Modified particles

BACKGROUND OF THE INVENTION
The present invention relates to modified particles. More particular, it relates to modified particles which show excellent dispersing properties, namely excellent dispersion facility, dispersion homogeneity and dispersion stability, in constituting materials of water-based paints, a process for producing such modified particles, a water-based paint containing said modified particles, and a magnetic recording sheet obtained by coating on water-based paint containing the modified particles as magnetic particles.
Inorganic colored particles such as iron oxide particles and ferric oxide hydroxide particles have been popularly used as a pigment by dispersing the inorganic colored particles in a vehicle as these particles are stable in the air because of being an oxide and also have various colors depending on the difference of their crystal structure, presence or absence of crystal water and other factors.
There has been ever rising requests in recent years for higher performance and quality of the coating films formed on various substrates with paints. For meeting these requests, there has been required an improvement of the properties of the pigment which is considered the most influential factor on the qualities of the coating films such as clearness of color tone, tinting strength, hiding power (obliterating power) and gloss. In other words, it is essential that the pigment used in the paint has excellent dispersing properties, especially excellent dispersion facility, dispersion homogeneity and dispersion stability in the paint vehicle.
This fact is pointed out, for instance, in "The Latest Techniques for Pigment Dispersion", published by the Technical Information Society in 1993, which states on page 15: "Pigment is never used singly and it is always used after dispersed in a binder resin, solvent or other suitable material. The fine pigment particles need to be easily dispersible and also homogeneously dispersed in the binder for obtaining a clear color tone, high tinting strength and other desired performance. However, since finer particles have less stability, it is a matter of great account to maintain stable dispersibility of the pigment particles.", and "The properties required for the pigment may be defined and classified as follows from the various viewpoints. . . . Dispersibility is classified as a matter that affects the physical properties, but it also has close relation to and influences the optical, chemical and specific functional properties. That is, the improvement of dispersibility of the pigment for allowing uniform dispersion not only means enhancement of clearness of color tone, tinting strength, hiding power and gloss of the coating film, but also leads to improvement of chemical properties such as fastness and workability. . . . "
Also, magnetic recording sheets are used expandingly, for the purpose of labor saving and improvement of working efficiency. Such magnetic recording sheets are practically used, for example, for magnetic railway tickets, commutation-tickets, express highway passes, credit cards, ID (identity) cards, telephone cards, orange cards, etc.
These magnetic recording sheets are generally of a structure comprising a non-magnetic support made of a plastic material such as polyvinyl chloride or paper, and stripe-like of magnetic layer formed on one side of the said support by applying thereon a magnetic coating having magnetic particles dispersed in its vehicle, or a magnetic layer being formed over the entirety of one side of the said support, while an image(s) or mark(s) such as picture(s), character(s), letter(s), etc., being printed on the other side of the support.
Paints or coating compositions are divided into two types depending on the solvent used: solvent-type paints using an organic solvent as main solvent and water-based paints using water as main solvent. Water-based paints are favored in terms of safety, hygiene and environmental protection as water-based paints have no serious atmospheric pollution problem, are more advantageous in saving of resources and energy, and also have little risk of causing a fire.
However, since the dispersion mechanism of the particles in a water-based paint is different from that in the conventional solvent-type paints, it is impossible to disperse the particles in a vehicle by the same dispersion techniques as used for the solvent-type paints. An aqueous resin (color developer) is used in a water-based paint. A solvent-type resin (color developer) exists in a dissolved state with a certain spread, but an aqueous resin exists mostly in the form of particles such as emulsion polymer particles or colloidal particles. Consequently it becomes a problem how it should be dispersed the particles in the vehicle and how long it should take until effected, that is, dispersion facility and dispersion homogeneity of particles such as magnetic particles, pigment particles or the like, becomes the problem of primary consideration. Then dispersion stability comes into question since the particles tend to reagglomerate due to less extension of aqueous resin. This problem of dispersibility is serious especially in case the particles dispersed in a water-based paint have magnetization because, in this case, there takes place magnetic agglomeration of the particles.
For example, imperfect dispersion of magnetic particles in a water-based paint is causative of poor smoothness of the magnetic coating surface or deterioration of magnetic properties such as squareness, resulting in serious troubles such as variation of output and dropout of the produced magnetic recording sheet.
It has thus been strongly required to provide particles such as magnetic particles, pigment particles or the like which are excellent in dispersion facility, dispersion homogeneity and dispersion stability by improving the dispersibility of the particles in a water-based paint.
For improving dispersibility of inorganic particles in vehicle, it has been propose to coat inorganic particle surfaces with various kinds of inorganic or organic compounds. For example, coating of the inorganic particle surfaces with organopolysiloxanes (Japanese Patent Publication (KOKOKU) Nos. 56-43264, 57-2641, 58-13099, 60-3430, 1-54379 and 5-4129, Japanese Patent Application Laid-Open (KOKAI) Nos. 57-67681, 59-15455, 61-127767, 62-87237, 63-113082, 63-168346, 63-202671, 1-182368, 2-212561, 3-163172, 4-68041, 5-111631, 5-214264, 5-339518, etc.), coating of the inorganic particle surfaces with organic silicon compounds (Japanese Patent Application Laid-Open (KOKAI) Nos. 50-44498, 51-40903, 57-200306, 62-87237, 4-170323, etc.) and coating of the inorganic particle surfaces with a silane coupling agent (Japanese Patent Application (Laid-open) Nos. 49-59608, 51-13489, 52-44794, 54-7310, 54-110999, 55-94968, 60-240769, 4-18930, 4-78433, 5-239446, etc.) have been proposed.
In Japanese Patent Application (Laid-open) No. 62-187772, the addition of a polyester-containing polysiloxane having effects of reducing tackiness and bettering lubricity, into the coating composition, and a lacquer or molding composition comprising a resin component and an effective anti-adhesive properties producing and lubricity increasing amount of a polyester-containing polysiloxane mixed with the resin component are described.
Thus, the conventional particles having their surfaces coated with organopolysiloxanes, organic silicon compounds or silane coupling agents mentioned above are unsatisfactory in dispersion facility, dispersion homogeneity and dispersion stability in vehicle as shown in the Comparative Examples described later.
Also, the lacquer or molding composition containing a polyester-containing polysiloxane described in Japanese KOKAI No. 62-187772 falls short of providing the desired improvements of dispersing properties such as dispersion facility, dispersion homogeneity and dispersion stability, of the particles in vehicle as shown in a Comparative Example described later.
It is more strongly required at present to provide particles which are improved in particle dispersibility in a water-based paint, i.e., are excellent in dispersion facility, dispersion homogeneity and high dispersion stability. However, no such particles are yet available.
The technical subject of the present invention is to provide the modified particles improved in dispersibility of the particles in water-based paints, which are easy to disperse, can be dispersed homogeneously and have excellent dispersion stability.
As a result of the present inventors' earnest studies, it has been found that by mixing inorganic particles such as inorganic colored particles and magnetic particles with a polysiloxane modified by a compound selected from the group consisting of polyethers, polyesters and aralkyls, the thus obtained modified particles comprising the inorganic particles having their surfaces coated with a polyethers-, polyesters- and aralkyls-modified polysiloxane, have excellent dispersibility and dispersion stability in the base composition of water-based paints. The present invention has been attained on the basis of this finding.
SUMMARY OF THE INVENTION
An object of the present invention is to provide modified particles having excellent dispersion facility (easy dispersibility), dispersion homogeneity (homogeneous dispersibility) and dispersion stability in vehicles, and a process for industrial production of such modified particles.
