AU736906B2 - Precipitated silica - Google Patents

Precipitated silica Download PDF

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AU736906B2
AU736906B2 AU97076/98A AU9707698A AU736906B2 AU 736906 B2 AU736906 B2 AU 736906B2 AU 97076/98 A AU97076/98 A AU 97076/98A AU 9707698 A AU9707698 A AU 9707698A AU 736906 B2 AU736906 B2 AU 736906B2
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din
precipitated silica
lacquer
size distribution
polyethylene wax
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AU9707698A (en
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Jochen Scheffler
Mustafa Siray
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Evonik Operations GmbH
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Degussa GmbH
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
    • C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/42—Gloss-reducing agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/10—Solid density
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    • C01P2006/12—Surface area
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/19—Oil-absorption capacity, e.g. DBP values
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • C—CHEMISTRY; METALLURGY
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    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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    • C01P2006/80—Compositional purity

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  • Paints Or Removers (AREA)
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Abstract

Precipitated silica with the specified physical-chemical parameters is new. Precipitated silica (I) with the following physical-chemical parameters is new: BET surface area = 400-600 m<2>/g to DIN 66131; dibutyl phthalate (DBP) value = 300-360 g/100 g to DIN 53601; tamped density = 70-140 g/l to DIN 53194; grindometer value = 15-50 mu m to ISO 1524; particle size distribution index I = less than 1.0 by Malvern method, I = (d90 - d10)/2d50. Independent claims are also included for (a) precipitated silica (II) coated with a polyethylene wax emulsion and having specified physical chemical parameters; (b) the production of (I); and (c) the production of (II).

Description

S F Ref: 439842
AUSTRALIA
PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT 00 0 0 0000 00 0 0 @000 0 00 00* 00* 00* 00* 0 0 0 oeeoo eee eeee eeee eo
ORIGINAL
Name and Address of Applicant: Actual Inventor(s): Address for Service: Invention Title: Degussa Aktiengesellschaft Welssfrauenstrasse 9 DE-60311 Frankfurt
GERMANY
Mustafa Siray and Jochen Scheffler Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Precipitated Silica The following statement is a full description of this invention, including the best method of performing it known to me/us:- 5845 960101 FH/AL 1 Precipitated silica The invention relates to a precipitated silica, a process for its preparation and its use as a matting agent.
It is known that synthetic, precipitated silicas or silica gels can be used as matting agents (DE-PS 24 14 478, DE-PS 17 67 332, DE-OS 16 69 123, DE-AS 15 92 865, DE-A 38 670).
The matting power of a silica depends on a variety of factors, such as, for example, the type of silica, the particle size, the particle size distribution, the refractive index and also the lacquer system. The shape and oo 15 size distribution of secondary particles in the silica are of particular importance.
In addition to being very efficient, expressed by the reduction in degree of gloss as compared with the non- 20 matted lacquer film, a silica which is used as a matting agent also has to satisfy a number of other requirements.
Thus, for example, there should be no undue thickening of g. •the lacquer system due to the silica which is introduced. A smooth surface to the lacquer should be produced on the corresponding thin lacquer coatings. Specks which have an adverse effect on the surface quality must be avoided.
The document DE-A 31 44 299 describes precipitated silicas and a process for preparing these precipitated silicas which are characterised by the following physico-chemical properties: BET surface area according to DIN 66131 in m 2 /g 400 600 DBP index according to DIN 53601 as a 320 360 and BET surface area according to DIN 66131 in m 2 /g 400 600 DBP index according to DIN 53601 as a 310 360 960101 FH /AL 960101 FH /AL Compacted density according to DIN 53194 in g/l "Alpine" sieve residue 63 pm in wt.% 75 120 0.1
S
SO
When preparing these silicas, an Alpine transverse flow mill or a jet mill is used to mill the product following spray drying. It is also specified in this document that these precipitated silicas are valuable, highly effective matting agents for lacquers. Precipitated silicas which are prepared using these types of mill lead to disadvantageous roughness of the surface due to the presence of large specks in the final lacquer. The grindometer value (according to ISO 1524) in black stoving enamel is greater than 100 pm and 85 to 90 pm respectively for the known precipitated silicas. Thus these precipitated silicas can 15 only be used to a limited extent as matting agents.
There is now the object of preparing a precipitated silica which does not have these disadvantages.
