of carbon atoms and oxygens atoms of at least 70, a is from 20 to 200, b is from 1 to 50, with the proviso that if none of the residues R is equal to R.sup.1, b is at least 3, and d) optionally further components.

15. The polymer composition according to claim 14, wherein the thermoplast is polypropylene.

Description

EXAMPLES

(1) General Methods and Materials:

(2) Viscosity:

(3) The viscosities were determined by means of a Brookfield LV-DV-I+ spindle viscosimeter. Brookfield viscosimeters are rotary viscosimeters having defined spindle sets as rotary bodies. The rotary bodies used were from an LV spindle set. Because of the temperature dependence of the viscosity, the temperatures of viscosimeter and measurement liquid were kept precisely constant to +/−0.5° C. Other materials used as well as the LV spindle set were a thermostatted water bath, a 0 to 100° C. thermometer and a time measurement device (gradations not greater than 0.1 seconds). To perform the measurement, 100 ml of the sample were introduced into a wide-necked bottle and measured under temperature-controlled conditions in the absence of air bubbles after prior calibration. To determine the viscosity, the viscosimeter was positioned relative to the sample such that the spindle dips into the product up to the mark. The measurement is triggered by means of the start button, with care being taken that the measurement was made in the favourable measurement range of 50% (+/−20%) of the maximum measurable torque, otherwise a suitable spindle had to be used. The result of the measurement was outputted on the display of the viscosimeter in mPas, and division by the density (g/ml) yields the viscosity (g/ml) in the unit [mm.sup.2/s].

(4) Particle Fineness Test:

(5) a) With Grindometer

(6) The determination is performed according to DIN EN 21524 (corresponding to ISO 1525).

(7) 3 g of the white pastes produced according to Example 5 (Z2) were stirred well with the spatula in a plastic beaker with the same quantity of DOP. To determine the fineness, the diluted paste was applied on the Hegman block (grindometer) firstly on the Hegman block 0 to 100 μm and then the samples of appropriate fineness were applied on the Hegman block 0 to 25 μm (Erichsen Co.). The visually determined fineness values in μm were noted.

(8) b) With Pressure Filter Test

(9) The determination of the pressure filter value was performed with the single-screw extruder Brabender Plasti-Corder LAB Station (screw diameter/length: 30 mm/25D). Different screen packs from GKD (PZ-Microdur 10 (Filter fineness 9 μm) and a supporting fabric of 315 μm mesh width were used. The extruder was heated to a temperature of 200° C. The temperature of the filter equipment was adjusted to 230° C. After thorough flushing of the extruder with LDPE, the filter holder with the screen pack was incorporated. After charging of the masterbatch pellets to be tested and emergence of the pigmented material at the bypass, the melt stream was passed through the screen pack and the computer-assisted measurement data capture started. The measurement data were recorded up to the attainment of a maximal pressure of 150 bar or else in case of a small pressure increase up to a duration of 60 minutes. The throughput was 40 g/min.

(10) Flame Retardancy Testing:

(11) To determine the fire resistance of plastic preparations, test pieces with a thickness of 4 mm were produced by injection moulding. The determination of the fire class was performed according to UL 94 (Underwriter Laboratories). The following fire classes are defined:

(12) V-0: no afterburning longer than 10 secs, in 10 flame treatments the sum of the afterburn times is not greater than 50 secs, no burning drips, the sample does not burn completely, after end of flame exposure the sample glows for not longer than 30 secs.

(13) V-1: after end of flame exposure the sample glows for not longer than 60 secs, in 10 flame treatments the sum of the afterburn times is not greater than 250 secs, other criteria as in V-0.

(14) V-2: The wadding ignites because of burning drips, other criteria as V-1.

(15) Not classifiable (ncl): does not meet fire class V-2.

(16) Spectroscopic Analyses:

(17) The recording and interpretation of NMR spectra is known to the skilled person. References include the book “NMR Spectra of Polymers and Polymer Additives”, A. Brandolini and D. Hills, 2000, Marcel Dekker, Inc. The spectra were recorded at room temperature with a Bruker Spectrospin spectrometer, with measurement frequencies when recording the proton spectra of 399.9 MHz, when recording the .sup.13C spectra of 100.6 MHz and when recording the .sup.29Si spectra of 79.5 MHz.

(18) Determination of Molecular Masses, in Particular the Weight Average Molecular Masses Mw:

(19) The gel permeation chromatographic analyses (GPC) were performed with a type 1100 instrument from Hewlett-Packard using an SDV column combination (1000/10000 Å, each 65 cm, internal diameter 0.8 cm, temperature 30° C.), THF as mobile phase with a flow rate of 1 ml/min and an RI detector (Hewlett-Packard). The system was calibrated against a polystyrene standard in the range from 162 to 2,520,000 g/mol.

(20) Determination of the SiH Content:

(21) The determinations of the SiH values of the hydrogen siloxanes used but also that of the reaction matrices are each performed by gas volumetry through the sodium butylate-induced decomposition of aliquot weighed out sample amounts using a gas burette. Inserted into the general gas equation, the measured hydrogen volumes enable the determination of the content of active SiH functions in the educts but also in the reaction mixtures and thus enable conversion monitoring. A 5 wt. % sodium butylate solution was used.

