FR2530650A1 - PIGMENT PRESERVING ITS IMPROVED COLOR FOR PAINT COMPOSITIONS USING LATEX VEHICLES - Google Patents

Abstract

A.COMPOSITION OF AQUEOUS EMULSION PAINT CONTAINING PRIMARILY ACRYLIC POLYMER EMULSION, THICKENER, DISPERSANTS AND PIGMENT COLOR; B. CHARACTERIZED IN THAT, IN ORDER TO IMPROVE THE COLOR STABILITY AND THE LIGHTFASTNESS OF THE PAINT COLOR, A COLORING PIGMENT IS ADDED TO THE FORMULATION, CONSISTING OF VERY FINALLY DIVIDED PARTICLES OF MANGANOMANGANIC OXIDE IN FUME.

Description

t 530650 1. "Pigment retaining its improved color for

  The invention relates in general to coating products using aqueous emulsions. More particularly, the invention relates to

  paint compositions based on aqueous emulsions

  holding a new dye with Enhanced Properties

  to increase the color stability of these paints.

  This request is a partial continuation of the request

  Serial 343 550 filed on January 28, 1982.

  emulsion-based paint compositions

  Aqueous solutions are prepared by dispersing a

  or more pigment dyes in water containing

  appropriate additives such as surfactants,

  stabilizers, dispersants and thickeners, and then mixing film-forming agents, such as acrylic polymers, acrylic copolymers and

  emulsions containing acrylic polymers A requirement

  this essential posed to a pigment whatever it is, is

  first, that it must give a distinctive and agreeable color

  ble when added to the paint composition, either alone or in combination with other pigments.

  The pigment must be stable in order to maintain its colora-

  for an extended period of time Another important requirement

  bearing is that the pigment must have a dimension of

  very small particles, usually less than 10

believe about.

  2. The thinness of the particles increases the ability of the dispersion to disperse in the belt mixture during operations, and at the same time ensures that the paint will be evenly distributed in a thin layer after application to the belts. a surface, without any scratches or

  Another imperfection This last requirement is very important

  load bearing, naturally, in cases where the paint is to be applied with a running brush, roller or

zmr nullv erisation.

  An important object of the invention is to

  An additional object of the invention is to provide an aqueous emulsion paint composition having an improved aqueous pigment for use in aqueous emulsion dyeing compositions.

  good color stability and light fastness

  - relatively important when exposed to the sun. According to the invention, an improved colored pigment is produced for use in

  aqueous emulsion paint compositions which

  holds an ammonanomanganic oxide (In 304) in smoke, or

  material containing the manganomanganic oxide in smoke

  main component The Ihn 304 dye in smoke is

  first dispersed in water containing surfactants

  active agents, dispersants, diluent antifoam, stabilizers, glycols and the like, and is then introduced into an aqueous emulsion based on acrylic polymers or acrylic copolymers.

  constitute from 5 to 50% by weight of the non-part

  total volatile paint composition.

  The invention is hereinafter described in a manner

  detailed reference, with reference to the appended drawing

  a single report showing the distribution of

  particle sizes for a recommended manganomanganic oxide, containing the material intended to be 3.-

  used as a pigment dye.

  The invention is based on this finding that manganomanganic oxide in smoke, or a material

  containing a predominant proportion of manganese

  Manganese in the form of fine dispersion is a new and ideal dye for use in a variety of Zn-specific aqueous emulsion paints,

  the colored pigment i 304 in smoke is especially used

  in applications where iron oxide pigments have been used in the preparation of paints in colored aqueous emulsions.

  for example, that manganomanganic oxide in fine smoke

  divided, when used as a pigment dye,

  a dark brown color or a red-brown color

  dark, which is similar, while being very easy to

  dye brown pigmentation given by a number of synthetic iron oxide pigments, that is to say yellow, tan or red-brown It has also been found that the pigment pigment In 304 in smoke is stable at temperatures up to about 6000 ° C., whereas, on the other hand, the common iron oxide yellow or havana pigments turn to red iron oxide when heated to temperatures of about 1770 ° C.