20 The object of the invention is a precipitated silica which is characterised by the following physico-chemical parameters: ff ft f 5.05 ft ooeo *o S 5055 0 S e oo oooooo ft ftf BET surface area according to DIN 66131 in m2/g DBP index according to DIN 53601 in g/100 g Compacted density according to DIN 53194 in g/l Grindometer value according to ISO 1524 in pm Size distribution index I measured with a Malvern instrument Size distribution index I d 90 -d,0 2d 5 0 400 600 300 360 70 140 15 Another subject of the invention is a process for preparing precipitated silicas according to the invention with the physical-chemical parameters: BET surface area according to DIN 66131 in m2/g 400 600 DBP index according to DIN 53601 in g/100 g 300 360 S960101 FH/AL i" 3 Compacted density according to DIN 53194 in g/l 70 140 Grindometer value according to ISO 1524 in pm 15 Size distribution index I measured with a Malvern instrument d -dlo Size distribution index I d 1 2do which is characterised in that a precipitated silica which has the following physico-chemical properties BET surface area according to DIN 66131 in m 2 /g 400 600 1* 0 DBP index according to DIN 53601 as a 340 380 Compacted density according to DIN 53194 in g/l 180 220 "Alpine" sieve residue 63 pm wt.% 25 is milled using a classifier mill or a fluidised bed C counter-flow mill.
The initial silica is described in the document DE-A 31 44 299.
00 20 In one embodiment of the invention, mentioned by way of example, a ZPS classifier mill (Zirkoplex® Alpine Aktiengesellschaft D-8900 Augsburg) or an AFG fluidised bed counter-flow mill may be used.
In another variant of the invention, the precipitated silica according to the invention may be classified after milling in order to adjust to a specific granular fraction.
In a preferred embodiment of the invention, the precipitated silica has the size distribution shown in figure 1.
Classifying may be performed, for example, using an ATP Turboplex fine classifier (Alpine Aktiengesellschaft D-8900 Augsburg).
960101 FH /AL 4 The invention also provides a precipitated silica coated with a polyethylene wax emulsion which is characterised by the following physico-chemical parameters: BET surface area according to DIN 66131 in m 2 /g DBP index according to DIN 53601 as a Carbon content as a Compacted density according to DIN 53194 in g/1 Grindometer value according to ISO 1524 in pm Size distribution index I 351 600 300 360 1 8 7 140 15
S
0000 *0 S *0
S
0 This precipitated silica can be prepared by adding polyethylene wax emulsion to a precipitated silica which has the following physico-chemical characteristics: BET surface area according to DIN 66131 in m 2 /g DBP index according to DIN 53601 as a Compacted density according to DIN 53194 in g/l "Alpine" sieve residue 63 pm wt.% 400 600 340 380 180 220 25 and then drying and milling the product using a classifier mill or a fluidised bed counter-flow mill.
In one embodiment of the invention, the precipitated silica can be prepared by liquefying the filter cake under the action of shear forces, adding polyethylene wax emulsion, spray drying and then milling using a classifier mill or a fluidised bed counter-flow mill.
A precipitated silica in accordance with DE-A 31 44 299 is preferably used as the starting silica.
Precipitated silica according to the invention has the following advantages: The advantages of precipitated silicas according to the invention are in particular their high matting efficiency, 960101 FH /AL in addition to further advantages such as the very smooth surface of the dry lacquer, high transparency and a small effect on the rheology (viscosity) of the lacquer.
Figure 1 shows the size distribution of classified precipitated silica.
Figure 2 shows the particle size distribution of precipitated silicas according to the invention compared to the particle size distribution of a precipitated silica in accordance with DE-A 31 44 299.
S
oeooo 960101 FH/AL 6 Examples Example 1 A precipitated silica prepared in accordance with example 1 from DE-A 31 44 299 is milled in a ZPS 100 Zirkoplex® classifier mill from the Alpine company, by varying the throughput and the process parameters such as speed of rotation of the classifier, milling throughput and milling air. The trial parameters, the physico-chemical data and the paint properties which are obtained in black stoving lacquer are given in table 1.
Example 2 0 00 0 A precipitated silica prepared in accordance with example 1 from DE-A 31 44 299 is milled in an AFG 200/1 fluidised bed counter-flow mill, from the Alpine company, while varying the throughput and the process parameters such as rate of S 20 rotation of the classifier, or the milling air. The trial parameters, the physico-chemical data and the paint properties which are obtained in black stoving lacquer are given in table 2.
Example 3 Precipitated silicas which are prepared in accordance with example lc or example 2c (see table 1 and 2) are classified in an ATP 50 turboflex fine classifier to give a finer and a coarser fraction. The process parameters, the physical data and the paint test results which are obtained in black stoving lacquer are given in table 3.
Example 4 (comparison example) The unmilled, spray-dried silica, prepared in accordance with DE 31 44 299 (example is milled on a UP 630 Alpine 960101 FH /AL 7 transverse flow mill. The physico-chemical data and paint properties of the product obtained are given in table 4.