(22) In the following examples, TP 6875 means TEGOPREN® 6875, trademark of Evonik Industries AG, Essen.

Example 1: Synthesis

(23) The polyethers used (table 1, PE) each have an allyl ether (PE1-PE8) or vinyl ether function (PE9) and a hydroxy group (PE1-PE9) at the chain ends and are characterized by different oxyethylene, oxypropylene and oxybutylene mass contents (EO/PO/BO mass contents, based on the polyether part without allyl/vinyl group) and molecular masses (Mw). The vinyl polyether PE9 has an oxybutylene residue as a fragment with the index o according to formula (III), in this case equal to —O—(CH.sub.2).sub.4—. Glycerine monoallyl ether, which was used in the polyether PE10 and trimethylolpropane monoallyl ether, which was used in the polyether PE11.

(24) TABLE-US-00001 TABLE #1 Composition of the polyethers used Polyether PO, [wt. %] EO, [wt. %] BO, [wt. %] Mw [g/mol] PE1 77 23 1057 PE2 80 20 518 PE3 100 0 414 PE4 68 32 1417 PE5 88 12 1336 PE6 72 28 1219 PE7 90 10 1180 PE8 80 10 10 1194 PE9 83 10 7 1194 PE10 90 10 1248 PE11 90 10 1298

(25) The hydrogen siloxanes used (Table #2, SH) are characterized by different SiH contents and viscosities.

(26) TABLE-US-00002 TABLE #2 Properties of the hydrogen siloxanes used Hydrogen siloxane SiH content, [mmol/g] Viscosity, 25° C., [mPa*s] SH1 2.29 116 SH2 0.90 159 SH3 1.40 61 SH4 3.52 101

(27) The polyether-modified siloxanes (Table #3, O) were prepared by hydrosilylation by the following method.

(28) The hydrogen siloxane SH used and the hydroxy functional terminally unsaturated PE used were placed in the ratio of 1.35 moles allyl polyether per mole equivalent SiH in a 500 ml four-necked flask with attached KPG stirrer, reflux condenser and internal thermometer, and heated with stirring at 70° C. 5 ppm of platinum in the form of the Pt.sub.2(divinyltetramethyl-disiloxane).sub.3 complex (Karstedt catalyst, 1.5% Pt in deca-methylcyclopentasiloxane) were added to this with a syringe. The conversion determined by gas volumetry was quantitative within 1 to 3 hours postreaction time at 70-80° C. After filtration, yellow-brownish, clear, viscous liquids were obtained.

(29) TABLE-US-00003 TABLE #3 Siloxanes prepared according to Example 1, the mixture cited in O13 is an equimolar mixture of the stated polyethers Example Hydrogen siloxane Polyether O1 SH2 PE1 O2 SH2 PE5 O3 SH1 PE1 O4 SH2 PE3 O5 SH2 PE6 O6 SH3 PE1 O7 SH4 PE2 O8 SH1 PE2 O9 SH4 PE3 O10 SH4 PE1 O11 SH2 PE4 O12 SH2 PE7 O13 SH4 PE1 + PE5 O14 SH2 PE8 O15 SH2 PE9 O16 SH2 PE10 O17 SH2 PE11

Example 2: Emulsions

(30) 185 g of O12 were added within 20 minutes with cooling to an emulsifier solution made from 40 g of an ethoxylated stearic acid with an HLB value of ca. 18.8 and 60 g demineralized water with shearing (Mizer disc, 2000 rpm). The mixture was then sheared for a further 20 minutes. A paste of elevated viscosity was formed. Next, 214 g demineralized water were added within 10 minutes with shearing. A white emulsion with a solids content of ca. 45 wt. % was obtained. For preservation of the emulsion, 0.15% of an aqueous solution of 20 wt. % methylisothiazolinone (MIT) were added at the end.

Example 3: Surface Treatment of Particles

(31) V1: Treatment of Inorganic Pigments in Dry Phase

(32) 495 g of the particles were placed in a Henschel mixer and then in each case 5 g of the surface treatment agents (according to Table #3: O1 to O17, and surface treatment agents of the state of the art) were added. For this, the mixer was run for 15 minutes at a speed of 900 rpm, during which heating to up to 70° C. can occur.

(33) Iron oxide: Particles P-FO-1 to P-FO-17

(34) Calcium carbonate: Particles P-KC-1 to P-KC-17

(35) Talc, particles P-T-1 to P-T-17

(36) ATH, particles P-ATH-1 to P-ATH-17

(37) MDH, particles P-MDHT-1 to P-MDHT-17

(38) In addition, comparison particles were prepared by means of surface treatment agents of the state of the art:

(39) TABLE-US-00004 Surface treatment Calcium agent carbonate Talc ATH MDH None P-KC-18 P-T-18 P-ATH-18 P-MDHT-18 TP 6875 P-KC-19 P-T-19 P-ATH-19 Silicone oil 1000 P-KC-20 P-T-20 P-ATH-20
V2: Treatment of Inorganic Pigments in Wet Phase

(40) The quantity of post-treatment agent is based on the solids content of the dispersion of the pigment, flame retardant or filler. In the wet treatment, the stated quantity ratios relate to the solids content of compounds of the formula (I) in the slurries.