To accomplish the aim, in a first aspect of the present invention, there are provided modified particles comprising inorganic particles as core particles, and at least one polysiloxane modified with at least one selected from the group consisting of polyethers, polyesters and aralkyls, which is coated on the surfaces of the core particles.
In a second aspect of the present invention, there is provided modified particles comprising inorganic colored particles as core particles, and at least one polysiloxane modified with at least one selected from the group consisting of polyethers, polyesters and aralkyls, which is coated on the surfaces of the core particles.
In a third aspect of the present invention, there is provided modified particles comprising magnetic particles as core particles, and at least one polysiloxane modified with at least one selected from the group consisting of polyethers, polyesters and aralkyls, which is coated on the surfaces of the core particles.
In a fourth aspect of the present invention, there is provided modified particles comprising inorganic particles as core particles, squaric acid which is coated on the surfaces of the core particles, and at least one polysiloxane modified with at least one selected from the group consisting of polyethers, polyesters and aralkyls, which is coated on the squaric acid-coated particle surfaces of the core particles.
In a fifth aspect of the present invention, there is provided modified particles comprising inorganic colored particles as core particles, squaric acid which is coated on the surfaces of the core particles, and at least one polysiloxane modified with at least one selected from the group consisting of polyethers, polyesters and aralkyls, which is coated on the squaric acid-coated particle surfaces of the core particles.
In a sixth aspect of the present invention, there is provided modified particles comprising magnetic particles as core particles, squaric acid which is coated on the surfaces of the core particles, and at least one polysiloxane modified with at least one selected from the group consisting of polyethers, polyesters and aralkyls, which is coated on the squaric acid-coated particle surfaces of the core particles.
In a seventh aspect of the present invention, there is provided a pigment comprising modified particles comprising inorganic colored particles as core particles, and at least one polysiloxane modified with at least one selected from the group consisting of polyethers, polyesters and aralkyls, which is coated on the surfaces of the core particles.
In an eighth aspect of the present invention, there is provided a pigment comprising modified particles comprising inorganic colored particles as core particles, squaric acid which is coated on the surfaces of the core particles, and at least one polysiloxane modified with at least one selected from the group consisting of polyethers, polyesters and aralkyls, which is coated on the squaric acid-coated particle surfaces of the core particles.
In a ninth aspect of the present invention, there is provided a water-based paint comprising a paint base material and a pigment comprising modified particles comprising inorganic colored particles as core particles, and at least one polysiloxane modified with at least one selected from the group consisting of polyethers, polyesters and aralkyls, which is coated on the surfaces of the core particles.
In a tenth aspect of the present invention, there is provided a water-based paint comprising a paint base material and a pigment comprising modified particles comprising inorganic colored particles as core particles, squaric acid which is coated on the surfaces of the core particles, and at least one polysiloxane modified with at least one selected from the group consisting of polyethers, polyesters and aralkyls, which is coated on the squaric acid-coated particle surfaces of the core particles.
In an eleventh aspect of the present invention, there is provided a magnetic water-based paint comprising a paint base material and magnetic particles comprising modified particles comprising magnetic particles as core particles, and at least one polysiloxane modified with at least one selected from the group consisting of polyethers, polyesters and aralkyls, which is coated on the surfaces of the core particles.
In a twelfth aspect of the present invention, there is provided a magnetic water-based paint comprising a paint base material and magnetic particles comprising modified particles comprising magnetic particles as core particles, squaric acid which is coated on the surfaces of the core particles, and at least one polysiloxane modified with at least one selected from the group consisting of polyethers, polyesters and aralkyls, which is coated on the squaric acid-coated particle surfaces of the core particles.
In a thirteenth aspect of the present invention, there is provided a magnetic recording sheet comprising a non-magnetic support and a magnetic layer formed by applying a magnetic water-based paint comprising a paint base material and magnetic particles comprising modified particles comprising magnetic particles as core particles, and at least one polysiloxane modified with at least one selected from the group consisting of polyethers, polyesters and aralkyls, which is coated on the surfaces of the core particles, on at least a part of said support and at least one side of said support,
the surface roughness of said magnetic layer being not more than 0.35 .mu.m and the squareness of said magnetic layer being not less than 0.87.
In a fourteenth aspect of the present invention, there is provided a magnetic recording sheet comprising a non-magnetic support and a magnetic layer formed by applying a magnetic water-based paint comprising a paint base material and magnetic particles comprising modified particles comprising magnetic particles as core particles, squaric acid which is coated on the surfaces of the core particles, and at least one polysiloxane modified with at least one selected from the group consisting of polyethers, polyesters and aralkyls, which is coated on the squaric acid-coated particle surfaces of the core particles, on at least a part of said support and at least one side of said support,
the surface roughness of said magnetic layer being not more than 0.35 .mu.m and the squareness of said magnetic layer being not less than 0.87.
In a fifteenth aspect of the present invention, there is provided a process for producing modified particles, which comprises mixing, at not less than 80.degree. C., inorganic particles and at least one polysiloxane modified with at least one selected from the group consisting of polyethers, polyesters and aralkyls to coat the surfaces of said particles with said modified polysiloxane.
In an sixteenth aspect of the present invention, there is provided a process for producing modified particles, which comprises adding squaric acid to an aqueous suspension containing the inorganic particles, followed by filtering and drying to coat the particle surfaces with squaric acid, and then mixing, at not less than 80.degree. C., said squaric acid-coated inorganic particles and at least one polysiloxane modified with at least one selected from the group consisting of polyethers, polyesters and aralkyls to overlay said squaric acid-coated particle surfaces with said polysiloxane.
DETAILED DESCRIPTION OF THE INVENTION
The inorganic particles usable as core particles in the present invention include inorganic colored particles of various kinds of pigment such as white pigment, black pigment, yellow pigment, orange pigment, brown pigment, red pigment, violet pigment, blue pigment, green pigment, etc., and magnetic particles such as magnetoplumbite-type ferrite particles, magnetic iron oxide particles, etc.