Example 5 (comparison example) The unmilled, spray-dried silica, prepared in accordance with DE 31 44 299 (example is milled using an MC 500 Microgrinding air jet mill. The physico-chemical data and paint properties are given in table 4.
The effectiveness and matting efficiency of the precipitated silicas prepared according to examples 1 to 3 are tested in a black stoving lacquer. The Lange gloss values, at angles of reflection of 600 and 850, and the 15 Hegman grindometer value were also assessed.
The B. Lange gloss meter was used to determine the degree of gloss, which is a measure of the matting power of the matting silica tested. The B. Lange gloss meter uses angles 20 of incidence and reflection of 600 and 850. The degrees of gloss measured are cited as percentages. The lower this value, the better is the matting capacity of the Sprecipitated silica. As a result, less matting agent has to be used in order to achieve a quite specific degree of gloss or a specified matting effect.
The grindometer value is determined using a grindometer.
The grindometer value, which is measured in mu (micrometers) is a measure of the largest particles which can be found after stirring the precipitated silica into the final, sprayable lacquer mixture. It can be related to the production of specks in the dry lacquer film, so undesired specks or sprayed granules can be detected using the grindometer (ISO 1524).
The quality of the lacquer film surface is determined using the scanning section method developed by the Hommelwerke 960101 FH /AL 8 company and is cited as an average roughness value (Ra) according to DIN 4768/1, DIN 4762/1E and as an average depth of roughness (RZD) according to DIN 4768/1.
The black stoving lacquer used had the following composition: Parts by a 4.
0e
S.
C
a.
C.
S
S. C *g e Carbon black paste, tack 1 Jagalyd R40, 60 strength in xylene Maprenal MF 800, 55 strength in butanol Baysilone paint additive OL 17,1 in xylene Thinner 50.8 25.9 13.3 100.0 Thinner Xylene Butanol Ethoxypropanol 75.0 10.0 15.0 100.0 4 g of precipitated silica are stirred into 100 g of lacquer with a blade stirrer at 2000 rpm for 10 minutes.
The viscosity of the mixture is adjusted to a flow time of seconds using xylene (DIN; 4 mm nozzle).
The lacquer is sprayed to give an approximately 30 pm thick dry layer on sheet metal, air dried and fired at 180*C for minutes.
Example 6 The paint properties of the precipitated silicas prepared according to examples la to c, a precipitated silica prepared according to DE 38 15 670 and a commercially available product (Nipsil 1009) are tested in two other test lacquer systems.
960101 FH /AL CC lacquer Alftalat AN 950, 60% in Solvesso 1 5 0/Butylglycol Solvesso 150 Titanium dioxide Kronos 2059 Aerosil R 972 Dispersion: 40 h ball mill KU 5, 60 rpm, 4900 g Alubite beads 19 mm Alftalat AN 950, 60 in Solvesso 150/Butyl glycol Maprenal MF 900, 100 Maprenal MF 577, 50 in butanol Butyl glycol Solvesso 150 Xylene DOW CORNING PA 57 p-Toluylsulfonic acid, 20 in butanol Total Parts by wt.
29.30 2.60 33.60 0.20 13.00 8.10 0.80 2.00 2.90 6.70 0.60 0.30 100.00 *4 0@ Y 4 B 4 *9
B.
B.
a.
dO 99 Before use, 3.2 g of matting agent are dispersed in 150 5 parts by weight of lacquer using a blade stirrer at 2000 rpm.
DD lacquer CAB 381-0,5 Butyl acetate, 98 strength Ethoxypropyl acetate Desmophen 800 Desmophen 1100 Mowilit, 50 strength in ethyl acetate Baysilone-lacquer additive Xylene Total Parts by wt.
0.3 11.0 16.5 15.0 20.0 0.1 34.1 100.00 Firstly 0.3 parts by weight of CAB 381-0.5 are carefully dissolved in 11.0 parts by weight of butyl acetate (98.0 strength) and 16.5 parts by weight of ethoxypropyl acetate using a high speed stirrer. Then the other components are S960101 FH /AL added in the sequence given above and the mixture is homogenised by stirring.
Before use, the gloss lacquer is homogenised with the blade stirrer. The matting agent (amount see table 6) is dispersed in 100 parts by weight of lacquer using a blade stirrer at 2000 rpm. After a degassing time of 15 minutes, g of the hardener Desmodur L 75 are added and homogenised with the blade stirrer for 2 minutes at 1000 rpm. The mixture is applied to a thoroughly pre-cleansed glass block and to a black, high gloss, lacquered glass S. block using a spreader with a 200 pm slit.
