SURFACE TREATMENT OF PARTICLES AND THEIR USE

Abstract

Surface treatment of titanium dioxide, barium sulfate, zinc sulfide, and/or lithopone particles, and mixtures of said particles with specific alkoxylated siloxanes for the improvement of dispersion in plastics.

Claims

1. A surface-treated particle obtained by a process for treating a surface of a primary particle, comprising contacting the primary particle at least one 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 moiety of formula (III)
Z(OC.sub.mH.sub.2m-(n-1)).sub.o[O-(AO)R.sup.3].sub.n (III) where Z is a branched alkylene moiety or an unbranched alkylene moiety having from 2 to 4 carbon atoms, m is from 2 to 4, n is from 1 to 3, o is 0 or 1, AO identically or differently is an oxyalkylene moiety comprising an oxyethylene moiety, an oxypropylene moiety, and/or an oxybutylene moiety moieties, R.sup.3 identically or differently is hydrogen or an alkyl moiety having from 1 to 4 carbon atoms, with the proviso that in R.sup.1 a total number of carbon atoms and oxygen atoms is at least 70, a is from 20 to 200, b is from 1 to 50, with the proviso that if none of moieties R is R.sup.1, b is at least 3, where 0.01 to 2% by weight of the compound of the formula (I) is contacted with the primary particle, based on a mass of the primary particle to be treated, wherein the surface-treated particle is a TiO.sub.2 particle, a BaSO.sub.4 particle, a ZnS particle, and/or a lithopone particle.

2. The particle as claimed in claim 1, wherein R.sup.1 identically or differently is (CH.sub.2).sub.pO-EO.sub.xPO.sub.yBO.sub.zR.sup.3, with the proviso that in R.sup.1 the total number of carbon atoms and oxygen atoms is at least 70, 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.

3. The particle as claimed in claim 1, wherein a numeric ratio of a to b is from 8:1 to 18:1.

4. The particle as claimed in claim 2, index wherein x is between 0.05 and 1.2 times a sum of y and z.

5. The particle as claimed in claim 2, wherein R is methyl, A is from 80 to 95, B is from 5 to 8, R.sup.3 is hydrogen, x is from 3 to 5, y is from 10 to 25, z is 0.

6. The particle as claimed in claim 1, which is a surface-treated is TiO.sub.2 particle.

7. The particle as claimed in claim 1, which has a dust value of at most 80 mg per 100 g of surface-treated particles.

8. 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 moiety of formula (III)
Z(OC.sub.mH.sub.2m-(n-1)).sub.o[O-(AO)R.sup.3].sub.n (III) where Z is a branched alkylene moiety or an unbranched alkylene moiety having from 2 to 4 carbon atoms, m is from 2 to 4, n is from 1 to 3, o is 0 or 1, AO identically or differently is an oxyalkylene moiety comprising an oxyethylene moiety, an oxypropylene moiety, and/or an oxybutylene moiety, R.sup.3 identically or differently is hydrogen or an alkyl moiety having from 1 to 4 carbon atoms, with the proviso that in R.sup.1 a total number of carbon atoms and oxygen atoms is at least 70, a is from 20 to 200, b is from 1 to 50, with the proviso that if none of moieties R.sup.1, b is at least 3, where 0.01 to 2% by weight of the compound of the formula (I) is contacted with the primary particle, based on a mass of the primary particle to be treated, wherein the primary particle is a TiO.sub.2 particle, a BaSO.sub.4 particle, a ZnS particle, and/or a lithopone particle.

9. A process for producing a polymer composition, comprising mixing the particle of claim 1 with a polymer.

10. The process as claimed in claim 9, wherein the polymer composition is processed to give a plastic molding or a plastic film.

11. A composition, comprising a polymer, which comprises a particle as claimed in claim 1.

12. The composition as claimed in claim 11, wherein the polymer is a thermoset or thermoplastic.

13. The composition as claimed in claim 11, which is a masterbatch, a plastic molding, or a plastic film.

14. The particle of claim 2, which is a surface-treated TiO.sub.2 particle.

15. The particle of claim 1, wherein Z is a branched alkylene moiety or an unbranched alkylene moiety comprising 3 carbon atoms, m is 3, n is 1 or 2, o is 0, a is from 30 to 170, and b is from 2 to 30, where 0.05 to 1% by weight of the compound of the formula (I) is contacted with the primary particle, based on the mass of the primary particles to be treated.