The inorganic colored particles according to the present invention are the particles having high tinting strength and, when kneaded with a color developer, capable of giving a color to a coating film or molded product. Specifically, such particles include white colored particles such as particles of zinc white (ZnO), white lead (2PbCO.sub.3.Pb(OH).sub.2), basic lead sulfate (3PbSO.sub.4.PbO.about.2PbSO.sub.4.PbO), lead sulfate (PbSO.sub.4), lithopone (ZnS+BaSO.sub.4), zinc sulfate (ZnS), titanium oxide (TiO.sub.2) and antimony oxide (Sb.sub.2 O.sub.3); black colored particles such as particles of carbon black (C), black lead (C) and black iron oxide (FeOx.Fe.sub.2 O.sub.3 (0<.times..ltoreq.1)); yellow colored particles such as particles of chrome yellow (PbCrO.sub.4), zinc yellow (ZnCrO.sub.4), barium chromate (BaCrO.sub.4), cadmium yellow (CdS), yellow ferric oxide hydroxide (FeOOH.nH.sub.2 O), loess (Fe.sub.2 O.sub.3.SiO.sub.2.Al.sub.2 O.sub.3), titan yellow (TiO.sub.2.NiO.Sb.sub.2 O.sub.3), lead cyanamide (Pb(CN).sub.2) and calcium plumbate (Ca.sub.2 PbO.sub.4); orange colored particles such as particles of chrome orange (PbCrO.sub.4.PbO) and chrome vermilion (PbCrO.sub.4.PbMoO.sub.4.PbSO.sub.4); brown colored particles such as particles of brown iron oxide (.gamma.-Fe.sub.2 O.sub.3) and umber (Fe.sub.2 O.sub.3 +MnO.sub.2 +Mn.sub.3 O.sub.4); red colored particles such as particles of red iron oxide (hematite, .alpha.-Fe.sub.2 O.sub.3), red lead (Pb.sub.3 O.sub.4), vermilion (HgS), cadmium red (CdS+CdSe), cadmium mercury red (CdS +HgS) and antimony vermilion (2Sb.sub.2 S.sub.3.Sb.sub.2 O.sub.3 or Sb.sub.2 S.sub.3.Sb.sub.2 O.sub.3); violet colored particles such as particles of cobalt violet (Co.sub.3 (PO.sub.4).sub.2, Co.sub.3 (PO.sub.4).sub.2.8H.sub.2 O), cobalt violet (Co.sub.3 (AsO.sub.4).sub.2, Co.sub.3 (AsO.sub.4).sub.2.8H.sub.2 O) and manganese violet (Mn.sub.2 (PO.sub.4).sub.3, (NH.sub.4).sub.2 Mn(P.sub.2 O.sub.7).sub.2); blue colored particles such as particles of ultramarine (3NaAl.SiO.sub.4.Na.sub.2 S.sub.2, 2(Na.sub.2 O.Al.sub.2 O.sub.3.2SiO.sub.2).Na.sub.2 S.sub.2), prussian blue (Fe.sub.4 �Fe(CN).sub.6 !.sub.3.nH.sub.2 O), cobalt blue (CoO.nAl.sub.2 O.sub.3) and cerulean blue (CoO.nSnO.sub.2.mMgO (n=1.5 to 3.5, m=2 to 6); and green colored particles such as particles of chrome green (prussian blue+chrome yellow), zinc green (zinc yellow+prussian blue), chromium oxide (Cr.sub.2 O.sub.3), veridiam (Cr.sub.2 O(OH).sub.4), emerald green (Cu(CH.sub.3 CO.sub.2).sub.2. 3CuO(AsO.sub.2).sub.2) and cobalt green (CoO.ZnO.MgO).
Among them, zinc white (ZnO), white lead (2PbCO.sub.3.Pb(OH).sub.2), titanium oxide (TiO.sub.2), antimony oxide (Sb.sub.2 O.sub.3), black iron oxide (FeOx.Fe.sub.2 O.sub.3 (0<.times..ltoreq.1)), chrome yellow (PbCrO.sub.4), zincyellow (ZnCrO.sub.4), cadmium yellow (CdS), yellow iron oxide hydroxide (FeOOH.nH.sub.2 O), titan yellow (TiO.sub.2.NiO.Sb.sub.2 O.sub.3), chrome vermilion (PbCrO.sub.4.PbMoO.sub.4.PbSO.sub.4), brown iron oxide (.gamma.-Fe.sub.2 O.sub.3), red iron oxide (.alpha.-Fe.sub.2 O.sub.3), cadmium red (CdS+CdSe), cadmium mercury red (CdS+HgS), cobalt blue (CoO.nAl.sub.2 O.sub.3), chrome green (prussian blue+chrome yellow), and chromium oxide (Cr.sub.2 O.sub.3) are preferred. Black iron oxide (FeOx.Fe.sub.2 O.sub.3 (0<.times..ltoreq.1)), red iron oxide (.alpha.-Fe.sub.2 O.sub.3), brown iron oxide (.gamma.-Fe.sub.2 O.sub.3), yellow iron oxide hydroxide (FeOOH.nH.sub.2 O), titanium oxide (TiO.sub.2), chrome yellow (PbCrO.sub.4), and chromium oxide (Cr.sub.2 O.sub.3) are more preferred.
The inorganic colored particles according to the present invention don't include particles of extender pigments which are low in tinting strength and become transparent or semitransparent when kneaded with a vehicle, for example, particles composed of sulfates, silicates, oxides, hydroxides or carbonates of Ba, Ca, Al, Si or Mg.
Magnetoplumbite-type ferrite particles usable as magnetic particles in the present invention include barium ferrite particles, strontium ferrite particles, barium-strontium ferrite particles and particles wherein at least one element such as Co, Ti, Zn, Sn, Al and Ni, is contained in the above-mentioned particles for controlling the magnetic properties. The particle shape is not specified and it may be, for instance, plate-like or irregular, but in view of orientability in the paint, plate-like particles are preferred.
As magnetic iron oxide particles, there can be used magnetite (FeOx.Fe.sub.2 O.sub.3) particles, maghemite particles, particles wherein the above-mentioned particles are doped with Co, particles wherein the surfaces of the above-mentioned particles are coated or modified with a Co compound, particles at least one element such as Al, Si, Zn, P or Sn is contained in the above-mentioned particles, and particles wherein the surfaces of the above-mentioned particles are coated with a Al, Si, Zn, P and/or Sn compound for improving magnetic properties. The particle shape is not defined and it may be granular, acicular-like, spindle-shaped, plate-like, etc.
The average diameter of the inorganic particles of the present invention is 0.01 to 20 .mu.m.
An aspect of the present invention is explained in detail using as the inorganic colored particles, iron oxide-based particles and iron oxide hydroxide-based particles, and as the magnetic particles magnetoplumbite-type ferrite particles and magnetic iron oxide particles.
In the inorganic colored particles used in the present invention, iron oxide-based particles such as red iron oxide (.alpha.-Fe.sub.2 O.sub.3) particles, black iron (FeOx.Fe.sub.2 O.sub.3 (0<.times..ltoreq.1)) particles, brown iron oxide (.gamma.-Fe.sub.2 O.sub.3) particles, etc., and yellow iron oxide hydroxide-based particles such as goethite (.alpha.-FeOOH) particles, akaganeite (.beta.-FeOOH) particles, lepidocrocite (.gamma.-FeOOH) particles, etc., may be of any suitable shape such as granular (cubic, octahedral, spherical, etc.), acicular-like, spindle-shaped, plate-like, etc.
In the case of granular particles, the average particle size (average particle diameter) of the iron oxide-based particles or yellow iron oxide hydroxide-based particles used in the present invention is 0.01 to 10 .mu.m, preferably 0.1 to 0.5 .mu.m in view of tinting strength and hiding power (obliterating power). In the case of acicular-like or spindle-shaped particles, The average major axial diameter thereof is 0.1 to 20 .mu.m, preferably 0.1 to 1.0 .mu.m, and the average aspect ratio (average major axial diameter/average minor axial diameter) thereof is 2/1 to 20/1, preferably 3/1 to 10/1 in view of tinting strength and hiding power. In the case of plate-like particles, the average diameter (plate surface diameter) thereof is 0.01 to 20.0 .mu.m, preferably 0.1 to 10.0 .mu.m, and the average thickness thereof is 0.005 to 2.0 .mu.m, preferably 0.01 to 1.0 .mu.m in view of tinting strength and brilliancy.
As the inorganic colored particles other than the said colored iron oxide-based particles and yellow iron oxide hydroxide-based particles, those commercially available as colored particles are usually used. The particle size is preferably 0.01 to 10 .mu.m, more preferably 0.05 to 1.0 .mu.m, still more preferably 0.1 to 0.5 .mu.m in view of tinting strength.
The average particle size of magnetoplumbite-type ferrite particles used as the magnetic core particles in the present invention is preferably 0.01 to 10.0 .mu.m, more preferably 0.1 to 1.0 .mu.m, and the BET specific surface area thereof is preferably 1.0 to 15 m.sup.2 /g, more preferably 2.0 to 10 m2/g. The average plate ratio (plate surface area/thickness) of the particles is preferably 1.5/1 to 20/1, more preferably 3/1 to 10/1, and the coercive force Hc thereof is preferably 100 to 6,000 Oe, more preferably 200 to 5,000 Oe. The saturation magnetization .sigma.s of the particles is preferably 50 to 65 emu/g, more preferably 55 to 65 emu/g.