W The test results in CC lacquer are given in table 5 and in 15 DD lacquer in table 6. For comparison the precipitated SS silicas according to DE 38 15 670 and the commercial product NIPSIL E 1009 are also given. A comparison of the data determined can be obtained from the tables.
*o r.*
S
0@ S 0 0 0 0 *OS
S
S
S S. 0 S S S 55 005 S S.
0 0 5 5 5 0 0 5 S S S S 0 5 0 0@ 0 0 Table 1 Ex. Speed Speed of Class- Throu Particle size (Malvem) Grindo Gloss Sheen Roughness Viscosity Thickness of of mill classifier ifier air -ghput coating rpm rpm m 3 /h Ikg/h d 4.3 1d10 d50 d 90 pmn 600 850 RZD Ra s pm 1 a 10700 '11000 175 10 8.34 4.48 7.03 12.89 123 23.8 '72.0 48.2 2.27 0.27 36 l b 10000 10500. 180 15 9.76 4.53 7.11 15.84 27 21.8 70.3 48.5 2.37 0.28 36 I c 10000 9000 200 30 9.34 4.52 8.03 13.87 28 24.7 67.9 43.2 34 28 I d 10000 10000' 145 15 9.97 4.27 6.78 16.13 33 26.0 73.4 47.4 38 29 Table 2 I I r I Ex. Speed of Milling Throu Particle size (Malvern) micrometers (prn) Grindo Gloss Sheen Roughness Viscosity Thickness of coating rpm m 3 /h kg/h d 4.3 dlO d50 d 90 pm 608 850 RZD Ra s Pm 2 a 11000 150 20 6.49 3.74 5.95 9.7 23 16.6 66.4 49.8 2.24 0.28 36 2 b 11000 150 40 12.9 3.69 6.68 24.3 123 21.9 58.0 136.1 2.00 0.24 39 39 2 c 10000 150 20 11.5 4.99 8.47 17.9 27 16.6 58.8 42.2 3.24 0.42 2 d 8000 150 30 12.2 5.76 11.5 19.5 39 15.6 43.8 28.2 4.30 0.55 36 42 2 e 11000 150 30 7.6 3.55 6.1 i12.44 24 121.1 55.4 34.3 0 0 0 0 0 0 Table 3 Classifying precipitated silica, prepared according to example ic Ex. Fraction Speed Class- Throu Particle size (Malvem) Grindo Gloss Sheen Roughness Viscosity Thickness o ifier air -ghput of coating rpm m/h kg/h d4.3 d 10 d 50 d 90 pm 600 85° RZD Ra s pm 3a fine 16000 53 4.3 7.42 4.24 6.78 11.13 22 25.3 75.7 50.4 23 coarse 12.07 8.05 11.28 16.99 33 12.1 27.6 15.5 21 3 b fine 16000 66 2.0 6.84 3.95 6.30 10.11 23 26.2 74.9 48.7 23 coarse 11.18 8.26 10.93 14.45 33 12.3 26.4 14.1 21 3 c fine 13000 117 6.0 7.42 4.24 6.82 11.07 22 23.1 71.9 48.8 2.13 0.26 23 coarse 11.08 8.03 10.73 14.48 33 13.9 35.6 21.7 21 Classifying precipitated silica, prepared according to example 2c Fract- Yield Speed of Milling Throu- Particle size (Malvem) Grindo Gloss Sheen Roughness Viscosity Ex. ion classifier air ghput rpm m 3 /h kg/h d4.3 d 10 d50 d90 pm 600 85° RZD Ra s 4 a fine 85 13000 2.1 6.84 3.95 6.26 10.10 29 19.8 70.3 50.7 2.2 0.27 26 coarse 15 10.17 8.32 9.91 12.35 29 10.9 31.2 20.3 24 4 b fine 66 16000 2.1 7.37 3.01 4.84 11.08 17 21.8 77.6 55.8 26 coarse 34 9.36 8.45 9.28 10.4 27 10.5 36.2 25.7 24 go 0@0
S
S 0 0@ S 0 S S S. 0 @50 S seS S 5O S S S S S S S Se 0* 0 5 5 0 SO 6O* 5@ *0 0 Table 4 Particle size (urn) Grindo Gloss Sheen d 4.3 dl10 d 50 d 90 urn 600 850 Comparison example 4 18.7 6.4 14.9 35.1 100 10.5 15.2 4.7 Comparison example 5 28 3.4j 6.2 20.7 85 18.4 62.4 44.0 air bubblesl Table CC lacquer Example according to: DE 38 15 670 1 a 1 b 1 C NIPSIL E 1009 Flowtime in.DIN seconds at 23 00 140 149 148 135 118 Thickness of coating in umn 23 23 24 23 23 600 reflectometer value (DIN 67530) 36.9 36.7 36.3 37.7 44.4 850 reflectometer value (DIN 67530) 79.3 78.9 77.7 77.5 86.5 Sheen 42.4 42.2 41.4 39.8 42.1 0 S. S S
S
OS
SOS SO S S 0 0 0 0@ S S 000 00 0 000 0 500 00 S *e 0 0 0 S S 0 0 0 OS 00 0 0 0 5 5 S S S S 5 0 0 *0 S 5 S Table 6 DD lacquer Example according to: DE 38 15 670 1 a 1 b 1 C NIPSIL E 1009 Amount of matting agent added 7.5 7.5 7.5 7.5 Flowtime in D IN seconds at 23 OC 31 42 41 32 23 600 reflectometer value (DIN 67530) 19.5 30 30.2 43.7 90.4 850 reflectometer value (DIN 67530) 55.6 68.1 68.2 74.9 97.5 Macbeth RD 918 densitometer value 2.12 2.31 2.17 2.16 2.3 measured using yellow filter 960101 FH /AL Example 7 The matting efficiency is determined in a number of different lacquer systems, wherein the preparation and application of the lacquer took place under identical conditions each time.