  The colored pigment of In 304 in smoke can also be

  duit with a wide margin of joint dimensions that approach or are equal to the particle size

  iron oxide pigments common in the art

  As has been indicated, it is desirable that

  the pigment dye has particular dimensions

  of very fine division, in order to render the pigment

  able to be uniformly distributed throughout the entire

  During the preparation process, the manganomanganic oxide constituting the pigment

  particle size less than about 10 microns.

  As has been said, the pigment dye 4. used in the practice of the inrention is

  the manganomaganic oxide in smoke, or can be a

  position or a platform containing a predoni-

  more than about 60% by weight, of margzanomanganic oxide in smoke. The smoke smoke of the invention is pre-sprayed so that it is not necessary to heat a stream of ozrgene in a ferromanganese melt or on the surface of that bath. The ferroanganese

  produced in a blast furnace, or in an oven

  metallurgical and other at temperatures of 1200 C or more, can contain up to 6% by weight of carbon is usually reduced the carbon content, for example 1.5, ', blowing oxygen, or a oxygen mixture

  and air, through or on the surface of a ferro-

  molten manganese This operation is carried out in a separate ladle which contains a ferro-manganese melt bath melted from the electric furnace and which is at a temperature of 1000 O or more and

  preferably at about 13000 C or higher.

  A method for reducing the carbon content of molten ferroarangese is described in the U.S. Patent.

  3 305 352 issued on 21 November 1967, the description of which

  tion is incorporated herein by reference.

  recommended process, to produce manganomanganese oxide

  that in smoke of the invention, ferro-manganese is poured, from the electric furnace in which it was produced, in a cuvie treatment, such as a pocket or a furnace with a temora, -re about 130000 or more The whole slag is removed from the ground and then

  oxygen from above, on the surface of the ferro-

  man Eanèse melted by any suitable means such as

  one or more common lances blowing oxy-

  the gene, held at about 25 mm above the surface, so as to direct one or more jets of oxygen under a pressure of about 7.75 k / cm 2 to about 10 kg / cm 2 which will come The flow rate of oxygen is about 1,800 kg to 2,260 kg per minute for a melt of 226 kg, in a pocket having about

  7 75 cm in height and 50 cm in inner diameter This procedure

  can be pushed as much as desired.

  thus produced contain very fine particles

  of nano-organic oxide of spherical

  that is easily recovered from lost gases

  using a standard recovery device.

  If desired, manganomanganic oxide

  in smoke of the inr: ention, can be produced as sub-

  product of the specific process described in US Pat. No. 3,305,352 for reducing the carbon content of the ferro-manganese bath. In this case, the ferro-manganese bath will be at a temperature of about 125 ° C., and will blow oxygen at a rate sufficient to heat the bath

  at a temperature of 1700 C before the carbon content

  molten metal has been reduced to 1.5%. The oxygen blowing will be continued until the bath temperature reaches about 1750 C, as described in the patent. The anomanganic oxrde man in smoke is recovered.

  from the lost gases in the usual way.

  The terms Mn 304 in smoke and manganese oxide

  Zanic in smoke used in the specification and in

  the claims, here mean particle smoke

  finely divided, recovered from a

  oxygen blowing in ferro-manganese

describes me above.

  The data below relate to some typical characteristics of manganese oxide fume as specified above for carrying out the invention. Chemical formula: Essentially IM 304 ypically 90 3 9 in 3 oids and more of 4 anoanganic oryde, the rest 39 to 95% by weight and more of oxide m-anganomanganic, the rest

  The use of calcium oxides in manu-

  potassium hydroxide composition with about 1 l of free manganese metal, 5-fold type of chemical analysis, by weight: 65 27 lin; 023 Fe; 0 029 A 1; 0 28 Si, 0 17 C; 0 040 P; O 045 As; 0 46 Ca;

  1.43 Zg; 0 072 X; 0.023 Cr; and O 002 Pb.

  Bulk density: 675 to 1350 kg / m 3: Moisture: typically 0.22% (1 hour at 1070 ° C) Particle size: 98% less than 10 microns (rs = 325 mesh sieve) 13 (50% M 304 in distilled H 20) Shape: spherical Jensity: 4.6 to 4.75 g / cm 3

  53 tability, ermque: no change up to 600 C.