16. The particle as claimed in claim 2, wherein x is from 3 to 15, y is from 8 to 50, and p is 2 or 3

17. The particle as claimed in claim 3, wherein the numeric ratio of a to b is from 9:1 to 15:1.

18. The particle as claimed in claim 4, wherein x is between 0.07 and 0.8 times the sum of y and z.

19. The particle as claimed in claim 7, which has a dust value in a range of 8 to 75 mg per 100 g of surface-treated particles.

20. The process as claimed in claim 8, wherein Z is a branched alkylene moiety or an unbranched alkylene moiety comprising 3 carbon atoms, m is 3 n is 1 or 2, and o is 0.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0146] FIG. 1: The figure shows the principle of the dusting chamber, the mode of functioning of which is described in detail in example 3 in E1. The meanings of the numerals are as follows: 1) Drop box, 2) unlocking lever, 3) glass cylinder, 4) slide, 5) rubber seal, 6) sample tube (packed with quartz wool), 7) +9) wash bottle (packed with quartz wool), 8) vacuum pump, 10) gas meter; the letter G at the outlet of the gas meter indicates the outlet for the gas removed by suction.

[0147] FIG. 2: The figure shows the principle of the measurement cell of the RST-XS ring-shear tester, the mode of functioning of which is described in detail in example 4 in E6. : Rotation of measurement cell, F.sub.1 and F.sub.2: forces for retaining the cover of the measurement cell, F.sub.N: normal force exerted by the cover on the measurement cell.

EXAMPLES

[0148] General Methods and Materials

TABLE-US-00001 Lupolen Purell 1800 SP 15 Low-density Lyondell Basell polyethylene Palapreg P17-02 Polyester resin DSM Palapreg H814-01 Polyester resin DSM TEGOMER DA626 Evonik Industries AG TEGOMER M-Si2650 Evonik Industries AG Trigonox C AkzoNobel Polymers Millicarb OG Omya Coathylene HA 1681 DuPont Dioctyl phthalate (DOP) BASF Methylisothiazolinone Thor Chemie (MIT)

[0149] Viscosity:

[0150] Viscosities were determined by using a Brookfield LV-DV-I+ spindle viscometer. Brookfield viscometers are rotary viscometers with defined spindle sets as rotary bodies. The rotary bodies used were from an LV spindle set. Because the viscosity is temperature-dependent, the temperatures of viscometer and test liquid were kept precisely constant to +/0.5 C. during measurement. Other equipment used in addition to the LV spindle set were a thermostatable water bath, a 0 to 100 C. Thermometer, and a timer (scale values no greater than 0.1 second). For the measurement, 100 ml of the sample were charged to a wide-necked flask; the measurement was made under temperature-controlled conditions and in the absence of air bubbles, after prior calibration. The viscosity determination was carried out by positioning the viscometer in relation to the sample in such a way that the spindle was immersed in the product up to the mark. Measurement is initiated by using the start key, and care was taken here that measurement was made within the advantageous measurement range of 50% (+/20%) of the maximal measurable torque; in other circumstances it was necessary to use an appropriate spindle. The measurement result was displayed in mPas on the viscometer display, whereupon division by the density (g/ml) gives the viscosity in the unit [mm.sup.2/s].

[0151] Spectroscopic Analyses:

[0152] The recording and interpretation of NMR spectra is known to the person skilled in the art. A reference that may be mentioned is the book NMR Spectra of Polymers and Polymer Additives, A. Brandolini and D. Hills, 2000, Marcel Dekker, Inc. The spectra were recorded by using a Bruker Spectrospin spectrometer at room temperature, the measurement frequency being 399.9 MHz for recording the proton spectra, 100.6 MHz for recording the .sup.13C spectra, and 79.5 MHz when recording the .sup.29Si spectra.