A high matting efficiency means a low requirement (concentration) of matting agent in order to achieve a specific degree of gloss (measured at an angle of 60 0
C
S The matting efficiency of unknown matting agents is determined in a relative manner, i.e. by comparison with :known matting agents, so that variations in the determination of the degree of gloss (depending on the mode *00 *9O9 15 of preparation and application of the lacquer) are avoided.
One important physico-chemical parameter which has a critical effect on the matting efficiency of silica is the particle size distribution of the silica. Basically, it has been shown that with identical precipitation processes the 20 matting efficiency of the precipitated silica decreases with decreasing particle size (and vice versa). Fine fractions of precipitated silica have a lower matting S. efficiency than that of a more coarsely milled fraction.
The high matting efficiency of the precipitated silicas according to the invention is demonstrated as follows, in a variety of lacquer systems: 0 .0 S.oo oo 0o S Se. 0 *0 0.0 0 0 S S S. S S 0 0 0 S 0 0S 0 0.0 0 0 0 00 S S 0 0 0 Table 7: Test in alkyd/melamine lacquer Lacquer system: alkyd melamine in accordance with formulation Product from example 2c has higher matting efficiency than Syloid ED 5, although this product is more finely divided. Furthermore, product 2a is more efficient than Nipsil E 1009 and Syloid ED 3.
Product prepared Weight Partic- Partic- Partic- Partic- Grindo Gloss Gloss Sheen RZD Ra Visco- Thickaccording to added le size le size le size le size -meter 600 850 rough- rough- sity ness of example d4.3 dIO d50 d90 ness ness coating _(AIM)
I
T MM OM P S Pm 1 +3 4 12.32 6.58 11.48 18.83 32 16.0 43.0 27.0 3.43 0.46 34 32 1+3 4 11.85 5.99 10.90 18.70 34 16.0 46.0 30 37 32 2 4 12.22 5.76 11.53 19.50 40 16.4 45.0 28.6 4.30 0.55 36 42 OK 520 4 7.20 31 16.5 64.0 47.5 3.05 0.36 38 37 2 4 11.50 4.99 8.47 17.97 30 16.6 56.8 40.2 3.24 0.42 36 38 2 4 10.90 5.55 10.41 16.46 37 16.9 47.8 30.9 38 27 1 4 13.24 6.42 12.90. 20.40 33 17.8 43.6 25.8 36 1 3 4 12.32 6.58 11.48 18.83 33 17.9 50.2 32.3 3.43 0.46 33 Syloid ED 5 4 10.47 6.30 9.56 16.82 32 18.7 51.0 32.3 3.65 0.46 32 41 1+3 4 8.85 4.50 8.37 13.19 25 19.8 61.9 42.1 2.80 0.35 37 32 1+3 4 8.85 4.50 8.37 13.19 25 21.0 63.0 42.0 34 1 4 11.37 5.81 10.95 17.12 34 21.5 55.2 33.7 35 28 1 4 7.10 1_ 1_27 21.8 70.3 48.5 2.37 0.28 36 1 Syloid ED 3 4 6.04 3.62 5.54 8.88 21 22.0 73.0 51.0 2.03 0.24 35 34 S S OS 0 0 0 S I 0 0 0 00 0 000 *0 OS 00. 