CA1157711A - Inorganic pigments with improved gloss and distribution in lacquer binders - Google Patents

Abstract

Abstract of the Disclosure An inorganic pigment exhibiting improved gloss and distribution in lacquer binders, carrying a coating comprising a polyhydrogen siloxane and an alkanolamine.
Advantageously the alkanolamine comprises at least one of triethanolamine, trilsopropanolamine, diethanolamine, diisopropanolamine and 2-amino-2-methyl-propanol-1, the polyhydrogen siloxane ls a polymethylhydrogen siloxane having more than 5 Si atoms, and the pigment comprises T1O2 or a titanate carrying an inorganic coating, the polyhydrogen siloxane plus alkanolamine ranging from about 0.3 to 1 % by weight of the pigment and the ratio by weight of the polyhydrogen siloxane to alkanolamine ranging from about 1:2 to 1:5.

Description

INORGANIC PIGMENTS WITH IMPROVED GLOSS AND DISTRIBUTION
IN LACQUER BINDERS
The present invention relates to inorganic pigments which have improved gloss and distribution in lacquer binders as a result of treatment with organic auxil-iaries either before or during a final micronization.
Fog-free high glo-ss coatings and good distri-bution when incorporated in lacquer binders are im-portant requirements of high quality pigments.
Apart from other properties, such as good resistance to weathering and good brightening or tinting power, the above constitute important criteria for assess-ing quality. There has been no lack of proposals in the past for achieving such an aim. One procedure which characterizes many of thepatents relating to this subject matter is the treatment of the pigment surface with organic auxiliaries before or during a grinding operation which operation concludes the process of manufacturing the pigment. The grinding of the pigment is normally carried out in a pin mill, a ball mill or a ring roll mill such as a Raymond mill, but exceptionally high quality pigments may be obtained by micronizationin jet mills such as air jet or steam jet mills. Numerous compounds are known for use as organic auxiliaries for modify-ing the surface of pigments. Apart from polyols, alkylene oxides, phenols, long chain fatty alcohols and fatty acid esters, to name but a few examples, it has also been proposed to use organosilicon compounds.
The use of organosilicon compounds is aimed 3 at rendering pigments or fillers hydrophobic and at improving their dispersibility and incorporation in synthetic materials. German Offenlegungsschrift No.

2,012,017, for example, describes the treatment of TiO2 with sodium methyl siliconate to improve its dispersibility in polystyrene. It is also customary Le A 19 541 to render pigments hydrophobic with polysiloxanes, e.g. with octamethylcyclotetrasiloxane (British Patent No. 959,211) to improve their incorporation in poly-amides or to treat them with silanes, e.g. with tri-alkoxysilanes, as described in British Patent No.825,404.
In addition, the preparation of stable dispersions in water with the aid of polymethylsiloxanes contain-ing Si-H groups has been disclosed in Spanish Patent No. ~9,831.
With the surface treatments described above, however, it is not possible to obtain pigments which produce an excellent fog-free gloss in lacquer binders.
It is also known to treat pigments with alkanol-amines. The use of trialkanolamines, for example, hasbeen proposed in US Patent No. 3,345,187 and the use of diisopropanolamine in German Patent No. 2,442,678.
In the process according to German O~fenlegungsschrift No. 1,792,022, triethanolamine is brought into contact with the pigment surface in the course of a so-called double steam jet milling process. US Patent No. 2, 737,460 relates to the milling of pigments with tri-alkanolamines in the pr~sence of finely divided B fillers such as Aerosil. It is also known to use salts of alkanolamines with organic acids such as, for example, lactic acid (~erman Patent No. 1,271,862) or benzoic acid (US Patent No. 3,172,772).
The procedures mentioned above are either tech-nically complicated or else expensive and the re-3o sulting p~gments, although showing marked improvementscompared with titamium dioxides which have not been organicallS treated, do not meet the highest demands for ~uality with regard to gloss distribution and subdivision, and this applies particularly to pigments which have been after-treated with SiO2 and A120~.

rf~ e Le A 19 541 11~7'711 It has now surprisingly been found that pigments with improved gloss and distribution in lacquer binders can be obtained easily by treatme~t with organic auxiliaries before the final micronization if a combination of poly-hydrogen siloxanes and alkanolamines is used.
The present invention provides inorganic pigments with improved gloss and distribution in lacquer binders having a coating of polyhydrogen siloxanes and alkanolamines and also a process for the preparation thereof by coating the pigments with the above mentioned compounds before or during the final micron-ization. White pigments based on TiO2 or titanates which have optionally been after-treated inorganically are particularly suitable inorganic pigments. The new pigments are suitable in particular for pigmenting polymer materials and aqueous suspensions. It has been found to be advantageous to use about 0.1 to

3% by weight of polyhydrogen siloxane plus alkanolamine, and a ratio by weight of polyhydrogen siloxane to alkanolamine within the range of about 2:1 to l:lO, - preferably about 1:2 to 1:5.
The polyhydrogen siloxanes used may have a straight chain, a branched chain or a cyclic structure containing for example the following units, option-ally in alternating arrangement:
[R2R'-SiOlt2] [RH-SiO] [R'-SiO3/2] and [SiO2]
wherein R and R' are the same or different and each may denote a hydrogen atom or an alkyl, cycloalkyl, aryl and/or alkenyl group, and the number of silicon atoms is greater than 5.
Polyhydrogen siloxanes which conform to the above definition include, for example, [SiMe3] end blocked linear polyhydrogen methyl siloxanes, prefer-ably having chain lengths with an average of lO, 30 or 50 [SiMe2O] units.
Partially hydrogenated polysiloxanes of the .