[0153] Determination of molar masses, in particular of weight-average molar masses Mw:

[0154] The gel permeation chromatographic analyses (GPC) were carried out by using a Hewlett-Packard 1100 instrument, using an SDV column combination (1000/10000 , each 65 cm, internal diameter 0.8 cm, temperature 30 C.), THF as mobile phase with flow rate 1 ml/min and RI detector (Hewlett-Packard). The system was calibrated against a polystyrene standard in the range from 162 to 2 520 000 g/mol.

[0155] Determination of SiH Content:

[0156] The SiH values of the hydrogen siloxanes used, and also those of the reaction matrices, are determined in each case using a gas volumetric method by the butanolate-induced decomposition of weighed aliquots of samples, using a gas burette. When the hydrogen volumes measured are inserted into the general gas equation, they allow determination of content of active SiH functions in the starting materials, and also in the reaction mixtures, and thus allow monitoring of conversion. A 5% by weight sodium butanolate solution was used.

Example 1

Synthesis

[0157] The polyethers used (table 1, PE) have, at the chain ends, respectively an allyl ether (PE1-PE8) or vinyl ether function (PE9) and a hydroxy group (PE1-PE9), and are characterized by different mass contents of oxyethylene, oxypropylene, and oxybutylene (EO/PO/BO mass contents, based on the polyether moiety without allyl/vinyl group) and molar masses (Mw). The vinyl polyether PE9 has an oxybutylene moiety as fragment with the index o according to formula (III), in this case O(CH.sub.2).sub.4.

[0158] Glycerol monoallyl ether, used in the polyether PE10, and trimethylolpropane monoallyl ether, used in the polyether PE11.

TABLE-US-00002 TABLE 1 Composition of the polyethers used PO EO BO Mw Polyether [% by wt.] [% by wt.] [% by wt.] [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

[0159] The hydrosiloxanes used (table 2, SiH), are characterized by different SiH contents and viscosities.

TABLE-US-00003 TABLE 2 Properties of the hydrosiloxanes used SiH content, Viscosity, 25 C., Hydrosiloxane [mmol/g] [mPa*s] SH1 2.29 116 SH2 0.90 159 SH3 1.40 61 SH4 3.52 101

[0160] The polyether-modified siloxanes (table 3, O) were produced by means of hydrosilylation by the following process.

[0161] The hydrosiloxane SiH used and the hydroxy-functional terminally unsaturated PE used were charged in a ratio of 1.35 mol of allyl/vinyl polyether per molar equivalent of SiH in a 500 ml four-necked flask with stirrer with precision glass gland, reflux condenser, and internal thermometer, and heated to 70 C., with stirring. 5 ppm of platinum in the form of Pt.sub.2(divinyltetramethyldisiloxane).sub.3 complex (Karstedt catalyst, 1.5% Pt in deca-methylcyclopentasiloxane) were added with a syringe. Conversion determined by a gas volumetric method was quantitative within from 1 to 3 hours of continued reaction time at from 70-80 C. Filtration gave clear, viscous liquids of yellow-brownish color.

TABLE-US-00004 TABLE 3 Siloxanes produced as in example 1; the mixture cited in O13 is an equimolar mixture of the polyethers listed Example Hydrosiloxane 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

[0162] 185 g of O12 were added within 20 minutes with cooling, under conditions of shear (Mizer disc, 2000 rpm) to an emulsifier solution made of 40 g of an ethoxylated stearic acid with HLB value of about 18.8 and 60 g of demineralized water. The mixture was then subjected to shear for a further 20 minutes. This gave a paste with increased viscosity. 214 g of demineralized water were then added within 10 minutes under conditions of shear. This gave a white emulsion with about 45% by weight solids content. Finally 0.15% of an aqueous solution of 20% by weight of methylisothiazolinone (MIT) was added to preserve the emulsion.

Example 3

Surface Treatment of Particles

[0163] V1: Dry-Phase Treatment of TiO.sub.2 Particles

[0164] Starting material for the dry surface treatment of titanium dioxide with polyethersiloxanes was a TiO.sub.2 in rutile form with an inorganic modification system made of silicon oxide and aluminum oxide. The quantity stated in table 4 of polyethersiloxane (surface treatment agent) was admixed with said powder, and the mixture was homogenized for 60 seconds in a LOdige mixer. The polyethersiloxane-wetted TiO.sub.2 was then dry-milled in a steam-jet mill using steam at 18 bar. The milling can alternatively be achieved by means of a pin mill, air-jet mill, roll mill, or tubular ball mill.