5 5 0@ S 0 S 5 0 5 *S 0 5 S S 0 S 0 0 S 0 5 *5 5 0 Product prepared Weight Partic- Partic-. Partic- Partic- Gr indo Gloss Gloss Sheen RZD RZD Visco- Thickaccording to added le size le size le, size le size -meter 600 850 rough- rough- sity ness of example d4.3 dlO d50 dg0 ness ness 1 oating (NM) (AIM)_ Nipsil E 1009 4 7.92 4.34 6.97 12.51 27 22.0 70.0. 48.0 2.44 0.28 38 32 OK 607 4 4.60 4.20 18 22.5 78.5 56.0 1.70 0.20 35 32 2 +3 4 6.84 3.95 6.26 10.10 22 22.9 74.6 51.7 2.20 0.27 35 39 2 4 12.47 4.03 7.17 29.37 27 23.1 174.1 51.0 2.08 0.26 34 41 1 4 8.34 4.48 7.03 12.89 23 23.8 72.0 148.2 2.27 0.27 36 1 4 10.10 5.03 7.80 14.71 23 24.1 70.7 46.6 1 4 8.52 4.84 7.57 12.94 23 24.4 71.0 46.6 1 4 9.34 4.52 8.03 13.87 28 24.7 67.9 43.2 34 '281 1 +3 4 7.42 4.24 6.82 11.07 24 125.0 73.0 48.0 12.13 10.26+ _38 134 S 0O 0 S 0 SO S .9 *0 9 S S @00 Se 55 5 S @00 0 S 5* 0 0 0 0 S. S B *5 S 1 Table 8: Tests in DD lacquer Lacquer system: DD lacquer in accordance with formulation Comparison example: Syloid ED 3 Product Weight Malvern Particle Particle Particle Grindo- Densito- Gloss Gloss Sheen Rough- Rough- Visco- Thick- Lacquer ref. added value size size size meter meter 60° 850 ness ness sity ness of system d4.3 d10 d50 d90 (AIM) value RZD Ra coating g pm pm pm pm pm (NM) (AM) s Spm 2b 7.65 12.93 3.69 6.68 24.35 25 2.11 25.0 66.2 41.2 2.00 0.24 n.m. ca. 40 DD 2d 8.00 12.22 5.76 11.53 19.50 40 2.16 24.7 40.3 15.6 4.30 0.55 32 ca. 40 DD 3c 8.2 7.42 4.24 6.82 11.07 22 2.12 25.0 65.6 40.6 2.13 0.26 53 ca. 40 DD 2a 8.24 6.49 3.74 5.95 9.70 24 2.11 24.5 59.7 35.2 2.24 0.28 55 ca. 40 DD 1a 8.41 8.34 4.48 7.03 12.89 25 2.08 25.0 60.9 35.9 2.27 0.27 n.m. ca. 40 DD Precip.
silica 10.1 7.83 4.67 7.17 11.56 23 2.01 25.0 61.9 36.9 1.95 0.24 53 ca. 40 DD Syloid ED 3 10.7 6.04 3.62 5.54 8.88 21 2.24 25.0 68.2 43.2 2.03 0.24 52 ca. 40 DD 00 0 00* 0 0 0 0 0 00 0 0* 00 @0 00 000 0 0 00..
A- I 1 Table 9: Tests in DD lacquer Lacquer system: DD lacquer in accordance with formulation Comparison example: Nipsil E 1009 Product Weight Particle Particle Particle Particle Grindo- Densito- Gloss Gloss Sheen Rough- Rough- Visco- Thick- Lacquer ref. added size size size size meter meter 60* 85" ness ness sity ness of system d4.3 dl0 d50 d90 value value RZD Ra layer g pm pm pm pm pm s pm 2b 7.65 12.93 3.69 6.68 24.35 25 2.11 25.0 66.2 41.2 2.00 0.24 n.m. ca. 40 DD la 8.41 8.34 4.48 7.03 12.89 25 2.08 25.0 60.9 35.9 2.27 0.27 n.m. ca. 40 DD Nipsil E 1009 11.3 7.92 4.34 6.97 12.51 27 1.96 25.0 60.5 35.5 2.44 0.28 35 ca. 40 DD 0 OS 0 0 00 0O
S
OS. OS
S
0 5 0 *5 0 5 OS S S@e S.