  Current coating technology tends to use pigment dyes with very small particle sizes in order to increase dye yield (dye and dye), prorities

  suspension and uniformity of the distribution of the pig-

  It has been found that, when using a pigment dye according to the invention, the N 304 must have a particle size of less than about 10 microns.

  smoke as described above may contain

  generally about 1 to 2% of particles larger than about 10 microns. As a result, it may be desirable or even necessary in some

  case, to eliminate these particles of large diameter from the fu-

  This is, for example, the pink of the L 304

  in common or by processes

  by shocks, such as by ball milling

  manganomrananic of which 99.5; particles are

  Below about 10 microns can be readily dispersed in the Lre formulation with medium shearing equipment, for example using a Cowles solution-dissolving apparatus. Painting compositions containing smoked 304 having dimensions.

  joints of this order can usually be

  plicated on the surface to be treated without appearing scratches or other imperfections. A typical particle size distribution curve for In 304 in smoke is shown

  in the graph which constitutes the single figure annexed.

  We will be satisfied by the curve that, in the case

  particular of 30 i 4 sorted that has been examined, the distribution

  average particle size bution is about

0.68 micron.

  Below are some types of composi-

  Aqueous emulsion dyes containing flaxseed 304 as the colored pigment according to the invention, which are described below: Ingredients Proportion by weight 40-65 Thickener O, 5-12 dispersant / stabilizer 0.2 -2.0 surfactants 0.2-2.0 antifoam 0.1-1.0 coalescing agent 0.3-6.0 preservatives 0.1-1.5 diluent 0.0-15.0 In 304 smoke 590-30 "'i O 2 0.0-25.0 Nitel O, 0-8.0 2 alkyd or vegetable oil 0.0-10.0 water QS per 100 Emulsion paints

  aqueous solution using a pigment dye

  According to the invention, the ganomanganic smoke compositions can be prepared by the usual methods which are well known in the prior art. For example, the paint compositions can be prepared by first dispersing, in water, additives such as dispersants, thickeners, protective colloids, antifoams, surfactants, etc. The rigorous dye is then dispersed, in common with a diluent, in the aqueous solution, using aearne shear aearne such as an apparatus. of

  : Cowles suspended suspension or a roller mill.

  nes solid particles of Slow pigm and the dilutive are put

  in uniform suspension The pigmented aqueous solution and

  if obtained is then mixed with the latex, the co-agent

  and the rest of the components The physical and characteristic properties of the paint are then examined.

  and, according to the needs, the surface tension is adjusted

  the, the pH, the viscosity and the dispersant of the pigment On

  of course, employ other processes and equi-

with equal success.

  The latex or emulsion that serves as a vehicle

  used in the paint composition according to the invention

  may be any of the film trainers

  well-known, based on acrylic polymer or copolymer

  acrylic latex type, commonly used in the paint industry Rhorlex AC 507 latex, Rhoplex IV 9 and Rhoplex 1 i-23, produced by ohnm & Haas CO, and TUCAR 336, UCAR 515, UCAR 4341 and UCAR 4358, rar products Union Carbide Corp are typical emulsions, among the many emulsions that can be found in

  the trade that can be used for practicing

than the invention.

  Protective emulsifiers and colloids

  are used in the composition of paint in order to

  to the desired consistency and viscosity.

  The viscosity and the viscosity must be such that the paint can be easily cleaned on the surface to be treated, in a uniform film or film of 9.- the desired edger These additives also play the role protective colloids that protect against coagulation of pigments and diluents in the presence of electrolytes or excessive shearing Thickening agents, in particular

  v common with surfactants, maintain the pigments

  in suspension and stabilize the viscosity of the paint.

  The choice of a particular enumerant will depend on a number of factors, such as, for example, the type of emulsion and the volume concentration of the pigment, and

of the rheology of the coating.

  In general, thickeners, of the cellulosic type or of acid salts of acrylic polymers, commonly used in the paint industry can

  be used in emulsion

  aqueous solution containing 304 nr.

  For example, the salts of the acid may be

  lycarboxylic such as acrysol G-110 (registered trademark

  from Rohm to Haas Co.) or cellulosic thickeners

  such as QP 4400 (trademark of Union Carbide Corp). As other thickeners, mention may be made of those sold under the trade names Epaississant 845,

  Thickener 4358 and Thickener E 845 (manufacturer's marks

only from Rohm t- & Haas Co).