[0165] V2: Liquid-Phase Treatment of TiO.sub.2 Particles

[0166] Starting material for the wet surface treatment of TiO.sub.2 with polyethersiloxanes was a TiO.sub.2 filter cake after inorganic modification, where the TiO.sub.2 was in the rutile modification, and the inorganic modification system was made of silicon dioxide and aluminum oxide. Said filter cake was redispersed in water by means of a dissolver, and the quantity stated in table 4 of polyethersiloxane emulsion as in example 2 was added to the suspension. Said suspension was spray-dried, and then the spray-dried grains were dry-milled with the aid of a steam-jet mill using steam at 18 bar.

[0167] V3: Dry-Phase Treatment of BaSO.sub.4 Particles

[0168] Starting material for the dry surface treatment of barium sulfate with polyethersiloxanes was a barium sulfate precipitated by a chemical reaction in the liquid phase (known as blanc fixe) which had not yet been dry-milled, i.e. by way of example steam-jet-milled. The quantity stated in table 4 of polyethersiloxane was admixed with said powder, and the mixture was homogenized for 60 seconds in a Lodige mixer. The polyethersiloxane-wetted BaSO.sub.4 was then dry-milled in a steam-jet mill using steam at 10 bar. The milling can alternatively be achieved by means of a pin mill, air-jet mill, roll mill, or tubular ball mill.

[0169] V4: Dry-Phase Treatment of ZnS Particles

[0170] Starting material for the dry surface treatment of zinc sulfide with polyethersiloxanes was a zinc sulfide precipitated by a chemical reaction in the liquid phase (known as Sachtolith) which had not yet been dry-milled, i.e. by way of example steam-jet-milled. The quantity stated in table 4 of polyethersiloxane was admixed with said powder, and the mixture was homogenized for 60 seconds in a Lodige mixer. The polyethersiloxane-wetted ZnS was then dry-milled in a steam-jet mill using steam at 10 bar. The milling can alternatively be achieved by means of a pin mill, air-jet mill, roll mill, or tubular ball mill.

[0171] V5: Dry-Phase Treatment of Lithopone Particles

[0172] Starting material for the dry surface treatment of lithopone with polyethersiloxanes was lithopone which had been produced by coprecipitation of BaSO.sub.4 and ZnS in a chemical reaction from a liquid phase, and which had not yet been dry-milled, i.e. by way of example steam-jet-milled. The quantity stated in table 4 of polyethersiloxane was admixed with said powder, and the mixture was homogenized for 60 seconds in a Ldige mixer. The polyethersiloxane-wetted lithopone was then dry-milled in a steam-jet mill using steam at 10 bar. The milling can alternatively be achieved by means of a pin mill, air-jet mill, roll mill, or tubular ball mill.

[0173] The particles P4, P7, P8, P9, P16, P18, P20, P21, P23, P24, P25, P26, P27, and P31 listed in table 4 are not of the invention. P25A are titanium dioxide particles with inorganic posttreatment which have been steam-jet-treated, without any organic surface treatment or surface treatment of the invention. P25B are titanium dioxide particles with inorganic posttreatment which have been steam-jet-treated, with silicone oil surface treatment. P26 are commercially available rutile pigments for plastics applications, produced by the sulfate process, source: Europe

TABLE-US-00005 TABLE 4 TiO.sub.2, BaSO.sub.4, ZnS, and lithopone particles which were surface-treated by the processes of example 3, AS: commercial alkylsiloxane from Evonik Industries AG TMP: trimethylolpropane from BASF Quantity: % by weight of treatment agent, based on mass of particles without surface treatment of the invention. Surface- Particle Method treatment agent Quantity P1 V1 O1 0.42 P2 V1 O2 0.43 P3 V1 O3 0.46 P4 V1 O4 0.34 P5 V1 O5 0.42 P6 V1 O6 0.42 P7 V1 O7 0.44 P8 V1 O8 0.44 P9 V1 O9 0.48 P10 V1 O10 0.46 P11 V1 O11 0.42 P12A V1 O12 0.40 P12B V1 O12 0.20 P12C V1 O12 0.80 P13 V1 O13 0.42 P14 V2 O3 0.40 P15 V2 O5 0.40 P16 V2 O7 0.43 P17 V3 O12 0.42 P18 V3 TMP 0.35 P19 V4 O12 0.45 P20 V4 AS 0.45 P21 V4 TMP 0.35 P22 V5 O12 0.42 P23 V5 AS 0.45 P24 V5 TMP 0.35 P25A none 0 P25B V1 silicone oil 0.41 P26 silicone oil 0.4 to 0.5 P27 V1 AS 0.40 P28 V1 O14 0.40 P29 V1 O15 0.40 P30 V1 O16 0.40 P31 V1 O17 0.40