Example 4: Preparation of Compounds Comprising Surface-Modified Particles which were Prepared According to or Analogously to Example 3

(41) The following filler compound formulae were prepared with a Leistritz extruder 27 mm (twin-screw extruder from Leistritz) at 200 rpm:

(42) TABLE-US-00005 Ingredients Mass [g] Polypropylene, MFI 21 76.84 surface-treated particles 20 Irganox PS 802 0.6 Irganox 1010 0.2 Uvinul 4050 0.13 Uvinul 5050 0.13 Calcium stearate 0.1 Carbon black masterbatch 2

(43) The compositions according to the invention Z-T-1 to Z-T-17 are obtained.

(44) The compositions according to the invention Z-FO-1 to Z-FO-17 (iron oxide) and the compositions not according to the invention Z-FO-18 (without surface treatment) to Z-FO-20 (containing the comparison particles P-FO-19 to P-FO-20) are obtained.

(45) In a similar manner, fire retardant compounds containing surface-treated ATH particles are prepared with the formula:

(46) TABLE-US-00006 Ingredients Mass [g] Escorene UL 0328 25.73 Exxon LL 1004 YP 12.67 surface-treated particles 61.4 Irganox 1010 0.2

(47) The compositions according to the invention Z-ATH-1 to Z-ATH-17 (ATH) and the compositions not according to the invention Z-ATH-18 to Z-ATH-20 (containing the comparison particles P-ATH-18 to P-ATH-20) are obtained.

(48) In a similar manner, flame retardant compounds containing surface-treated MDH particles are prepared with the formula:

(49) TABLE-US-00007 Ingredients Mass [g] Escorene UL 00328 23.05 Exxon LLDPE 1004 YP 11.35 surface-treated particles 61.4 Fusabond MB226 4 Irganox 1010 0.2

(50) The compositions according to the invention Z-MDH-1 to 17 (MDH) and the compositions not according to the invention Z-MDH-23 to Z-MDH-28 (containing the comparison particles P-MDH-23 to P-MDH-28) are obtained

Example 5: Testing of the Properties of the Particles According to Example 3

(51) (Determination of the Bulk Density):

(52) To determine the bulk density, sample quantities of 15 g or 30 g were placed at room temperature in a 100 ml measuring cylinder. After 10 mins, the volumes were read off. The bulk density is calculated as the quotient of the sample weight and the volume found.

(53) In the following table, the “*” stands for talc, ATH and MDH; i.e. the first three particles are P-T-1, P-ATH-1 and P-MDH-1.

(54) TABLE-US-00008 Bulk density Bulk density Bulk density Talc (T) ATH MDH Particle [g/ml] [g/ml] [g/ml] P-*-1 0.218 0.442 0.45 P-*-2 0.217 0.431 0.47 P-*-3 0.219 0.432 0.46 P-*-4 0.220 0.436 0.42 P-*-5 0.216 0.432 0.44 P-*-6 0.220 0.439 0.43 P-*-7 0.219 0.440 0.45 P-*-8 0.218 0.439 0.44 P-*-9 0.217 0.438 0.43 P-*-10 0.220 0.441 0.42 P-*-11 0.220 0.440 0.45 P-*-12 0.219 0.442 0.46 P-*-13 0.218 0.438 0.43 p-*-14 0.217 0.439 0.45 P-*-15 0.219 0.441 0.44 P-*-16 0.218 0.438 0.44 P-*-17 0.220 0.435 0.45 P-*-18 (none) 0.214 0.429 0.41 P-*-19 (TP 6875) 0.214 0.427 0.42 P-*-20 (silicone oil 1000) 0.200 0.411 0.39

Example 6A: Tensile Strength, Elongation at Break and Impact Resistance

(55) In order to be able to assess the mechanical properties of the filler compounds, shouldered rods were prepared by injection moulding (Engel Germany). Tensile test rods type 1A were prepared as described in DIN ISO 527-2.

(56) The tensile strength was obtained by means of a tensile test device from Zwick (23° C., 50% rel. atmospheric humidity). The machine parameters: initial load=20 N, speed up to initial load=1 mm/min, test speed=5 mm/min, clamping length=120 mm and measurement length of the incremental pick-up=80 mm, thickness of the test piece 4 mm corresponding to the tensile test rod type 1A were used.

(57) Impact Resistance (Charpy):

(58) The tests were performed with a 5 J impact pendulum according to ISO 179.

(59) Results of the mechanical tests: Z-T-18 and Z-ATH-18 are test pieces whose particles were not post-treated.