When the average particle size is too small, the particles may tend to agglomerate magnetically, impairing dispersion of the particles in vehicle. When the average particle size is too large, the obtained magnetic layer surface may tends to have poor smoothness, which is unfavorable to magnetic recording in terms of spacing loss.
When the BET specific surface area is too small, the particles may become coarse and the produced magnetic layer surface has poor smoothness, which is disadvantageous to magnetic recording. When the BET specific surface area is too large, the particles may be either very fine or porous, so that it is hardly possible to obtain good dispersion of the particles.
When the plate ratio is too small, the orientation of the particles under the magnetic field may become insufficient. When the plate ratio is too large, the stacking may generate between particles, so that the particles may tend to agglomerate and the noise may generate.
When the coercive force Hc of the particles is too small, the magnetic product may become susceptible to the external magnetic field, resulting in imperfect protection of recorded information. When the coercive force is too large, since a very strong magnetic field may be required for erasing written information, a structural enlargement of the apparatus may be necessitated, which is undesirable in industrial and economical terms.
In the case of granular particles, the average particle size of the magnetic iron oxide particles is preferably 0.01 to 10.0 .mu.m, more preferably 0.1 to 1.0 .mu.m in view of dispersibility. In the case of acicular-like or spindle-shaped particles, the average major axial diameter thereof is 0.1 to 20 .mu.m, more preferably 0.1 to 1.0 .mu.m, and the average aspect ratio (average major axial diameter/average minor axial diameter) of 2/1 to 20/1, more preferably 3/1 to 10/1 in view of dispersibility and orienting characteristics. In the case of plate-like particles, the average particle diameter (average plate surface diameter) thereof is 0.01 to 20.0 .mu.m, more preferably 0.1 to 10.0 .mu.m, and the average thickness thereof is 0.005 to 2.0 .mu.m, more preferably 0.01 to 1.0 .mu.m in view of dispersibility and orienting characteristics.
In the case of magnetite particles, the coercive force Hc of the magnetic iron oxide particles is preferably 100 to 500 Oe, more preferably 250 to 400 Oe. In the case of maghemite particles, the coercive force Hc of the magnetic iron oxide particles is preferably 210 to 400 Oe, more preferably 250 to 380 Oe. In the case of magnetite or maghemite particles doped with Co or having their surfaces coated or modified with a Co compound, the coercive force Hc of the magnetic iron oxide particles is preferably 300 to 1,500 Oe, more preferably 400 to 900 Oe.
In the case of magnetite particles, the saturation magnetization .sigma.s of the magnetic particles is preferably 75 to 90 emu/g, more preferably 78 to 90 emu/g. In the case of maghemite particles, the saturation magnetization .sigma.s of the magnetic particles is preferably 70 to 85 emu/g, more preferably 75 to 85 emu/g. In the case of magnetite or maghemite particles doped with Co or having their surface coated or modified with a Co compound, the saturation magnetization .sigma.s of the magnetic particles is preferably 70 to 90 emu/g, more preferably 75 to 90 emu/g.
The polysiloxanes modified with at least one compound selected from the group consisting of polyethers, polyesters and aralkyls, which can be applied to coat the surfaces of the inorganic particles of the present invention (these polysiloxanes are hereinafter referred to as "modified polysiloxanes"), include the following:
Polyether-modified polysiloxanes represented by the following formula (I): ##STR1## wherein R.sup.1 represents .paren open-st.CH.sub.2 .paren close-st..sub.l.spsb.1 -- wherein l.sup.1 is a number of 1 to 15, preferably 1 to 11; R.sup.2 represents .paren open-st.CH.sub.2 .paren close-st..sub.m.spsb.1 --CH.sub.3 m.sup.1 is a number of 0 to 15, preferably 0 to 12; R.sup.3 represents H, OH, COOH, NCO, NH.sub.2, --CH.dbd.CH.sub.2, --C(CH.sub.3).dbd.CH.sub.2 or .paren open-st.CH.sub.2 .paren close-st..sub.n.spsb.1 --CH.sub.3 wherein n.sup.1 is a number of 0 to 15, preferably 0 to 11; R.sup.4 represents H or .paren open-st.CH.sub.2 .paren close-st..sub.p.spsb.1 --CH.sub.3 wherein p.sup.1 is a number of 0 to 15, preferably 0 to 11; q.sup.1 is a number of 1 to 15, preferably 2 to 11; x.sup.1 is a number of 1 to 50, preferably 1 to 20; and y.sup.1 is a number of 1 to 300, preferably 4 to 150.
Polyester-modified polysiloxanes represented by the following formula (II): ##STR2## wherein R.sup.5 represents .paren open-st.CH.sub.2 .paren close-st..sub.l.spsb.2 -- wherein l.sup.2 is a number of 1 to 15, preferably 1 to 11; R.sup.6 and R.sup.7 represent .paren open-st.CH.sub.2 .paren close-st..sub.m.spsb.2 -- or ##STR3## and may be same or different wherein m.sup.2 is a number of 1 to 15, preferably 2 to 12; R.sup.8 represents H, OH, COOH, NCO, NH.sub.2, --CH.dbd.CH.sub.2, --C(CH.sub.3).dbd.CH.sub.2 or .paren open-st.CH.sub.2 .paren close-st..sub.n.spsb.2 --CH.sub.3 wherein n.sup.2 is a number of 0 to 15, preferably 0 to 11; R.sup.9 represents H or .paren open-st.CH.sub.2 .paren close-st..sub.p.spsb.2 --CH.sub.3 wherein p.sup.2 is a number of 0 to 15, preferably 0 to 11; q.sup.2 is a number of 1 to 15, preferably 2 to 10; x.sup.2 is a number of 1 to 50, preferably 1 to 20; and y.sup.2 is a number of 1 to 300, preferably 4 to 150.
Aralkyl-modified polysiloxanes represented by the following formula (III): ##STR4## wherein R.sup.10 represents .paren open-st.CH.sub.2 .paren close-st..sub.1.spsb.3 -- wherein 13 is a number of 1 to 15, preferably 1 to 12; R.sup.11 represents H, OH, COOH, NCO, NH.sub.2, --CH.dbd.CH.sub.2, --C(CH.sub.3).dbd.CH.sub.2 or .paren open-st.CH.sub.2 .paren close-st..sub.m.spsb.3 --CH.sub.3 wherein m.sup.3 is a number of 0 to 15, preferably 0 to 12; R.sup.12 represents H or .paren open-st.CH.sub.2 .paren close-st..sub.n.spsb.3 --CH.sub.3 wherein n.sup.3 is a number of 0 to 15, preferably 0 to 11; x.sup.3 is a number of 1 to 500, preferably 1 to 300; and y.sup.3 is a number of 1 to 500, preferably 1 to 300.
The number-average molecular weight of the polyether-modified polysiloxanes represented by the formula (I) is 350 to 500,000, preferably 1,000 to 100,000, more preferably 2,000 to 50,000.
The number-average molecular weight of the polyester-modified polysiloxanes represented by the formula (II) is 400 to 500,000, preferably 1,000 to 100,000, more preferably 2,000 to 50,000.
The number-average molecular weight of the aralkyl-modified polysiloxanes represented by the formula (III) is 350 to 500,000, preferably 1,000 to 100,000, more preferably 2,000 to 50,000.
Examples of the above-described modified polysiloxanes usable in the present invention include BYK-320, BYK-325 and BYK-080 (trade names, produced by BYK Chemie Co., Ltd.) as polyether-modified polysiloxanes; BYK-310 (trade name, produced by BYK Chemie Co., Ltd.) as polyester-modified polysiloxane; and BYK-322 (trade name, produced by BYK Chemie Co., Ltd.) as aralkyl-modified polysiloxane.