0 S S ~O 0 5 S S.
S@ 0 0 0 0 S S. SO* @0 *5 S
I
Table 10: Tests in coil coating lacquer Lacquer system: coil coating lacquer in accordance with formulation Product prepared Weight Particle IParticle Particle Particle Grindo- Gloss Gloss Sheen Viscoaccording to added size size size size meter 600 850 sity example dlO d50 d90 HK 125 2.7 4.9. 9.65 17.35 30 24.0 45.0 21.0 Syloid C 812 2 6.40 12.50 20.80 40 27.0 44.0 17.0 1 2 12.36 6.20 11.33 19.31 32 27.0 48.0 21.0 101 1 2 14.56 6.82 13.31 23.30 40 28.0 48.0 20.0 102 Lovel HF 2 113.22 22.961 44 129.0 42.0 113.0 177 S OS S 0 0 0 00 00 0 06 .0 S 0
S
0. 00 0 000 0 @0 S 090 00 0 0 0 0 0 SO 00 0 0 0 0 0 S 60 @05 00 00 0 Table 11: Test in an acrylic dispersion (aqueous) Lacquer system: acrylate dispersion Comparison product: AQ 75 N (MB 2399-134), aqueous, from the Rohm and Haas company Product name Weight added Grindometer Densitometer Gloss 600 Gloss 850 Sheen g Jim value TS 100 (Commercial 0.25 41 2.5 69.3 92.3 23.0 product from Degussa AG) TS 100 (Commercial 0.5 41 2.4 56.1 87.0 30.9 product from Degussa AG) TS 100 (Commercial 0.75 412.28 44.7 82.0 37.3 product from Degussa AG) TS 100 (Commercial 1 41 2.17 30.4 73.4 43.0 product from Degussa AG) Precipitated silica 1 29 2.09 31.3 53822.5 according to example l b AQ 75 N (Commercial 12 .53. 822.
product frm Crosfield) 12 .53. 822.
Precipitated silica 1.5 29 1.89 18.1 35.2 17.1 according to example lb TS 100(Commercial 1.5 41 1.82 18.7 59.5 40.8 product from Degussa AG) AQ 75 N(Commercial 1.5 28 1.91 31.9 61.0 29.1 product from Crosfield)________ Precipitated silica 2 29 1.79 12.4 25.2 12.8 according to example lb115_____ TS 100(Commercial 2 41 1.8 15.3 66.0 50.7 product from Degussa AG) AQ 75 N (Commercial 2 28 1.89 27.7 53.3 25.6 product from Crosfield AQ 75 N(Commercial 2.5 28 1.87 21.3 51.5 30.2 product from Crosfield) AQ 75 N (Commercial4281.35836 Iproduct from Crosfield) 4 28 12. 3582.
I e 960101 FH/AL 22 Particle sizes are determined using a laser beam diffractometer from the Malvern company. Before the measurement, the silica is dispersed in water using a stirrer and ultrasound. This silica dispersion is then pumped round the instrument into the path of the beam (cell) using a pump.
Sheen is the difference in the degree of gloss measured at an angle of 850 and the degree of gloss measured at an 0 angle of 600 The viscosity is determined using a 4 mm DIN cup. The flow time in seconds of the lacquer is measured in accordance with DIN 53 211.
15 o t Key to the abbreviations: CC lacquer: DD lacquer: :20
S
coil coating lacquer Desmodur Desmophen lacquer Desmodur is a hardener based on isocyanates Desmophen is a polyalcohol, used as the binder component Desmodur/Desmophen are the registered trade names of Bayer AG cellulose acetobutyrate alkyd/melamine lacquer
CAB
A/M
Example 8 Coating with polyethylene wax emulsion.
Precipitated silica is prepared according to DE-OS 31 44 299, example 1. A wax emulsion (5 wax with respect to silica) is added to the filter cake which has been liquefied under the action of shear forces (solids content 10.8 and then stirred vigorously for a further minutes. The wax emulsion is prepared in an autoclave which 960101 FH /AL is steam-heatable and has a disperser. 4.8 parts by weight of an alkylpolyglycol ether (Marlowet® CFW) in 81.0 parts by weight of water at about 100 0 C is initially introduced.
Then 14.2 parts by weight of low pressure polyethylene wax are added and heated to 130 0 C. On reaching 130 0 C, the disperser is switched on and dispersion takes place for minutes. During this time the temperature is held at between 130"C and 140 0 C. After switching off the disperser and cooling to about 110 0 C, the final emulsion is 10 discharged.
mA a. a.
S..