(60) TABLE-US-00009 Tensile Elongation Impact strength at break resistance Test sample σ.sub.M [MPa] εtB [%] [kJ/m.sup.2] Z-T-1 26.3 25 6.05 Z-T-2 26.5 28 6.32 Z-T-3 26.6 29 5.94 Z-T-4 26.4 26 5.99 Z-T-5 26.5 18 6.05 Z-T-6 26.7 19 6.09 Z-T-7 27.0 23 6.32 Z-T-8 26.8 22 6.51 Z-T-9 26.9 24 6.09 Z-T-10 26.8 18 6.26 Z-T-11 26.9 19 6.39 Z-T-12 27.2 22 6.58 Z-T-13 27.2 26 5.99 Z-T-14 27.0 23 5.95 Z-T-15 26.6 25 5.99 Z-T-16 26.4 21 6.28 Z-T-17 26.9 20 6.42 Z-T-18 26.2 15 5.81 Tensile Elongation Example strength at break ATH σ.sub.M [MPa] εtB [%] Z-ATH-1 11.8 67 Z-ATH-2 10.9 73 Z-ATH-3 10.4 85 Z-ATH-4 10.9 110 Z-ATH-5 10.8 91 Z-ATH-6 11.2 78 Z-ATH-7 10.7 90 Z-ATH-8 11.3 72 Z-ATH-9 11.1 71 Z-ATH-10 11.7 84 Z-ATH-11 11.0 85 Z-ATH-12 11.9 103 Z-ATH-13 11.5 108 Z-ATH-14 10.7 101 Z-ATH-15 10.9 81 Z-ATH-16 10.6 76 Z-ATH-17 11.5 71 Z-ATH-18 10.2 58
Compositions Containing Surface-Treated MDH Particles

(61) In order to be able to assess the mechanical properties of the filler compounds, using a single-screw extruder Brabender Plasti-Corder LAB Station (screw diameter/length: 30 mm/25D) compound strips of 1.7 mm thickness were continuously produced from the compounds previously prepared according to the above description by means of twin-screw extruders and shouldered rods were stamped out of these compound strips with a tool, which according to DIN ISO 527-2 yield type 5A rods.

(62) The tensile strength was obtained with a tensile test device from Zwick (23° C., 50% rel. atmospheric humidity). The machine parameters were: initial load=20 N, speed up to initial load=1 mm/min, test speed=5 mm/min, clamping length=120 mm and measurement length of the incremental pick-up=80 mm.

(63) The fire classes were tested in a combustion chamber according to UL 94. Z-MDHT-18: The MDH were not surface-treated.

(64) TABLE-US-00010 Tensile Elongation Example strength at break MDH σ.sub.M [MPa εtB [%] Z-MDHT-1 12.1 220 Z-MDHT-2 12.0 200 Z-MDHT-3 12.3 180 Z-MDHT-4 12.5 190 Z-MDHT-5 11.9 220 Z-MDHT-6 12.0 210 Z-MDHT-7 12.1 200 Z-MDHT-8 12.4 200 Z-MDHT-9 12.3 200 Z-MDHT-10 12.0 220 Z-MDHT-11 11.7 220 Z-MDHT-12 12.2 210 Z-MDHT-13 12.0 210 Z-MDHT-14 11.9 180 Z-MDHT-15 11.9 190 Z-MDHT-16 12.2 210 Z-MDHT-17 12.3 220 Z-MDHT-18 10.8 160

Example 6B: Fire Class

(65) 5 specimens (test pieces) were always tested, and these are also the type 1A rods produced for the mechanical testing.

(66) Specimens containing 59 and 61.4% were tested analogously, as to the manner described in UL 94. The fire classes were tested in a combustion chamber according to UL 94, and the fire class is stated with the number of test pieces which pass V2, V1 or V0, or if necessary as failed if none of the classes is attained.

(67) Z-ATH-18 is based on a composition the ATH particles whereof were not surface-treated. Z-ATH-19 is based on compositions the particles whereof were treated with silicone oil according to the state of the art.

(68) TABLE-US-00011 Example Fire class ATH 59% 61.4% Z-ATH-1 5x V0 5xV0 Z-ATH-2 4xV0, 1xV1 5xV0 Z-ATH-3 5x V0 5xV0 Z-ATH-4 4xV0, 1xV1 5xV0 Z-ATH-5 4xV0, 1xV1 5xV0 Z-ATH-6 5x V0 5xV0 Z-ATH-7 5x V0 5xV0 Z-ATH-8 4xV0, 1xV1 5xV0 Z-ATH-9 5x V0 5xV0 Z-ATH-10 5x V0 5xV0 Z-ATH-11 5x V0 5xV0 Z-ATH-12 5x V0 5xV0 Z-ATH-13 4xV0, 1xV1 5xV0 Z-ATH-14 4xV0, 1xV1 5xV0 Z-ATH-15 5x V0 5xV0 Z-ATH-16 5x V0 5xV0 Z-ATH-17 4xV0, 1xV1 5xV0 Z-ATH-18 failed 2xV0, 3xV1 Z-ATH-19 failed 2xV2, 3xV1

(69) From the results it can be seen that fire class V-0 is attained, although a lower content of fire retardant (ATH) is contained in the compound.