Example 4

Determination of Properties of the Surface-Treated Particles

[0174] E1: Determination of Dusting:

[0175] 100 g of the substance to be tested was weighed into the drop box 1) in an apparatus as shown in FIG. 1. The drop box was locked by using the lever 2), and suspended in the glass cylinder 3) (height 800 mm, diameter 150 mm). Quartz wool was charged to the sample tube 6), which was weighed and inserted into the glass cylinder 3). One end of the sample tube 6) was sealed by way of the slide 4). The other end was connected by way of a wash bottle 7) filled with quartz wool via a vacuum hose to a vacuum pump 8). A gas meter was attached by way of another safety bottle 9) filled with quartz wool.

[0176] The drop box 2) was unlocked. The sample dropped into the glass cylinder, and dusting occurred. Ten seconds after the unlocking procedure, the rubber seal 5) was removed from the inlet of the sample tube by means of the slide 4). The drop box is carefully removed. 20 sec. after opening of the slide, the vacuum pump was started, and precisely 20 l of air were sucked through the glass cylinder, the top of which was open. The performance of the vacuum pump was 10 l/min. Once the vacuum pump had been switched off, the weighed sample tube 6) was removed, and again weighed. The weight difference in [mg/100 g] of powder has been stated as measure of dusting. The determination used two measurements. Table 5 states the average values of said measurements.

TABLE-US-00006 TABLE 5 Determination of dusting in example 4 for the surface-treated particles from example 3 Mass of dust Particle [mg/100 g] P1 33 P2 29 P3 46 P4 120 P5 68 P6 59 P7 95 P8 86 P9 86 P10 37 P11 46 P12A 61 P12B 36 P12C 75 P13 45 P14 51 P15 63 P16 77 P17 8 P18 84 P19 45 P20 96 P21 89 P22 17 P23 88 P24 95 P25A 12 P25B 87 P26 95 P27 98 P28 14 P29 45 P30 29 P31 76

[0177] The dust mass for the particles not of the invention is more than 80 mg/100 g.

[0178] E6: Powder-Flowability

[0179] Powder-flowability is determined by using an RST-XS ring-shear tester. The sample of flowable solid is charged to the measurement cell and loaded from above, by way of a cover, with a force (normal force) of 3.5 kPa. During the measurement the shear cell rotates slowly (). Two tension rods prevent rotation of the cover. This results in a shear deformation of the sample of flowable solid. The force required (F.sub.1 and F.sub.2) is measured. The flowability ff.sub.c of the flowable solid is determined from the ratio of consolidation stress .sub.1 to yield strength .sub.c.

[0180] Table 6 shows the measurement results.

[0181] The greater the flowability ff.sub.c, the better the flow of the flowable solid. The following ranges of different flowability are defined (D. Schulze, Pulver and Schttgter [Powders and flowable solids], Springer, 2006, chapter 3.1.4, p. 42):

[0182] ff.sub.c smaller than or equal to 1, non-flowing, hardens

[0183] ff.sub.c greater than 1 and less than or equal to 2, very cohesive (to non-flowing)

[0184] ff.sub.c greater than 2 and less than or equal to 4, cohesive

[0185] ff.sub.c greater than 4 and less than or equal to 10, slightly flowing

[0186] ff.sub.c greater than 10, free-flowing.