  It is also possible to use a dispersing agent and a stabilizer combined in the paint formulation.

  to ensure that all the pigment and other ingredients

  are uniformly dispersed in the painting On

  may use, for this purpose, different types of agents

  persistant, anionic, nonionic and polymeric, such as those produced under the trademark 2 amol 731 and: amol 850 (Rohm and Hlass Co) As other dispersants than

  Triton X-100 (phenoxycyclohexyl) can be used.

  polyethoxyethanolalkoylaryl), Triton X-301 (ether sulfate)

  aloylaryl) and Triton X-405 (polyether alcohols

  laryl) all trademarks of Rohm & Hass Co. 10. The paint formulations of the invention may also include other ingredients which are useful in the paint industry.

  for example an antifoam agent such as Nopco NDW

  Bricked by I Nopco Chemical Compar 4 yo We can also use

  common driers, in cases where the paint is

  an alkyd resin such ingredient These ingredients

  co-operate with cobalt and zinc driers, for example

  It is also possible to use a coalescing agent such as

  2,2,4-trimethyl-1,3-pentane-butyl monoisorate

  diol, produced by East-man Xodak under the tradename Texanol. One can also use, in the comnpositions

  other ingredients known as

  ordinarily, preservatives, anti-alcohols (for example ethylene-

glycol) and modifiers.

  In some experiments, it has been found that n 304 can be combined with pigments in smoke.

  such as titanium dioxide (Ti 02), for

  For example, in one of these tests, a smoke of Mn 304 was mingled with di ff erent pro rtings of '02, and noted the different types of color.

  In the same tests, we have also

  lemeht prepared, for comparison, control samples containing 100% I Mn 304 in smoke and 100% p of 2 i O 2 It was found that the film of the emulsion was in the case of 100% of Ii 02 (O% mih 304) "basically white", 10 Sn (O "light brown" or "beige" "nh (60, J i O 2)" medium brown "and 100% M Mn 304 (O 't 3, 4

  '02) brown roncê or dark red brown.

  The color of the film of the test in the tests described above can be specified from the following sources: Color, Color, Color, Baltimore, Aryland Colors, colors and Chroma (color) were determined for each emulsion film according to the 11-procedures outlined in:> usell Color 3 ook and are

  data in Table 1 below. In the column

  : 10 :: unsell, the first numeric value and the letter of designation indicate the "nuance", the number following the designation by letter represents the "value", and the

  last number represents the "chroma" (color).

2 to 3 LZAU I

  Definition of color g Xi O 2 '% i N 354 of unsel O. 100 O i 9 5 / go 10 o 5 YR 8/2 O t O 7 5 YR 5/2 O 1 o 00 5 YIR 3/4 In based on the quotation in: X xnsel 17 of Table 1, it will be easily seen that the 'oxide dye

  anganomanganese in smoke of the invention, will have an effect

  coloring and modification on pigments such as O 2 and on those fui produce defined nuances

-L 2

  such as yellow iron oxide, iansa yellow, chromium oxide green, phthalocyanine blue and green

phthalocyanine.

  The following examples will illustrate

the practice of the invention.

3 C.-2 THE 1 -

  An aqueous emulsion paint composition has been prepared using the white dioxide pigment

  of titanium of rutile quality which is the standard

  neral The composition was prepared by melarnging first

  60 g of rutile titanium dioxide together with 70 g of

  ## STR2 ## 0 (p H 9,7), that is to say a 20% aqueous solution of the 745 thickener (Ronhm Haas Co), 2 g of dispersant /

  stabilizer, the Tamol 850 (Rohm & Haas Co), 10 g of

  noxypoly 4thoxy ethanolalcoylaryl, the Triton 100 (Rohm &

  Haas Co), 1.5 g of antifoam, Hevi-Duty A F (Inters-

  Chemicals Inc), 2 g of propylene glycol, 20 g of a medium, and a mean of The results of the tests in box 2 in box II Each ovation 2 5 p Z_ 1 is linked to the 2 nd sonier 2.-