The amount of the modified polysiloxane coating the modified particles of the present invention is preferably 0.01 to 10% by weight, more preferably 0.05 to 5.0% by weight (calculated as C) based on the inorganic colored particles as the core particles. When the coating amount of the said modified polysiloxane is less than 0.01% by weight, it may be hardly possible to obtain the modified particles having excellent dispersibility. When the coating amount exceeds 10% by weight, although it is possible to obtain the desired modified particles with excellent dispersibility, the effect of the modified polysiloxane is at saturation and it is of no avail to add more than 10% by weight.
As for the dispersibility of the inorganic colored particles coated on the surface thereof with a modified polysiloxane (modified polysiloxane-coated inorganic colored particles) according to the present invention when used in a solvent-type paint, in the case of red iron oxide particles, gloss of the coating film is not less than 85% when the dispersion time is 45 minutes, and not less than 90% when the dispersion time is 90 minutes, with the reduction percentage of gloss being not more than 6%. In the case of yellow iron oxide hydroxide particles, gloss of the coating film is not less than 80% when the dispersion time is 45 minutes and not less than 85% when the dispersion time is 90 minutes, with the reduction percentage of gloss being not more than 8%. In the case of black iron oxide particles, gloss of the coating film is not less than 80% when the dispersion time is 45 minutes and not less than 85% when the dispersion time is 90 minutes, with the reduction percentage of gloss being not more than 10%. In the case of brown iron oxide particles, gloss of the coating film is not less than 80% when the dispersion time is 45 minutes and not less than 85% when the dispersion time is 90 minutes, with the reduction percentage of gloss being not more than 10%.
As for the dispersibility of the modified polysiloxane-coated inorganic colored particles other than the said colored iron oxide particles and yellow iron oxide hydroxide particles according to the present invention when used in a solvent-type paint, gloss of the coating film is not less than 77% when the dispersion time is 45 minutes and not less than 81% when the dispersion time is 90 minutes, with the reduction percentage of gloss being not more than 10%.
When the modified polysiloxane-coated inorganic colored particles of the present invention are used for a water-based paint, in the case of red iron oxide particles, gloss of the coating film is not less than 80% when the dispersion time is 45 minutes and not less than 85% when the dispersion time is 90 minutes, with the reduction percentage of gloss being not more than 10%. In the case of yellow iron oxide hydroxide particles, gloss of the coating film is not less than 80% when the dispersion time is 45 minutes and not less than 85% when the dispersion time is 90 minutes, with the reduction percentage of gloss being not more than 10%. In the case of black iron particles, gloss of the coating film is not less than 70% when the dispersion time is 45 minutes and not less than 75% when the dispersion time is 90 minutes, with the reduction percentage of gloss being not more than 15%. In the case of brown iron oxide particles, gloss of the coating film is not less than 70% when the dispersion time is 45 minutes and not less than 75% when the dispersion time is 90 minutes, with the reduction percentage of gloss being not more than 15%.
As for the dispersibility of the modified polysiloxane-coated inorganic colored particles other than the said colored iron oxide particles and yellow iron oxide hydroxide particles when used in a water-based paint, the gloss of the coating film is not less than 75% when the dispersion time is 45 minutes and not less than 80% when the dispersion time is 90 minutes, with the reduction percentage of gloss being not more 10%.
As for dispersibility of the modified polysiloxane-coated magnetic particles of the present invention when used in a solvent-type paint, the squareness is not less than 0.87, preferably not less than 0.88, the roughness (Ra) of the coating film is not more than 0.37 .mu.m, preferably not more than 0.35 .mu.m, the Mean-Square Roughness (RMS) of the coating film is not more than 0.44 .mu.m, preferably not more than 0.42 .mu.m, and the changing percentage of Ra after dilution of the coating material showing dispersion stability is not more than 8.9%, preferably not more than 8.5%.
As for the dispersibility of the modified polysiloxane-coated magnetic particles of the present invention when used in a water-based paint, the squareness ratio is not less than 0.86, preferably not less than 0.88, the roughness (Ra) of the coating film is not more than 0.35 .mu.m, preferably not more than 0.30 .mu.m, the RMS is not more than 0.41 .mu.m, preferably not more than 0.36 .mu.m, the changing percentage of Ra on the coating film formed by applying a coating composition after dilution of the coating material, showing dispersion stability is not more than 15%, preferably not more than 10%, and the changing percentage of Ra on the coating film formed by applying a coating composition after preservation of the paint, showing storage stability is not more than 0.45 .mu.m, preferably not more than 0.35 .mu.m.
In the modified particles of the present invention, it is preferable that a coating film of squaric acid (3,4-dihydroxy-3-cyclobutene-1,2-dione) be formed between the inorganic particle surface and the modified polysiloxane coating layer.
The coating amount of squaric acid in the modified particles according to the present invention is preferably 0.01 to 10% by weight (calculated as C) based on the inorganic particles as the core particles. When the coating amount of squaric acid coat is less than 0.01% by weight, it may be hardly possible to obtain the modified particles with excellent dispersibility. When the coating amount exceeds 10% by weight, although it is possible to obtain the desired modified particles with excellent dispersibility, the effect of the squaric acid is saturated and it is of no significance to add the squaric acid more than 10% by weight.
The weight ratio of the coating amount of modified polysiloxane to that of squaric acid in the modified particles according to the present invention is preferably 1:1,000 to 1,000:1, more preferably 1:100 to 100:1, even more preferably 50:1 to 1:50.
As for the dispersibility of the inorganic colored particles coated on the surface thereof with squaric acid and further coated on the surface of the coating layer of squaric acid with a modified polysiloxane (double-coated inorganic colored particles) according to the present invention when used in a solvent-type paint, in the case of red iron oxide particles, gloss of the coating film is not less than 85% when the dispersion time is 45 minutes and not less than 90% when the dispersion time is 90 minutes, with the reduction percentage of gloss being not more than 5%. In the case of yellow iron oxide hydroxide particles, gloss of the coating film is not less than 85% when the dispersion time is 45 minutes and not less than 90% when the dispersion time is 90 minutes, with the reduction percentage of gloss being not more than 5%. In the case of black iron particles, gloss of the coating film is not less than 85% when the dispersion time is 45 minutes and not less than 90% when the dispersion time is 90 minutes, with the reduction percentage of gloss being not more than 5%. In the case of brown iron oxide particles, gloss of the coating film is not less than 80% when the dispersion time is 45 minutes and not less than 85% when the dispersion time is 90 minutes, with the reduction percentage of gloss being not more than 5%.
As for the dispersibility of the said double-coated inorganic colored particles other than the said colored iron oxide particles and yellow iron oxide hydroxide particles according to the present invention when used in a solvent-type paint, gloss of the coating film is not less than 80% when the dispersion time is 45 minutes and not less than 83% when the dispersion time is 90 minutes, with the reduction percentage of gloss being not more than 10%.
As for the dispersibility of the said double-coated inorganic colored particles of the present invention when used in a water-based paint, in the case of red iron oxide particles, gloss of the coating film is not less than 80% when the dispersion time is 45 minutes and not less than 85% when the dispersion time is 90 minutes, with the reduction percentage of gloss being not more than 5%. In the case of yellow iron oxide hydroxide particles, gloss of the coating film is not less than 80% when the dispersion time is 45 minutes and not less than 85% when the dispersion time is 90 minutes, with the reduction percentage of gloss being not more than 5%. In the case of black iron particles, gloss of the coating film is not less than 80% when the dispersion time is 45 minutes and not less than 85% when the dispersion time is 90 minutes, with the reduction percentage of gloss being not more than 5%. In the case of brown iron oxide particles, gloss of the coating film is not less than 80% when the dispersion time is 45 minutes and not less than 85% when the dispersion time is 90 minutes, with the reduction percentage of gloss being not more than 5%.