SSSS
15
S
The polyethylene used is characterised by the following properties: Average molecular weight Solidifying point Dropping point Density (g/cm 3 1000 100 104 °C 110 117 °C 0.93 0 0O S. Sq 0* *5 S
SO
S
20 The silica suspension coated with wax in this way is then dried in a rapid dryer a spray drier) by atomising two-fluid nozzle, 2.8 bar of atmospheric air). The dried product is milled in a mechanical classifier mill of the ZPS 50 type from the Alpine company. The physicochemical data are given in table 12: Table 12 8a 8b N2 surface area 2/g 373 373 CTAB-surface area m2/g 333 333 DBP absorption g/100 g 330 330 C content 3.4 3.4 pH 7.2 7.2 Compacted density g/1 106 87 Particle size distribution (Malvern) in pm 26.25 12.28 d9o d 50 14.85 8.21 dlo 6.91 4.66 960101 FH/AL 24 Table 13: Alkyl melamine lacquer I
I
Comparison exam ple I 4
I-
Flow time in DIN- seconds at I 8a 8 b Ann FlwtmeI IN-scod t23 C 31J 29 30O- 32 Grindometer value Pm 41 26 25
U
WaIUI p 29 value (DIN 67530) J 11.0 17.3 19.0 f 21.0 0 -Refiectometer value (DIN 67530) I24.3 42.9 69.5 j 76.9
VU"II
13.3 256A t; n r A 0 006 000 0 eg 0 9 .4 a a Degussa commercial product Table 14: DD lacquer Comparison example 86 8 b OK 500 OK 520 Flow time in DIN- seconds at 23 0 C 23 27 29 Weight of matting agent added 8.5 8.5 8.5 60*-Reflectometer value (DIN 67530) 21.6 34.4 69.9 8.6 0 -Refiectometer value (DIN 67530) 33.2 67.4 88.2 32.5 Sheen 11.6 33.0 18.3 23.9 Densitometer value Macbeth RD 918 2.12 2.32 2.31 1.69 Degussa commercial product

Claims (10)

1. Precipitated silica characterised by the following physico-chemical parameters: BET surface area (DIN 66131) in m 2 /g DBP index (DIN 53601) in g/100 g Compacted density (DIN 53194) in g/l Grindometer value (ISO 1524) in pm Size distribution index I measured with a Malvern intrument Size distribution index I d -do 2d 0 400 600 300 360 70 140 15 a. a *960 S 99* 595 a a. a a 0554 9C 0 a.
2. Process for preparing precipitated silica with the physico-chemical data BET surface area (DIN 66131) in m2/g 400 600 DBP index (DIN 53601) in g/100 g 300 360 Compacted density (DIN 53194) in g/l 70 140 Grindometer value (ISO 1524) in pm 15 Size distribution index I measured with a Malvern intrument Size distribution index I -d,0 2do according to Claim 1, characterised in that a precipitated silica which has the following physico- chemical characteristics: BET surface area (DIN 66131) in m2/g DBP index (DIN 53601) as a Dompacted density (DIN 53194) in g/l "Alpine" sieve residue 63 pm wt.% 400 600 340 380 180 220 25 is milled using a classifier mill or a fluidised bed counter-flow mill. t 960101 FH /AL 26
3. Precipitated silica coated with a polyethylene wax emulsion, characterised by the following physico- chemical parameters: BET surface area (DIN 66131) in m 2 /g DBP index (DIN 53601) as a Carbon content as a Compacted density (DIN 53194) in g/l Grindometer value (ISO 1524) in pm Size distribution index I 351 600 300 360 1 8 70 140 15 1.0. o *r I be p
4. Process for preparing precipitated silica coated with polyethylene wax emulsion in accordance with Claim 3, characterised in that a polyethylene wax emulsion is added to a precipitated silica which has the following physico-chemical characteristics: *a 4* A p 5* oCdI a C BET surface area (DIN 66131) in m 2 /g DBP index (DIN 53601) as a 20 Compacted density (DIN 53194) in g/l "Alpine" sieve residue 63 pm wt.% 400 600 340 380 180 220 25 and the mixture is then dried and milled using a classifier mill or a fluidised bed counter-flow mill.
Process according to Claim 4, characterised in that the precipitated silica is prepared, the filter cake is liquefied under the action of shear forces, polyethylene wax emulsion is added and the mixture is spray dried and milled using a classifier mill or a fluidised bed counter-flow mill.
6. Use of precipitated silica in accordance with Claim 1 or 3 as a matting agent in lacquer systems. v 27
7. A precipitated silica, substantially as hereinbefore described with reference to any one of the examples but excluding the comparative examples.
8. Process for preparing precipitated silica, substantially as hereinbefore described with reference to any one of the examples but excluding the comparative examples.
9. Precipitated silica coated with a polyethylene wax emulsion, substantially as hereinbefore described with reference to any one of the examples but excluding the comparative examples. Process for preparing precipitated silica coated with polyethylene wax emulsion, substantially as hereinbefore described with reference to any one of the examples but excluding the comparative examples. Dated
10 December, 1998 Degussa Aktiengesellschaft Patent Attorneys for the Applicant/Nominated Person to SPRUSON FERGUSON t** t 54 [Ilibff]01167:MEF
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CN114891391B (en) * 2022-06-15 2023-01-03 广州市印道理印刷有限公司 Ink with matte effect and preparation process thereof
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