a Car-i, -1 Morbid 'the o-ra 2 -

  ## EQU1 ## where: ## EQU1 ## Thus on the surface -br 4 tes Sai -'a -175 _x 225 n, in sl-_f_'ora-_at to Fine 2.5

We have left 5 1-_rclrS dl-5-

_Gles' a

sai; 1 -

  and then self-help them to

  at the end of the lab: L c, -e Il 1 ztli sant l) a S, e es't

on -lessai and ex-

  The length of this pressure is as follows at the ASMI G 25-70 padéoreter. The slides are tested periodically at the color of the eye and at the same time. The Code is as follows: 13.- According to the code dominated in Canada, the word "FI" is used to indicate that the tl is one, test of solidity to it Fact in the following exe: Li-ole when the colorant t -icgenta 4 ie is the 210 L e pigment 2 li prdi-niguation essentiellemoent blarcn e

  who, after two years of exposure to the ultra-

  violet diminishes in Table II, the abbreviation "la" is used to indicate the attenuatlion

  the liveliness of the complexion-are of this example.

LX 222 -

  A composition of aqueous emulsion paint was prepared using the same ingredients as in the composition of Example 1, except that in this case the 60 g of 2-i were replaced. 57 g of washed OO were then obtained. The Mn O was heated to a temperature of 73 ° C. It was used in the same manner. 73 g of acylated polycarboxylic acid were used. that is, the 485 (Oohm Elaas Ca) enamelizer at the same time as 480 g latex, 71 CAR 4, 398 (Union Carbide Corp) instead of 622 g, which was added. The test was carried out on test poles of the same material, which is described in Example 1, and tested for the same light fastness tests.

  the film was "dark brown" or "dark brown".

lX 3 i Y__LE 3 -

  An emulsion-type paint composition was prepared by dispersing diluents and pigments in a nrrreen emulsion blending a long-lived alkyd into oil, eg Airoplaz 1271 (Spencer Zelg CC), co) containing cobalt siccatives. "and zirconium, with

  In 350 parts of allkyde, we have introduced

  4 g of calcium siloxane ester, Y 4400 (Union Carbide Corp), 8 g of an α-nionic dispersing agent, α-830 (.qohm -: aas Co), 5 g of a surfactant, nonionic active ingredient, C 2 -C 10 (Rohm 1, Haas Co), of the alkyl-aryl-thi th type, unicyclo-zoster, 1-phenyl-2 F, 20 g of To this end, in this process, 150 g of ferric iron oxide were introduced and dispersed in the form of sodium hydroxide. In this case, 35 g of a diluent, Kieia 325 (due to the English ica Coir arn), 75 g of Ca 003 OD g of a rust inhibitor -Bi barium etaborate, 3 usan 1171-I (Trademark of ': Shelter, Ue of Buckman Labs, Inc.) After mixing

  intmeon added 500 g of a styrene copolymber latex

  acrylic, '' Li 4341 (Trademark of Union Carrbide

Coru) and a coalescent agentU.

  As in the previous examples, we have

  -1 14 e) e p 2 e ture on aluminum test plates

  nium nu msrn envi ron 75 x 2259 = with an am-ijator

  for a cell with a metallic wire between

  The mixture was then rolled to a dry film of 2.5 microns in thickness. The film was allowed to cure with the coating at room temperature. The Claauettes were then placed. tests on test racks and subjected to the same tests of solidity to the emulsion An emulsion paint composition was prepared by mixing an emulsion of acrylic, the Rhoplex

  23 (R> ohm & TH 1 aas Co) in commiun with -, n 3 O 4 in smoke.

  The reaction was as follows: 59 g of water, 25 g of a thickening polyacrylate at a concentration of 20 eo,

  845 (Rob Lm & Haas Co), 17.6 g of a disper-

  in the concentration range of 40 to 5, the R-a-81 40 (aohm &

  E: alas Co), 2 g of an ensio-active product of addition of ben-

  octyl benzyl ether, ethylene oxide, 2-iriton CF 10 2: 1-aa o), 28 g of ethyl 2-ene glycol, 5.7 g of 3 sele 7 'oara: stler _ , 3 'J (Dia-mond Shamrock Go), 12 Z a -flat'et zinc oxide, 1' AZO 77 (American Zinc Go), 53 g Ga CO 3 2.1 g Skane i (Rohm & - aas Go) which is a 1 5 -