As for the dispersibility of the said double-coated inorganic colored particles other than the said colored iron oxide particles and yellow iron oxide hydroxide particles according to the present invention when used in a water-based paint, gloss of the coating film is not less than 82% when the dispersion time is 45 minutes and not less than 85% when the dispersion time is 90 minutes, with the reduction percentage of gloss being not more than 8%.
As for the dispersibility of the magnetic particles coated on the surface thereof squaric acid and further coated on the surface of the coating layer of squaric acid with a modified polysiloxane (double-coated magnetic particles) according to the present invention when used in a solvent-type paint, the squareness is not less than 0.88, preferably not less than 0.89, the roughness (Ra) of the coating film is not more than 0.35 .mu.m, preferably not more than 0.33 .mu.m, the Mean-Square Roughness (RMS) is not more than 0.43 .mu.m, preferably not more than 0.42 .mu.m, and the changing percentage of Ra is not more than 8.0%, preferably not more than 7.5%.
As for the dispersibility of the said double-coated magnetic particles when used in a water-based paint, the squareness is not less than 0.86, preferably not less than 0.88, Ra of the coating film is not more than 0.35 .mu.m, preferably not more than 0.30 .mu.m, RMS is not more than 0.40 .mu.m, preferably not more than 0.35 .mu.m, the changing percentage of Ra on the coating film foamed by applying a coating composition after dilution of the coating material, showing dispersion stability is not more than 12.0%, preferably not more than 10.0%, and the Ra on the coating film formed by applying a coating composition after preservation of the coating material, showing storage stability is not more than 0.40 .mu.m, preferably not more than 0.30 .mu.m.
As for the ratio of the modified particles to the base material of the paint in the present invention, the amount of the said modified particles is 0.1 to 200 parts by weight, preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight based on 100 parts by weight of the base material of the paint in view of handling of the coating material.
The paint base material used for solvent-type paints in the present invention comprises a resin, a solvent and optionally suitable additives such as extender pigment, drying accelerator, surfactant, curing promoter, auxiliaries, etc.
The amount of the solvent in the paint according to the present invention is 50 to 5,000 parts by weight, preferably 100 to 2,000 parts by weight based on 100 parts by weight of the resin. When the amount of the solvent is less than 50 parts by weight based on 100 parts by weight of the resin, the vehicle viscosity may become too high to perform homogeneous mixing and dispersion. When the amount exceeds 5,000 parts by weight, the solvent moiety in the coating composition increases to such an extent that dispersing Shear force does not act to the particles during mixing and dispersion.
The resins usable as a component of the base material of the paint in the present invention include those commonly used for solvent-type paints, such as vinyl chloride-vinylacetate copolymer resin, vinyl chloride resin, vinyl acetate resin, nitrocellulose resin, polyvinyl butyral resin, acrylic resin, alkyd resin, polyester resin, polyurethane resin, epoxy resin, phenol resin, melamine resin, amino resin, etc. For water-based paints, the commonly used resins such as water-soluble alkyd resins, water-soluble acrylic resin, water-soluble urethane resin, water-soluble epoxy resin, water-soluble melamine resin, acrylic emulsion resin, acryl-styrene emulsion resin, urethane emulsion resin, epoxy emulsion resin, vinyl acetate emulsion resin, etc., can be used.
As solvent, there can be used those commonly employed for solvent-type paints, such as toluene, xylene, butyl acetate, methyl acetate, methyl isobutyl ketone, butyl cellosolve, ethyl cellosolve, butyl alcohol, methyl ethyl ketone, cyclohexanone, etc. The paint base material used for water-based paints in the present invention comprises a resin, water and optionally a solvent. For water-based paints, butyl cellosolve, butyl alcohol and other commonly used solvents can be employed.
As defoaming agent, the commercially available products such as Nopco 8034 (trade name), SN Defoamer 477 (trade name), SN Defoamer 5013 (trade name), SN Defoamer 247 (trade name), SN Defoamer 382 (trade name) (the above products being available from Sannopco Ltd.), Antifoam 08 (trade name), Emulgen 903 (both being available from Kao Corp.), etc., can be used.
The magnetic recording sheets in the present invention are the ones in which a magnetic layer is formed at least partly on a non-magnetic substrate. A hiding layer for hiding the color of the magnetic layer may be provided on the magnetic layer. There may, further, be provided an adhesive layer for bettering adhesiveness between the magnetic layer and the non-magnetic substrate, and a protective layer for protecting the magnetic layer.
Non-magnetic substrates usable in the present invention include plastics such as vinyl chloride resin, polyesters, etc., paper-plastic composites (paper/polyester/paper, polyester/paper/polyester, etc.) and papers such as slick paper.
Usually, vinyl chloride resin substrate is used for bank card, credit card, cash card, POS card, key card, etc., polyester substrate is used for sealess type commutation ticket, program card, telephone card, etc., composite paper substrate is used for expressway coupon ticket, postal savings register, seal type commutation ticket, etc., and paper substrate is used for expressway pass, process management card, some-types of POS card, railway ticket, pari-mutuel ticket, etc.
In case of vinyl resin substrate, the thickness thereof is preferably 100 to 1,000 .mu.m, more preferably 500 to 900 .mu.m. In the case of polyester substrate, the thickness thereof is preferably 10 to 500 .mu.m, more preferably 100 to 300 .mu.m. In case of the composite paper substrate, the thickness thereof is preferably 50 to 500 .mu.m, more preferably 100 to 300 .mu.m. In case of the slick paper substrate, the thickness thereof is preferably 50 to 1,000 .mu.m, more preferably 100 to 800 .mu.m.
A magnetic layer is provided at a part on one side of the non-magnetic substrate, over the entirety of one side of the substrate, at a part on one side and entirety of the other side of the substrate, or over the entirety of both sides of the substrate. The thickness of the magnetic layer is preferably 0.5 to 20.0 .mu.m, more preferably 1.0 to 10.0 .mu.m.
A process for producing the above-described modified particles of the present invention is illustrated below.
The shape, size, BET specific surface area, coercive force Hc and saturation magnetization .sigma.s of the inorganic particles used as core particles in the present invention are substantially the same as those of the above-described modified particles which have been coated with a specific modified polysiloxane.
It is essential that the polysiloxane used for coating the inorganic particles in the present invention is modified by at least one compound selected from polyethers, polyesters and aralkyls. It should be noted that when using afore-mentioned known organopolysiloxanes such as polydimethylsiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, dimethylpolysiloxy chloride, alkoxypolysiloxane, amino groupend modified polysiloxane, etc., or silane coupling agents, it is impossible to obtain the modified particles with excellent dispersibility such as provided in the present invention, as noted from the Comparative Examples given later.
The afore-mentioned commercially available modified polysiloxanes usable in the present invention are all in the form of solution, and in use, they can be added in the form as they are to the core inorganic particles.
The amount of the modified polysiloxane which is added is preferably 0.05 to 20.0% by weight based on the inorganic particles. When the amount of the modified polysiloxane is less than 0.05% by weight, it may be hardly possible to obtain the magnetic particles with excellent dispersibility envisaged in the present invention. When the amount of the modified polysiloxane exceeds 20.0% by weight, although there can be obtained the desired inorganic particles with excellent dispersibility, the effect of polysiloxane addition is saturated and it is meaningless to add it more than necessary.