`711 type described are also suitable, particularly those having 5 [SiHMeO~ or 5 CSiMe2~ units. Polyvinyl hydrogen methyl siloxanes which are ~SiHMe~ end blocked are particularly preferred, especially those with 5 [SiHMeO~ units and 3 ~i(CH=CH2)MeO3 units.
Another preferred class of compounds is polyhydrogen siloxanes, an example of which is a LSiHMe2~ end blocked, simply branched permethylated polysiloxane having 9 [SiMe20~ units.
The a~nol~nes used may be tria~nolamunes, d~ nclamines a ~ or m~no~no1a~nes, e.g. amlnes carrying a~yl an~or hy~xKy-aIkyl groups of 1 to 4 ~ bon atoms. Trie~olamune, triisopr ~ nol-amune, 2-~no-2-methyl-p~nol-1 and 2-amuno-2-hyd~methyl-pnq~r diol-(1,3) are p~ti ~ arly suitable.
The organic auxiliaries are brought into contact with the pigment in known manner either before or during a final milling operation. It is immaterial whether they are added to the moist filter cake, paste or sludge obtained in the course of preparation of the pigment before it is dried or whether they are added to the dry substance before the final milling operation in some suitable manner, for example by spraying or even whether as in the case of milling in a steam jet mill, they are directly added to the steam before this is fed into the mill. Also, the effectiveness of the compounds to be used according to the present invention does not depend upon the sequence in which they are added. Regardless of whether mixtures of alkanolamines and polyhydrogensiloxanes are added or whether the alkanolamine is added first and the polyhydrogensiloxane later, or vice versa, the pigments obtained are superior in their gloss, fog and granularity after micronization than products which have been treated with alkanolamines alone or with polyhydrogensiloxanes alone. This clearly indicates a synergistic effect.

Le A 19 541 All inorganic white andcolored pigments are suitable for the process according to the present inven-tion. Particularly advantageous results are obtained with white pi~ments based on TiO2 or titanates or with colored pigments such as iron oxides. Pigments which have previously been subjected to an inorganic after-treatment may also be used.
The process according to the present invention for improving gloss and fog is independent of the process used for producing the pigments. Thus a TiO2 pigment may be improved by the process according to the present invention regardless of whether the pigment has been prepared by the sulphate process or the TiC14 combustion process and also regardless of whether the pigment is in the rutile or the anatase form.
To test the pigment ~or gloss and distribution in lacquer binders, it is dispersed in a la~quer binder by means of a dissolver. Dispersion is carried out in a highly viscous binder/solvent mi~ture containing 600/o of alkyd resin (ricinene-modified alkyd resin, oil length 35; Bayer Product A~dalOE~35) in xylene under the following conditions:
Pigment-volume concentration (PVK) of grinding stock 37 . 6~b 25 Diameter of dissolver disc 3.5 cm = D
Diameter of container 5 . 5 cm =1. 57 D
Distance of dissolver disc ~rom bottom 1. 75 cm =0.5 D
Height to which grinding stock fills container 3.5 cm = D
3 Peripheral speed of dissolver disc 11 m/s Dispersion time 5 minutes.
After 5 minutes' dispersion time, samples are removed and lacquered to a PVK of 15o~b with the alkyd resin and a melamine resin (trade product Maprenal MF
800, registered Trade Mark of Hoechst AG) so that the Le A 19 541 ratio of alkv~ resin to melamine resin is 77:23. The degree of fineness of dispersion is determined in the usual manner with a grindometer (DIN 53 203). The lac~uers prepared in this way are t,hen applied to glass plates to form films 120 ~m thic~ when wet, and the films are hardened at 120C for 30 minutes. The gloss is measured with a Gonio photometer at an angle of 25. The height of the peak obtained in the re-flection maximum is a measure of the gloss and the height of the scatter curve 1 next to the reflection maximum is a measure of the gloss fog value.
A high gloss lacquer is distinguished by high - gloss values and low gloss fog values.
The preparation of the pigments according to the present invention is described below:

Example 1 A TiO2 pigment having a rutile structure and prepared by the sulphate process was after-treated inorganically with 3.8~o SiO2 and 4% A1203 and was then dried after the usual washing and filtration. The pigment was sprayed with 0.12~ by weight (based on the dry pigment) of the polymethyl hydrogen siloxane having a structure corresponding to the following average formula CH3 1 3 /~ 3 CH3 - Si - O - Si ~0~-- Si - CH3 and 0.36~ of triethanolamine and was then micronized in a jet mill operated on superheated steam.
The fineness of the dispersion, tl-e gloss values and gloss fog values are set forth in Table 1.