  (2-r-α-ocyl-1-sothiazolone-3-one) and 1-dihydroxy-

  ## EQU1 ## in which ## EQU1 ## in which ## EQU1 ## is equal to 4, in the 667 mixture of acrylic latex, Rho-plex J 23 Good 3 C 0), 7 hydroxide (28 1,) and D 5.7 dlaz-ent coalescent, monoisobutyrate 1, 3-te-1'a-aiol-lexanol (Eastman Zo in-k Co) S-4 The results are as follows: The ratio of the: Ame rn-ni 2-b which is S -1 in the experiments 71 and 5, and it is allowed to The color of the film was dark. The color of the film was now dark red-brown. There was no change in the color of the film. -,: n Were washed and do not: Like no 3 4 washed, all of which were then submitted to

  They tried to be solidified in the light.

1 7 -S results of these tests e

  using it different from pe L-1-

  In Examples 4 and 4, shown in Table II, it is apparent from the 1-3 tests of lightfastness that 304 in fyze according to the invention, they show a stability of color and color, solid in the light which is equal to or greater than those of the two coats of paint con: 4 Thus, it will be appreciated in particular in connection with the examples of Examples 2 and 4, with the addition of 1 N 504 in smoke. co = - -e pigment dye ,,

* se-, le-ment a weak '12 uz aff: éblisser'in 1, -m-

  q 1 ue, of other-la: Zl -S-ant, in llexemule 3, a riz-ment oxjde I fer rouce 'Milk

  proof of bar rate bea- ico, zu higher attenuation-

  (2-10 to -90 h to F-3 to 1000 In another connar 2 _J-

  We will see, from 13 S Table I results, that paint corre- spondents used, the titanium dioxide 16.-

-0 1 _

  In this context, the first step is to increase the number of students at the same time.

3 4

  can be in a lie form -L Lia-

  zein-tures - using ingredients -Is -e_-Is -ue -_-_ s s issants, -dispersanus, etc without the;; Lrz aff' -45 favorable -UE-, We rer 2 c?, i It will be seen that the numbers of coli in the cola are not stable. com cosi-; J y using it _-O no 20 uuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuuu

T A B L E A U II

  Tl''ST DIAFFAIBLISSE 1,11 U 2 Duration (h)

100 200 300 400 500 600 750

  Exeln-nle 1 IL, iiio 1 2 2 1-smoke 1, Lvé 3 Oxide roue 4 Ilin O d e fuin, e j

att att att att.

att att.

att att.

att.

F-8 P-7

F-10 F-9

F-10 F-9

P-6 P-9 P-8

P-6 P-6

F-9 E-8

F-8 P-8

  F-5 P-3 P-8 F-5 F-3 FI-8 F-5 P-3 F-7 r%) Ln - LQ i C> C>, Ln - CD 1 18.-

R 3 Y N ITI <2 I O T S

  1 aqueous emulsion paint composition

  containing one of the acrylic polymers

  a thickener, dispersants and an oirmen-

  characterized in that, in order to improve the color stability and light fastness of the stain color, a coloring agent is added to the formulation

  composed of very finely divided particles of

annial in smoke.

  O O 2 Painting Composition according to the

  1, characterized in that the manganomanganic oxide pigment dye consists of fumed N 304 having the following characteristics: a) the chemical composition contains at least 90% by weight of manganomanganic oxide, the balance being a mixture

  oxides of calcium, magnesium, potassium,

  and silicon, and less than 1% o by weight of

  free metal ganesis and (b) the particle sizes are such that 98 5 'are

  less than about 10 microns.

  3. Painting composition according to the

  1, characterized in that it comprises from 40 to 65% by weight approximately of a latex composition, from 0.5 to 12 d by weight of a thickener, from 0.2 to 2% by weight

  of a dispersant, from 0.2 to 2% by weight of a surfactant

  0.1 to 1% by weight of an antifoam, 0.3 to 6% by weight of a coalescing agent, 0.1 to 1.5% by weight of a preservative From 0 to about 15% by weight of a diluent, from about 5 to about 30% by weight of

  0 to 25; in weight of about Ti O 2, the remainder being water.

  t. Paint composition according to the

  3, characterized in that it contains, in addition,

  from 0 to 8% by weight of antifreeze.

  v. Damping composition according to the

  characterized in that it contains, in addition,

  from 0 to about 10% by weight of an alkyd resin.