Example 6C: MFI (Melt Flow Index) and Water Absorption of the Dry Post-Treated MDH Particles (Flame Retardant Compound)

(70) Here, to determine the water absorption the tensile test rods described which correspond to type 1A, i.e. not the extruded strips resulting in the stamped out type 5A, were used. The test pieces are stored in the oven for 14 days at 80° C. and the weight increase then stated in %.

(71) The testing of the MFI was performed by means of DIN EN ISO 1133 with the instrument Meltfixer from SWO Polymertechnik GmbH.

(72) Z-MDHT-18 is based on a composition the particles whereof were not surface-treated.

(73) TABLE-US-00012 Example MFI at Water absorption MDH 190° C./21.6 kg in % Z-MDHT-1 7.58 0.34 Z-MDHT-2 8.31 0.38 Z-MDHT-3 8.02 0.33 Z-MDHT-4 7.79 0.38 Z-MDHT-5 7.91 0.40 Z-MDHT-6 8.31 0.29 Z-MDHT-7 8.09 0.31 Z-MDHT-8 7.88 0.36 Z-MDHT-9 7.81 0.29 Z-MDHT-10 8.54 0.28 Z-MDHT-11 9.01 0.29 Z-MDHT-12 8.87 0.26 Z-MDHT-13 7.69 0.26 Z-MDHT-14 7.42 0.28 Z-MDHT-15 7.92 0.27 Z-MDHT-16 8.03 0.34 Z-MDHT-17 7.56 0.39 Z-MDHT-18 6.72 0.55

(74) From the values it can be seen that through the surface treatment of the particles the water absorption of the compositions according to the invention fell to below 0.45%.

(75) Relative to the compositions based on untreated particles, the flowability increased by at least 5%.

(76) V4 Liquid Pastes Method:

(77) V4A: Production of Pigment Pastes with Surface-Modified Pigments

(78) For the liquid pastes production, pigments were used which had previously been coated with the compounds of the formula (I) by modification in the dry phase. 98 g of pigment are post-treated with 2 g of polyether-modified siloxanes and the aforesaid Henschel equipment is used for this. Next, 80 g of an epoxidized soya oil (e.g. Epoxol D 44, FACI) with 20 g of pigment Blue 15:3 which had been coated with the compounds according to the invention (e.g. Heliogen Blue K 7090, BASF) are weighed out into a 250 ml powder jar and dispersed for 5 mins at 2500 rpm with an H-Trieb with dissolver disc.

(79) Testing of the Liquid Pastes

(80) 3 g of the pigment pastes prepared are applied for the determination of the fineness on the Hegman block (grindometer) 0-25 μm (Erichsen). The visually determined fineness values in μm were noted.

(81) A fineness of greater than 15 μm indicates inadequate dispersion.

(82) Determination of the granularity: Z-P-18 is a paste the particles whereof had not been surface-treated, Z-P-19 is a paste the particles whereof had been surface-treated with silicone oil according to the state of the art.

(83) TABLE-US-00013 Example (Heliogen Blue) Fineness [μm] Z-P-1 13 Z-P-2 12 Z-P-3 12 Z-P-4 12 Z-P-5 13 Z-P-6 13 Z-P-7 12 Z-P-8 12 Z-P-9 12 Z-P-10 12 Z-P-11 12 Z-P-12 12 Z-P-13 13 Z-P-14 13 Z-P-15 12 Z-P-16 13 Z-P-17 12 Z-P-18 18 Z-P-19 25
Compositions Prepared by Mixing Polymers with Particles and Surface Treatment Agents in One Process Step
V5B: Production of Pigment Pastes where the Unmodified Particle is Dispersed into a Mixture of Continuous Phase and Special Alkoxylated Polyethers.

(84) For the production of pigment pastes as alternatives to solid pigment masterbatches, pigment pastes are produced according to the following formulae: The use of additives of the formula (I) leads to compositions according to the invention.

(85) The components are placed together with 200 g of glass beads (diameter 2 mm) in a 250 ml powder bottle and dispersed for 2 hrs in the Scandex (Lau GmbH):

(86) TABLE-US-00014 Ingredients Paste 1 Paste 2 Paste 3 Paste 4 Rape oil 78 78 Diisononyl phthalate 78 78 Phthalocyanine blue 20 20 (Heliogen Blue K 7090, BASF) Pigment Red 57:1 20 20 (Irgalite ® Rubine K 4270 FP, BASF) Additive 2 2 2 2 (Compound of the formula (I))
Thermoplastic Injection Moulded Parts Based on Polypropylene

(87) In order to determine the colouring power and dispersion quality of the pastes listed in Table #20, plates of 6×6×0.2 cm size are produced by injection moulding (Engel Germany). For this, 400 g of polypropylene (MFI 20) are mixed with 16 g of white masterbatch (TiO.sub.2 content=50%) and 4 g of pigment paste in the PE bag and the injection moulded part assessed by colorimetry.