Le A 19 541 _ 7 ~ 7 Comparison Example ~A) This comparison example shows that the use of triethanolamine solely results in a qualitatively inferior pigment. The rutile pigment used in Example l`is sprayed with 0.48~ triethanolamine a~ter it has been dried, and it is then micronized in a jet mill as described in Example 1. The dispersion properties are entered in Table l_ Comparison Example (B) This comparison example shows that the use of -polymethylhydrogen siloxane solely also results in a qualitative]y inferior pigment.
The rutile pigment used in Exa~nple 1 is dried and then sprayed with 0.48~ of the polymethylhydrogen siloxane described in Example 1 and then micronized;
see Table 1.

Example 2 0.15~ by,weight (based on the dry pigment) of the polymethylhydrogen siloxane used in Example 1 is added to the washed filter cake of the rutile pigment as used in Example 1 before it is,dried. After drying, the pigment is sprayed with 0. 45% triisopropanolamine and micronized as described in Example l; see Table 1.

Example 3 The rutile pigment used in Example 1 is dried and then sprayed with 0.12~ of the polymethylhydrogen siloxane described in Example 1 and 0.58~ of 2-amino-2 methyl-l-propanol and then milled in a steam jet mill as described in Example l; see Table 1, Example 4 ~5 The rutile,pigment used in Example 1 is not organ-ically after-treated; see ~able 1.

Le A 19 541 '`71~

Table 1 Example Organic treatmentGloss Fog Grind- Hegman (%) (%)ometer value value (h) 0.12% o(,~bis(tri- 88 24 12 7 methylsilyl)polyme-thylhydrogenosilox-ane 0.36% triethanol-amine A 0.48% triethanol- 77 37 20 6.4 amine B 0.48% O~ -bis(tri- 76 35 16 6.7 methylsilyl) poly-methylhydrogen-siloxane 2 0.15% OC,~-bis(tri- 89 22 10 7.2 methylsilyl)poly-methylhydrogen-siloxane 0.45% triisoprop-anolamine 3 0.12% O~,~-bis(tri- 86 26 14 6.9 methylallyl) poly-methylhydrogen-siloxane 0.58% 2-amino-2-methyl-l-propanol

4 None 49~ 10038 4.9 Samples 1, A and B show that a glven weight of mixture is better than the same weight of the individual components.

,,~.,,~
~, It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

Le A 19 541

Claims (11)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An inorganic pigment exhibiting improved gloss and distribution in lacquer binders, carrying a coating comprising a polyhydrogen siloxane and an alkanolamine.

2. An inorganic pigment according to claim 1, carrying about 0.1 to 3 % by weight of polyhydrogen siloxane plus alkanolamine, the ratio by weight of the polyhydrogen siloxane to the alkanolamine ranging from about 2:1 to 1:10.

3. An inorganic pigment according to claim 1, comprising TiO2 or a titanate.

4. An inorganic pigment according to claim 1, wherein the polyhydrogen siloxane has more than 5 Si atoms and comprises the units [R2R' - SiO1/2] ; [RH - SiO3] , [R'-SiO3/2] and [SiO2]

wherein R and R' each independently is hydrogen or an alkyl, cycloalkyl, aryl or alkenyl radical.

5. An inorganic pigment according to claim 4, wherein the polyhydrogensiloxane is a polyalkylhydrogen siloxane, a poly-arylhydrogen siloxane, a polyalkenylhydrogen siloxane, or a polyarylalkylhydrogen siloxane.

6. An inorganic pigment according to claim 5, wherein the polyhydrogen siloxane is a polymethylhydrogen siloxane.

7. An inorganic pigment according to claim 1, wherein the alkanolamine comprises at least one of triethanolamine, triiso-propanolamine, diethanolamine, diisopropanolamine and 2-amino-2-methyl-propanol-l.

8. An inorganic pigment according to claim 7, wherein the polyhydrogen siloxane is a polymethylhydrogen siloxane having more than 5 Si atoms, and the precoated pigment comprises TiO2 or a titanate carrying an inorganic coating, the polyhydrogen siloxane plus alkanolamine ranging from about 0.3 to 1 % by weight of the pigment and the ratio by weight of the polyhydrogen siloxane to alkanolamine ranging from about 1:2 to 1:5.

9. In the preparation of an inorganic pigment wherein the pigment is produced by chemical reaction and is thereafter micronized, the improvement which comprises coating the pigment before or during micronization with a polyhydrogen siloxane and an alkanolamine.

10. A process according to claim 9, wherein the alkanolamine comprises at least one of triethanolamine, triisopropanolamine, diethanolamine, diisopropanolamine and 2-amino-2-methyl-propanol-1, the polyhydrogen siloxane is a polymethylhydrogen siloxane having more than 5 Si atoms, and the pigment comprises TiO2 or a titanate carrying an inorganic coating, the polyhydrogen siloxane plus alkanolamine ranging from about 0.3 to 1 % by weight of the pigment and the ratio by weight of the polyhydrogen siloxane to alkanolamine ranging from about 1:2 to 1:5.

11. A polymeric material pigmented with a pigment according to claim 1.

Le A 19. 541?US