In the present invention, mixing of the inorganic particles and the modified polysiloxane is carried out at a temperature not less than 80.degree. C. When the mixing temperature is less than 80.degree. C., the modified polysiloxane viscosity becomes excessively high, thereby hindering uniform coating of the polysiloxane on the inorganic particle surfaces and making it unable to obtain the desired modified particles.
The inorganic particles, before mixed with a modified polysiloxane, are preferably heated at a temperature not less than 80.degree. C. to reduce the water content to not more than 0.2% by weight. When the water content of the inorganic particles is too high, the particles are strongly agglomerated each other by the action of water forming a liquid bridge between the particles, so that it may be hardly possible to effect uniform coating on the individual particles.
Mixing can be performed by a high-speed agitation-type mixer commonly used for mixing the inorganic particles and surface treating agents, such as Henschel mixer, speed mixer, ball cutter, power mixer, hybrid mixer, etc. Henschel mixer is recommended in view of uniform coating of modified polysiloxane.
As for the stirring time, it is essential that the inorganic particles and a modified polysiloxane be mixed up sufficiently in a high-speed agitation mixer, and it is preferable at least 5-minute stirring, more preferably not less than 10 minutes.
Squaric acid, which is available as powder, may be directly added to water or may be previously dissolved in water and added to water so as to adjust a concentration thereof to 0.1 to 50 g/l, preferably 0.5 to 10 g/l, and then added to the inorganic particles, the latter being preferred.
In the present invention, the squaric acid coating treatment can be accomplished by mixing the inorganic particles and an aqueous squaric acid solution at a temperature of 10.degree. to 90.degree. C., filtering and drying.
As for the order of addition of the inorganic particles and aqueous squaric acid solution, either of them may be added first, or both of them may be added at the same time.
The amount of squaric acid added is 0.01 to 30.0% by weight, preferably 0.02 to 25.0% by weight based on the inorganic particles. When its amount added is less than 0.01% by weight, it may be hardly possible to obtain the modified particles with excellent dispersibility. When the squaric acid amount exceeds 30.0% by weight, although there can be obtained the desired modified particles with excellent dispersibility, the effect of addition of squaric acid is saturated and it is of no significance to add it in a greater amount than 30.0% by weight.
As for the aqueous suspension stirring time, it is essential that the inorganic particles and squaric acid be mixed up sufficiently and it is preferable at least 5 minutes, preferably not less than 10 minutes.
For producing a magnetic recording sheet in accordance with the present invention, it is possible to employ various methods, for example, a direct coating method in which a magnetic coating material is directly coated on a non-magnetic substrate, a tape bonding method in which a separately produced magnetic tape is bonded on a non-magnetic substrate, and a magnetic layer transferring method in which a transfer-type magnetic tape is attached on a non-magnetic substrate and then the base is striped off.
The essential point of the aspect of the present invention is that the modified particles having their surfaces coated with a modified polysiloxane show excellent dispersibility, specifically excellent dispersion facility, excellent dispersion homogeneity and high dispersion stability, in both solvent-type and water-based paints.
Regarding the reason why the inorganic particles coated with a modified polysiloxane (namely the modified particles of the present invention) show excellent dispersibility especially in water-based paints, the present inventors refer to the following facts.
In a solvent-type paint, a resin is adsorbed on the inorganic particle surfaces with a spread, so that when the inorganic particles approach each other, there is produced a large repulsive force, so-called steric repulsion effect, by the adsorbed resin to hinder the approach of the inorganic particles to each other, thus allowing the particles to stay stably in the paint.
In a water-based paint, however, since a resin on the inorganic particles in the vehicles exists in the form of particles without a spread on the particle surfaces as mentioned above, the effect of steric repulsion between inorganic particles in a solvent-type paint tends to fail to take place or is slight if produced, so that dispersion of the particles can not be effected smoothly.
It is known that, generally, the higher the absolute value of zeta potential of the suspended particles in a paint, the better is the dispersibility of the suspended particles due to electrostatic repulsion. In the case of the modified particles having their surfaces coated with a modified polysiloxane according to the present invention, the zeta potential in a water-based paint is about -40 to -80 mV, specifically about -45 to -80 mV (in case of magnetic modified particles), or -25 to -55 mV, specifically about -30 to -55 mV (in case of inorganic colored modified particles), as shown in the Examples described later, and the absolute values of the zeta potential is high, so that in a water-based paint the particle surfaces tend to be charged negatively, producing a large electrostatic repulsion between the particles. Further, since the molecular chains of a polyether, polyester or aralkyl are adsorbed on the particle surfaces with a spread, the particle agglomerates tend to break up and the particles are allowed to disperse to a state approximating that of the primary particles due to a synergistic effect of the large electrostatic repulsion and steric repulsion. Thus, the said modified particles are easy to disperse and can be dispersed homogeneously.
Also, after once dispersed to a state approximating that of the primary particles, the said modified particles can be maintained in a dispersed state for a long time by virtue of electrostatic repulsion between the particles, thereby ensuring excellent dispersion stability of the said particles.
The modified particles according to the present invention are the colored particles which can be easily and homogeneously dispersed and have excellent dispersion stability in paints, especially in water-based paints, so that they are suited for use as colored particles for paints or varnishes.
The water-based paint according to the present invention has excellent storage stability owing to the said excellent dispersion characteristics of the modified particles blended in the base material of a paint, especially a water-based paint.
Also, the modified particles according to the present invention are suited for use as magnetic particles in magnetic recording sheets since the said modified particles are the magnetic particles showing excellent dispersibility and orientability in paints, especially in water-based paints, as explained in the Examples given below.
Further, the water-based paint produced by using the magnetic particles according to the present invention has good compatibility with paper because of good dispersibility and orientability of the magnetic particles contained therein and also because of aqueous preparation, so that the said water-based paint finds particularly advantageous application to the magnetic recording sheets using paper as non-magnetic substrate.

EXAMPLES
The present invention will now be described in more detail with reference to the following examples, but the present invention is not restricted to those examples and various modifications are possible within the scope of the invention.
The average diameter of the particles shown in the following Examples and Comparative Examples is the average of the measurements of diameter from an electron micrograph, and the specific surface area of the particles was measured by the BET method.
The thickness and plate ratio of the plate-like particles shown here are the values determined from the specific surface area of the particles measured by the BET method and their average diameter measured in the manner described above.
The particle shape was observed under a transmission electron micrograph and a scanning electron micrograph.
The coating amounts of the modified polysiloxane and squaric acid were shown by the amount of carbon measured by using Horiba Metallic Carbon and Sulfur Analyzer EMIA-2200 (mfd. by Horiba Seisakusho Ltd.).
The dispersibility of the modified inorganic pigment was shown in terms of gloss of the coating film as measured by a digital gloss meter UGV-5D (mfd. by Suga Testing Machine Co., Ltd.) at an angle of incidence of 20.degree.. The higher the gloss, the better is dispersibility. The practical value of gloss is not less than 70%.
The dispersion facility (easy dispersibility) of the modified inorganic pigment was in terms of gloss of the coating film formed by applying a paint obtained by blending the specific component materials at the specific ratios shown below and dispersing a mill base therein for 45 minutes, on a cold rolled steel plate (0.8 mm.times.70 mm.times.150 mm) (JIS G 3141) to a coating thickness of 150 .mu.m, followed by drying. The practical value of gloss is not less than 70%.
The dispersion homogeneity (homogeneous dispersibility) of the modified inorganic pigment was shown in terms of gloss of the coating film formed by applying a paint obtained by blending the specific component materials at the specific ratios shown below and dispersing a mill base therein for 90 minutes (at this point the dispersion is in a state of saturation), on a cold rolled steel plate (0.8 mm.times.70 mm.times.150 mm) (JIS G 3141) to a coating thickness of 150 .mu.m, followed by drying. The practical value of gloss is not less than 75%.