(88) Colorimetric Assessment and Calculation of the Colour Intensity:

(89) The colorimetric values of the plates produced are determined by means of a spectrophotometer (SP 68, X-Rite). The results are stated in Table #20 as L-a-b values. At the same time, the colour strength compared to a reference sample is calculated. The better the pigment was dispersed in the phase, the higher is the colour strength compared to the reference sample. The reference sample is by definition set at 100%.

(90) TABLE-US-00015 TABLE #20 The values stated were determined using paste 1, ZZ-P-18 is based on a composition which contained no compound of the formula (I). Colour strength Example L* a* b* [%] ZZ-P-1 61.76 −37.26 108 ZZ-P-2 61.33 −37.21 109 ZZ-P-3 61.19 −20.92 −37.37 109 ZZ-P-4 60.78 −37.10 112 ZZ-P-5 61.35 −37.09 109 ZZ-P-6 60.60 −37.13 113 ZZ-P-7 60.50 −36.92 116 ZZ-P-Z8 60.34 −20.69 −37.13 116 ZZ-P-9 60.58 −36.89 115 ZZ-P-10 61.75 −37.02 108 ZZ-P-11 61.55 −37.18 109 ZZ-P-12 60.37 −20.62 −36.78 116 ZZ-P-13 60.41 −36.95 116 ZZ-P-14 60.78 −37.01 112 ZZ-P-15 60.87 −37.14 112 ZZ-P-16 61.45 −37.42 108 ZZ-P-17 61.40 −37.15 109 ZZ-P-18 62.45 −20.82 −35.83 100

(91) As can be clearly seen from the values, the colour strength is increased by at least 8% through the polyether-modified siloxanes according to the description and the better dispersion becomes clear not only from this, but also from the reduced brightness values L*, which are typical for a better dispersed blue pigment. Since the red value a* scarcely changes and is not very characteristic, it is not also stated here for all compositions and the blue value also is only listed for completeness.

(92) V5C Production of Pigment Pastes for PU Foam Applications

(93) The components are placed together with 200 g of glass beads (diameter 2 mm) in a 250 ml powder bottle and dispersed for 4 hrs in the Scandex (Lau GmbH).

(94) The pigment pastes are produced according to the following formula:

(95) TABLE-US-00016 Paste Polyol (Caradol ED-03) 70 g Surface-treated carbon black (Monarch 800, Cabot) Carbon black (Monarch 800, Cabot) 20 g Additive 10 g (Compound of the formula (I))

(96) For the production of the PU foams, the following components are mixed and foamed in a plastic beaker. After the end of the reaction time, plates are sawn out of this foam and the colour strength calculated by means of a spectrophotometer (SP 68, X-Rite). As the reference sample, a foam with no additive which is defined with 100% colour strength is selected.

(97) Production of a PU foam for assessment of the dispersion quality which is assessed on the basis of the colour strength development:

(98) TABLE-US-00017 Ingredients Mass [g] Polyether polyol OHZ: 47 100.00 (Varanol CP 3322; Dow) Metal catalyst 0.22 (Kosmos 29, Evonik) Tegostab BF 2370, Evonik 1.00 Water 5.00 Dimethylethanolamine 0.15 Tolyl diisocyanate 58.40 Varonate T-80, Dow Pigment paste 1.00

(99) The composition Z-R-18 contained no compound of the formula (I), the composition Z-R-19 contained silicone oil.

(100) TABLE-US-00018 Example Colour strength [%] Z-R-1 108 Z-R-2 107 Z-R-3 108 Z-R-4 111 Z-R-5 110 Z-R-6 115 Z-R-7 110 Z-R-Z8 109 Z-R-9 108 Z-R-10 109 Z-R-11 109 Z-R-12 112 Z-R-13 109 Z-R-Z14 112 Z-R-15 113 Z-R-16 110 Z-R-17 109 Z-R-18 100 Z-R-19 78

(101) The colour strength is increased by at least 7%, whereas the use of a hydrophobizing silicone oil in the carbon black paste even results in marked worsening of the colourability of a PU foam, which can already be seen from the high paste viscosity.

(102) V6: Surface Modification of Flame Retardants in the Extrusion/Compounding of Unmodified Particles with the Special Alkoxylated Siloxanes

(103) Using a Leistritz extruder 27 mm (double screw extruder from Leistritz) the following flame retardant compound formula was produced at 200 rpm according to the following composition.

(104) TABLE-US-00019 Ingredients Mass [g] Escorene UL 00328 23.05 Exxon LLDPE 1004 YP 11.35 Non surface-treated particles (MDH) 61.4 Fusabond MB226 4 Irganox 1010 0.2 Additive 1.0 (Compound of the formula (I))

(105) The composition Z-MDHB-18 is based on a composition of the above table without addition of the additive.