TABLE-US-00007 TABLE 6 Powder-flowability ff.sub.c as in example 4 of the surface-treated particles from example 3 Particle ff.sub.c P1 1.9 P2 1.8 P3 1.8 P4 1.3 P5 1.9 P6 1.7 P7 1.2 P8 1.1 P9 1.3 P10 1.8 P11 1.7 P12A 1.9 P12B 1.7 P12C 2.2 P13 1.7 P14 1.6 P15 1.8 P16 1.5 P17 2.3 P18 1.4 P19 1.9 P20 1.3 P21 1.4 P22 1.7 P23 1.3 P24 1.5 P25A 1.0 P25B 1.4 P26 1.3 P27 1.4 P28 2.0 P29 1.8 P30 1.6 P31 1.5

[0187] The powder-flowability of the particles not of the invention is less than or equal to 1.5.

Example 5

Compositions

[0188] Z1: Masterbatches

[0189] The compositions with thermoplastics are also termed masterbatches. These masterbatches can be produced as specified below.

[0190] A dryblend was first produced from the surface-treated particles to be studied and polyethylene as example of a thermoplastic (LDPE: Lupolen Purell 1800 SP 15) in a concentration of 50% by weight, by weighing both components into a plastics bottle and then mixing for 15 min on a roller jar rolling mill. The resultant dryblend was then charged to the Brabender feed unit, and introduced by way of a conveying screw to the Leistritz DS ZSE 18HP twin-screw extruder for processing. The processing to give the masterbatch used a rotation rate of 150 revolutions per minute (rpm) and a temperature setting of 150 C. in all zones. The polymer strand was pelletized. This specification was used to produce the compositions Z1-P1 to Z1-P27.

[0191] Z2: White Paste

[0192] White pastes were produced as example of compositions with plasticizers.

[0193] 90 g of dioctyl phthalate (DOP) were weighed into a 250 ml dissolver vessel. 167 g of the surface-treated particles were incorporated in portions within 3 min, with gentle stirring by a 3 cm dissolver disk (about 5 m/sec). The rotation rate of the dissolver was increased to 12 500 rpm, and the mixture was dispersed for five min.

[0194] This specification was used to produce the compositions Z2-P1 to Z2-P27.

[0195] Z3: Thermoset Compositions

[0196] a: Concentrate paste: A dissolver was used to predisperse the pigments in the carrier resin (an unsaturated polyester resin; SMC). The concentration of the pigments in the paste was 70% by weight. Fine dispersion was achieved by way of a bead mill (1 h batchwise, 2 mm glass beads). The viscosity of the paste was about 0.6 Pa*s.

[0197] The compositions Z3a-P27 and Z3a-P12A were produced.

[0198] b: Semifinished products: The formulation constituents corresponding to table 7 were mixed by using a dissolver. The paste viscosity was in the range from 3 to 20 Pa*s.

TABLE-US-00008 TABLE 7 Compositions of the pastes for the production of semifinished products; the values stated are the parts by weight, the sum of which was more than 100; Z3b-P27 is not of the invention Component Function Z3b-P27 Z3D-P12 Palapreg P17-02 Polyester resin 70.0 70.0 Palapreg H814-01 Polyester resin 30.0 30.0 TEGOMER DA626 Dispersing additive 1.5 1.5 TEGOMER M-Si2650 Process additive 2.0 2.0 Trigonox C Initiator 1.5 1.5 Millicarb OG Calcium carbonate 170.0 170.0 Coathylene HA 1681 Release agent 5.0 5.0 P12A Particle 0 8.5 P27 Particle 8.5 0

[0199] The semifinished products were produced by processing these resin systems together with 25% of glass fibers (Vetrotex P204 2400 tex) to give prepregs.

[0200] Processing parameters for press: temperature=150 to 155 C., pressure=about 80 bar (1000 kN), time=150 to 180 sec, closure velocity=8 mm/s.

Example 6

Dispersibility Testing of Surface-Treated Particles

[0201] E2: Pressure Filter Test on Masterbatches

[0202] The pressure filter value was determined by using the Brabender Plasti-Corder Lab-Station single-screw extruder (screw diameter/screw length: 30 mm/25D). A screen pack from GKD with a PZ-Microdur 14 (filter fineness 14 m) and a supporting fabric with 315 m mesh width was used. The extruder was heated to a temperature of 200 C. The temperature of the filter equipment was set 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 discharge of the pigmented material at the bypass, the melt stream was passed through the screen pack, and computer-assisted capture of measured data was begun. The measured data were recorded until a maximal pressure of 150 bar was reached, or else if the pressure rise was small until a duration of 60 minutes was registered. Throughput was 40 g/min.