(106) TABLE-US-00020 Example MDH MFI Z-MDHB-1 7.96 Z-MDHB-2 7.59 Z-MDHB-3 7.59 Z-MDHB-4 7.85 Z-MDHB-5 7.58 Z-MDHB-6 7.77 Z-MDHB-7 7.95 Z-MDHB-8 7.82 Z-MDHB-9 7.58 Z-MDHB-10 7.99 Z-MDHB-11 7.91 Z-MDHB-12 7.68 Z-MDHB-13 7.54 Z-MDHB-14 7.87 Z-MDHB-15 8.01 Z-MDHB-16 7.55 Z-MDHB-17 7.68 Z-MDHB-18 6.72
V7: Surface Treatment of Pigments in the Masterbatch Extrusion as a Method, e.g. for Pigments

(107) The mixtures are processed in a twin-screw extruder from Leistritz (Model: Micro 27 GL 40D) at 200 rpm

(108) The pigment preparations were produced by premixing the individual components in the premix according to the formulation shown below:

(109) TABLE-US-00021 Masterbatch 1 Masterbatch 2 Polypropylene Homopolymer 56 g 56 g MFI = 55 (230° C./2.16 kg) (PPH 11012, Total) Pigment blue 57:1 40 g (Heliogen Blue D 6902, BASF) Pigment red 202 40 g (Cromophtal ® Magenta P, BASF) Additive  4 g  4 g (Compound of the formula (I))
Testing of the Dispersibility of Surface-Treated Particles
E2: Testing of the Masterbatches in the Pressure Filter Test

(110) The determination of the pressure filter value was performed with the single screw Brabender Plasti-Corder LAB Station (screw diameter/length: 30 mm/25D). A screen packet from GKD with a PZ-Microdur 10 (filter fineness 9 μm) and a supporting fabric with 315 μm mesh width was used. The extruder was heated to a temperature of 200° C. The temperature of the filter equipment was adjusted to 230° C. After thorough flushing of the extruder with LDPE, the filter holder with the screen pack was incorporated. After charging of the masterbatch pellets to be tested and emergence of the pigmented material at the bypass, the melt stream was passed through the screen pack and the computer-assisted measurement data capture started. The measurement data were recorded up to the attainment of a maximal pressure of 150 bar or else in case of a small pressure increase up to a duration of 60 minutes. The throughput was 40 g/min.

(111) The measure of the dispersion quality is the pressure filter value (PFV), which is calculated according to the following formula:

(112) $\mathrm{DF}=\frac{\left(p_{\max }-p_0\right)\times F\times 100}{\left(t\times K\times G\right)}\left[\mathrm{bar}\times {\mathrm{cm}}^2\text{/}g\right]$
p.sub.max: Final pressure [bar]
p.sub.0: Initial pressure [bar]
F: Filter area=6.16 cm.sup.2
t: Measurement time [mins]
K: Concentration [wt. %] of pigment based on total composition
G Throughput [g/min]

(113) Pressure filter values of Masterbatch 1 (Heliogen Blue, D6911)

(114) TABLE-US-00022 Example Pressure filter value Z-HB-1 0.99 Z-HB-2 1.29 Z-HB-3 1.34 Z-HB-4 0.89 Z-HB-5 1.27 Z-HB-6 1.56 Z-HB-7 1.49 Z-HB-8 1.22 Z-HB-9 0.97 Z-HB-10 0.89 Z-HB-11 1.11 Z-HB-12 1.01 Z-HB-13 1.43 Z-HB-14 1.29 Z-HB-15 1.53 Z-HB-16 1.33 Z-HB-17 1.09 Z-HB-18 3.4

(115) The lower the pressure filter value, the better is the dispersion of the pigment in the polymer. Pressure filter values ≧2 bar*cm.sup.2/g indicate inadequate dispersibility.

(116) Testing of Dispersion Quality by Determination of the Colour Strength in the Injection Moulded Part

(117) In order to assess the dispersion quality of the masterbatches produced, 300 g of the aforesaid polypropylene are mixed with 8.6 g of a white masterbatch (70% TiO.sub.2 content) and 3 g of the pigment masterbatch and plates of 6 cm×6 cm×0.2 cm size produced by injection moulding (Engel Germany) and then assessed by colorimetry according to the CIE Lab colour system. The higher the colour strength compared to a reference sample, the better is the distribution of the pigment, and the lower the agglomerate content in the original colour masterbatch. For the comparison, the colour strength of the reference samples is by definition taken to be 100%. The reference sample Z-HB2-18 was produced with no additive.

(118) TABLE-US-00023 Example Colour strength [%] Z-HB2-1 112 Z-HB2-2 118 Z-HB2-3 112 Z-HB2-4 114 Z-HB2-5 110 Z-HB2-6 116 Z-HB2-7 115 Z-HB2-8 118 Z-HB2-9 112 Z-HB2-10 117 Z-HB2-11 123 Z-HB2-12 121 Z-HB2-13 118 Z-HB2-14 110 Z-HB2-15 113 Z-HB2-16 115 Z-HB2-17 110 Z-HB2-18 100

(119) From the values in the above table, it can be seen that the colour strengths have increased by at least 10% due to the additives of the formula (I).

(120) Testing of the Masterbatch in Polymer Flat Films:

(121) The masterbatches in the above table were extruded into films by the following process. For this, the masterbatches were diluted with LDPE pellets (polymer PP 11012 powder) to a concentration of 10 wt. % pigment. For this, masterbatch and polymer pellets were placed in a plastic bag and shaken by hand for 0.5 mins. After this, from the mixtures, by means of a single screw extruder Brabender Plasti-Corder LAB Station (screw diameter/length: 30 mm/25D) films were produced with a film blowing machine. The film strand was drawn off via a conveyer belt, cooled and rolled up.

(122) 5 pieces about 50 cm long from the film strand were inspected (10 cm wide and 150 micrometers thick). The assessment of the number of undispersed agglomerates was made in transmitted light. In this, the size of the specks, which consist of incompletely dispersed agglomerates, had no influence on the rating.

(123) The results were rated using a five point system, the ratings meaning as follows: 1. no or max. 1 speck per piece, 2. isolated specks (2-3 specks per piece), 3. moderate number (4-6 specks per piece), 4. many specks, and 5. very many specks (>10 specks). At the end, the 5 pieces assessed are combined to give a whole number or if necessary the score for example stated as 1.5, if the number of foil specks would permit a rating of 1 or 2.

(124) TABLE-US-00024 Example Rating Z-F-1 1.5 Z-F-2 1.5 Z-F-3 1.5 Z-F-4 1.5 Z-F-5 2 Z-F-6 2 Z-F-7 1.5 Z-F-8 2 Z-F-9 1.5 Z-F-10 2 Z-F-11 2 Z-F-12 1.5 Z-F-13 2 Z-F-14 2 Z-F-Z15 2 Z-F-16 1.5 Z-F-17 1.5 Z-F-18 5
Testing in Unsaturated Polyester Resins Filled with Flame Retardant (UPES According to Römpp)

(125) In accordance with the following formula, the components were mixed in the dissolver and dispersed for 10 mins at 3,000 rpm in a disperser vessel, where the dispermat disc has ⅔ of the diameter of the vessel

(126) TABLE-US-00025 Ingredients Function Formula 1 [g] Distitron 416B1V12 Polyester resin 35.0 (Polynt/Italy) Apyral 24 Aluminium hydroxide 65.0 (Nabaltec AG, Germany) Butanox M 50 Curing agent 1.0 (Akzo Nobel) Accelerator NL 49 P Accelerator 0.3 (Akzo Nobel) Additive 0.5 Compounds of the formula (I)

(127) The resulting mixtures are cast in moulds in order to obtain shouldered rods in accordance with DIN ISO 527-2 type 5A rods.

(128) The tensile strength test was performed with a tensile tester from Zwick (23° C., 50% rel. atmospheric humidity). The machine parameters were: initial load=20 N, speed up to initial load=1 mm/min, test speed=5 mm/min, clamping length=55 mm and measurement length of the incremental pick-up=25 mm.

(129) In addition, 6 cm×6 cm plates, of 2 mm layer thickness are cast, and then used as test pieces for scratch resistance, and where the brightness value is determined before and after scratching in order to obtain the scratch resistance as a delta L value.

(130) The scratch resistance testing is performed in accordance with GMW 14688 Section A. As the testing instrument, a Scratch Hardness Tester 430 P from Erichsen, Hemer is used. A 6×6 cm test plate is clamped into the instrument. Using a test point which has a 1.0 mm diameter ball, 40 mm long scratches with a spacing of 2 mm are scratched into the plate at a speed of 1000 mm/min. After 20 scratches, the plate is turned through 90° and 20 scratches are again made. The resulting grid is used for assessment of the scratch resistance.

(131) For the metrological assessment of the scratch resistance, the plate is assessed by colorimetry with a spectrophotometer (SP 62, X-Rite) before clamping into the instrument. After the test, a second measurement is performed. In each case the brightness value (L*) is measured and the difference between the two L values used as the delta L value for the assessment.

(132) The lower the resulting delta L value, the better is the scratch resistance.

(133) The composition Z-UPES-18 is based on a composition which contained no compound of the formula (I).

(134) TABLE-US-00026 Elongation Example Scratch resistance Tensile strength at break UPES-ATH Delta L σ.sub.M [MPa] εtB [%] Z-UPES-1 1.43 24.6 6.8 Z-UPES-2 1.28 24.8 7.2 Z-UPES-3 0.79 24.9 6.8 Z-UPES-4 0.58 24.3 7.9 Z-UPES-5 0.89 24.5 8.1 Z-UPES-6 1.23 24.6 7.5 Z-UPES-7 1.45 24.5 8.9 Z-UPES-8 1.21 25.1 7.7 Z-UPES-9 1.09 25.3 7.9 Z-UPES-10 0.89 25.6 8.1 Z-UPES-11 0.97 25.7 8.5 Z-UPES-12 0.96 25.8 7.6 Z-UPES-13 0.95 24.9 8.1 Z-UPES-14 0.94 26.1 8.0 Z-UPES-15 1.22 26.0 7.5 Z-UPES-16 1.09 25.0 7.2 Z-UPES-17 1.06 24.8 7.9 Z-UPES-18 2.08 24.1 5.1
(Null Sample)

(135) The values show the marked improvement in the scratch resistance of the compositions according to the invention.