[0203] Table 8 shows the measurement results.

[0204] The measure of dispersion quality is the pressure filter value (PFV), calculated from the following formula:

[00001]$\mathrm{PFV}=\frac{\left(p_{\max }-p_0\right)F100}{\left(tKG\right)}.Math.\left[\mathrm{bar}{\mathrm{cm}}^2/g\right]$

[0205] P.sub.max: final pressure [bar]

[0206] p.sub.0: initial pressure [bar]

[0207] F: filter area=6.16 cm.sup.2

[0208] t: measured time [min]

[0209] K: pigment concentration [% by weight], based on entire composition

[0210] g throughput [g/min]

TABLE-US-00009 TABLE 8 Pressure filter values as in example 6 (E2) for compositions from example 5 (Z1) Pressure filter value Compositions [bar * cm.sup.2/g] Z1-P1 0.39 Z1-P2 0.48 Z1-P3 0.93 Z1-P4 1.65 Z1-P5 0.41 Z1-P6 0.88 Z1-P7 2.49 Z1-P8 3.90 Z1-P9 2.77 Z1-P10 0.33 Z1-P11 0.40 Z1-P12A 0.20 Z1-P12B 0.67 Z1-P12C 0.13 Z1-P13 0.89 Z1-P14 0.44 Z1-P15 0.38 Z1-P16 0.63 Z1-P17 0.82 Z1-P18 1.65 Z1-P19 0.65 Z1-P20 1.79 Z1-P21 4.23 Z1-P22 0.38 Z1-P23 1.10 Z1-P24 5.33 Z1-P25A 6.55 Z1-P25B 3.70 Z1-P26 2.38 Z1-P27 1.06 Z1-P28 0.45 Z1-P29 0.87 Z1-P30 1.79 Z1-P31 1.91

[0211] The lower the pressure filter value, the better the dispersion of the pigment in the polymer. Pressure filter values1 bar*cm.sup.2/g indicate lack of dispersibility.

[0212] E3: Testing of Masterbatches in Flat Polymer Films:

[0213] The masterbatches from example 5 (Z1) were extruded by the following process to give films. For this, the masterbatches were diluted with LDPE pellets (Purell PE 3020H) to a concentration of 10% by weight of pigment. To this end, masterbatch and polymer pellets were charged to a plastics bottle and shaken by hand for half a minute. The sample was then extruded in the Brabender Plasti-Corder Lab-Station (screw diameter/screw length: 30 mm/25D) at 15 rpm at a temperature of 190 C. A film of width about 8 cm was discharged by way of a slot die. The film was drawn off by way of a conveyer belt, cooled, and wound to give a roll.

[0214] 5 pieces of length about 50 cm from the film were subjected to assessment. The assessment was made in transmitted light in respect of the number of undispersed agglomerates at two different magnifications (0 times: no magnification; 30 times: magnification by a factor of 30). The size of the specks of undispersed material, consisting of incompletely dispersed agglomerates, had no effect on the grade allocated here.

[0215] The results were allocated grades within a five-level system, where grade 1 indicates no specks of undispersed material, grade 2 indicates a few specks of undispersed material (there being test areas with from 1 to 2 specks of undispersed material but also test areas with no specks of undispersed material), grade 3 indicates a moderate number of specks of undispersed material (all of the test areas having specks of undispersed material, on average less than 5 per test area), grade 4 indicates a large number of specks of undispersed material (all test areas having from 5 to 10 specks of undispersed material), and grade 5 indicating a very large number of specks of undispersed material (all test areas on average having at least 10 specks of undispersed material).

[0216] The values in table 9 are obtained as grade from the evaluation of 5 test areas.

[0217] At grade 3 and above, the masterbatches are unsuitable for the productin of films. Initial assessment was carried out here without magnification.

TABLE-US-00010 TABLE 9 Allocation of grades to the test areas from example 6 (E3) on the basis of compositions from example 5 (Z1) With magnification by a Compositions Without magnification factor of 30 Z1-P1 1.5 2.5 Z1-P2 1.5 2.5 Z1-P3 2 3 Z1-P4 1.5 2.5 Z1-P5 1.5 2.5 Z1-P6 1.5 2.5 Z1-P7 2.5 3 Z1-P8 1.5 2.5 Z1-P9 2.5 3.5 Z1-P10 2.5 4 Z1-P11 2.5 3.5 Z1-P12A 2 3 Z1-P12B 2.5 3 Z1-P12C 1.5 2 Z1-P13 1 2.5 Z1-P14 1.5 2.5 Z1-P15 1 1 Z1-P16 1 1 Z1-P17 1.5 1.5 Z1-P18 2 2 Z1-P19 1.5 2 Z1-P20 2 2.5 Z1-P21 3.5 4 Z1-P22 1.5 1.5 Z1-P23 2.5 3 Z1-P24 3.5 4 Z1-P25A 4 4 Z1-P25B 2 2.5 Z1-P26 1.5 2.5 Z1-P27 2 2

[0218] E4: Testing in Plasticizers

[0219] 3 g of the white pastes produced as in example 5 (Z2) were thoroughly mixed with a spatula in a plastics beaker with the same quantity of DOP. For fineness determination, the diluted paste was drawn on a Hegman block (grindometer), first on the 0 to 100 m Hegman block and then, in the case of appropriately fine samples, on the 0 to 25 m Hegman block (Erichsen). The fineness values determined visually in m were recorded and are shown in table 10.

[0220] Fineness greater than 20 m indicates inadequate dispersion.

TABLE-US-00011 TABLE 10 Determination of fineness as in example 6 (E4) of compositions from example 5 (Z2) Fineness Compositions [m] Z2-P1 15 Z2-P2 13 Z2-P3 50 Z2-P4 30 Z2-P5 20 Z2-P6 15 Z2-P7 22 Z2-P8 24 Z2-P9 65 Z2-P10 12 Z2-P11 18 Z2-P12A 17 Z2-P12B 19 Z2-P12C 16 Z2-P13 19 Z2-P14 15 Z2-P15 16 Z2-P16 17 Z2-P17 19 Z2-P18 22 Z2-P19 8 Z2-P20 26 Z2-P21 >100 Z2-P22 9 Z2-P23 >100 Z2-P24 >100 Z2-P25A >100 Z2-P25B 50 Z2-P26 22 Z2-P27 35 Not measurable: >100

[0221] E5: Properties of the Semifinished Products from Example 5 (Z3b)

[0222] Test samples were sawn from the semifinished product. A template was used to saw a piece with the following dimensions from the middle of the prepreg, perpendicularly to the direction of travel of the prepreg: 27 cm38 cm. The thickness of the sheet was 4 mm.

[0223] For the subsequent mechanical tests, strips of width 10 cm were cut from the test samples, transversely with respect to the direction of travel of the prepreg. For the impact resistance test, test samples of length 80 mm were sawn from the material. The length of the test samples for the tensile tests was 170 mm. All of the test samples were rinsed with mains water, dried with a cloth, and stored for at least 24 h in a cabinet under controlled conditions of temperature and humidity.

[0224] Tensile strength was tested with a tensile tester from Frank/Zwick (23 C., 50% rel. humidity). The machine parameters were: initial load=20 N, velocity up to initial load=1 mm/min, test velocity=5 mm/min, clamping length=120 mm, and measurement length of incremental pick-up=80 mm.

[0225] Impact Resistance (Charpy):

[0226] The tests were carried out in accordance with ISO 179 with a 5 J pendulum.

TABLE-US-00012 TABLE 11 Results of the mechanical tests as in example 6 (E5) on the semifinished products from example 5 (Z3b) Tensile strength Impact resistance [MPa] [kJ/m.sup.2] Z3b-P27 63.1 47.9 Z3b-P12A 71.6 59.3 Z3b-P28 71.4 60.1 Z3b-P29 72.6 58.9

[0227] The marked increase in tensile strength (at least 11%) and in impact resistance (at least 18%) when the particles of the invention are used can be seen when comparison is made with the example not of the invention.