As for dispersion stability of the modified inorganic pigment, a paint prepared by blending the specific component materials at the specific ratios shown below, dispersing a mill base therein for 90 minutes and then diluting the product by adding, in the case of a solvent-type paint, a thinner in an amount of 40% based on the solvent-type paint, and in the case of a water-based paint, water in an amount of 40% based on the water-based paint, was applied on a cold rolled steel plate (0.8 mm.times.70 mm.times.150 mm) (JIS G 3141) to a coating thickness of 150 .mu.m, followed by drying to form a coat and its gloss was measured. The dispersion stability was shown by the difference between gloss of the coating film formed by applying a paint after dilution and that before dilution. In the case of the present invention, the smaller the absolute value of the difference, the better is dispersion stability. The practical value of the differnce of gloss is not more than 15%.
The storage stability of a water-based paint containing the modified inorganic pigment was shown in terms of gloss of the coating film formed by applying a paint prepared by blending the specific component materials at the specific ratios shown below, dispersing a base mill therein for 90 minutes and allowing the preparation to stand for a day, on a cold rolled steel plate (0.8 mm.times.70 mm.times.150 mm) (JIS G 3141) to a coating thickness of 150 .mu.m, followed by drying. The practical value of gloss is not less than 60%.
The smoothness of the magnetic coat surface was shown by center line average roughness (Ra) and mean-square roughness (RMS) determined by measuring the surface smoothness of a coating film formed by applying a paint which was prepared by blending the component materials at the specific ratios described later and dispersing a mill base therein, on a paper-made base film, followed by magnetic field orientation and drying, by using a surface shape meter SURFCOM 575A (mfd. by Tokyo Seimitsu Co., Ltd.).
The uniform dispersibility of the magnetic modified particles is shown in terms of the degree of smoothness of the final magnetic coating film. The smaller the values of Ra and RMS, the better are surface smoothness of the coating film and uniform dispersibility of the magnetic particles in the vehicle.
The dispersibility of the modified magnetic particles was shown by dispersion facility, dispersion stability, storage stability, smoothness of the coating film surface and orientability of the particles in the magnetic layer.
The dispersion facility (easy dispersibility) of the modified magnetic particles was shown by a comparison (difference) of the properties of the magnetic layers formed by using two different kinds of magnetic paint prepared with different durations of mill base dispersion. The smaller the difference, the better is dispersion facility. The practical value of the difference of Ra is not more than 0.1 .mu.m. The practical value of the difference of RS is not more than 0.05.
As for dispersion stability of the modified magnetic particles, diluted paints were prepared by in case of a solvent-type paint, adding a solvent (MEK/toluene/cyclohexane=5/3/2) (40%) to a solvent-type paint obtained by blending the component materials in the specific ratios described later and mixing and dispersing a mill base (2) therein for 120 minutes, and in the case of a water-based paint, adding water (40%) to a water-based paint prepared by mixing and dispersing the said mill base for 60 minutes, and the respective diluted paint was applied to a base film to a thickness of 50 .mu.m and dried to form a magnetic layer and its surface roughness Ra was measured.
The dispersion stability of the said modified magnetic particles was shown by the percentage of increase of the said surface roughness Ra over that of the magnetic layer formed in the same way as described above by using a non-diluted paint. The smaller the percentage, the better is dispersion stability. The practical value is not more than 10%.
The storage stability of the modified magnetic particles in a water-based paint was shown in terms of surface roughness Ra of a coating film formed by applying a paint prepared by blending the component materials in the specified ratios described later and dispersing a base mill therein for 60 minutes, the thus prepared paint being allowed to stand for a whole day, on a paper-made base film to a thickness of 50 .mu.m, followed by drying. A smaller value indicates better storage stability. The practical value is not more than 0.5 .mu.m.
The orientability of the modified magnetic particles was shown in terms of squareness (RS) of a coating film formed by applying a paint obtained by blending the component materials in the specific ratios described later and dispersing a mill base therein, on a substrate, followed by magnetic field orientation and drying. The higher the squareness, the better is orientability of the particles, hence the more suited are the particles for magnetic recording sheets.
The zeta potential of the modified particles in a water-based paint was determined by a zeta potentiometer Model 501 (mfd. by Pen-Kem Corp.) using a suspension prepared by adding 0.5 g of a paint which had been obtained by blending the specific component materials in the specific ratios shown below and dispersing a mill base therein for 90 minutes, to 100 g of pure water, and dispersing the paint by an ultrasonic disperser C-10 (mfd. by Ultrasonic Industry Co., Ltd.) for one minute.
Production of colored iron oxide particles
Example 1
2.5 kg of granular red iron oxide (.alpha.-Fe.sub.2 O.sub.3) particles having an average diameter of 0.25 .mu.m were mixed in a 85.degree. C. Henschel mixer (10-litre capacity) operated at 1,200 r.p.m. for 10 minutes to remove water, reducing the water content of the said red iron oxide particles to 0.11% by weight.
With the Henschel mixer temperature maintained at 85.degree. C., 25 g of a polyether-modified polysiloxane BYK-080 (trade name, produced by BYK Chemie Co., Ltd.) (active ingredient: 100%) (corresponding to 1.0% by weight based on red iron oxide particles) was added at a rate of 2.5 g/min over a period of 10 minutes and mixed for 20 minutes to coat the red iron oxide particle surfaces with the said polyether-modified polysiloxane.
Then the Henschel mixer, with mixing contended, was cooled to room temperature to obtain the red iron oxide particles having their surfaces coated with the polyether-modified polysiloxane.
The obtained red iron oxide particles had a polyether-modified polysiloxane coat of 0.54% by weight.
Examples 2-6 and Comparative Examples 6-13
The same procedure as in Example 1 was carried out except that the kind, amount and heat treatment temperature of the iron oxide particles or iron oxide hydroxide particles and the kind, amount and mixing temperature of the modified polysiloxane were varied to obtain the treated iron oxide particles or iron oxide hydroxide particles. The treating conditions are shown in Tables 1 and 2.
Comparative Examples 1-5
For comparison, there were prepared the non treated iron oxide particles or iron oxide hydroxide particles. The properties of these iron oxide particles or iron oxide hydroxide particles are shown in Table 2.
TABLE 1______________________________________ Coating treatment Iron oxide particles or iron oxide hydroxide particles Major axial diameter Kind Shape (.mu.m)______________________________________Example 1 Red iron oxide Granular 0.25Example 2 Red iron oxide Granular 0.25Example 3 Red iron oxide Granular 0.20Example 4 Yellow iron oxide Acicular 0.41Example 5 Black iron oxide Granular 0.30Example 6 Brown iron oxide Granular 0.28Example 7 Red iron oxide Granular 0.25Example 8 Red iron oxide Granular 0.25Example 9 Red iron oxide Granular 0.20Example 10 Yellow iron oxide Acicular 0.41Example 11 Black iron oxide Granular 0.30Example 12 Brown iron oxide Granular 0.28______________________________________Coating treatmentIron oxide particles oriron oxide hydroxide particles Minor axial BET specific diameter surface area Amount (.mu.m) (m.sup.2 /g) (kg)______________________________________Example 1 -- 7.2 2.5Example 2 -- 7.2 2.5Example 3 -- 10.2 2.5Example 4 0.08 16.9 2.0Example 5 -- 5.5 2.5Example 6 -- 6.0 2.5Example 7 -- 7.2 2.5Example 8 -- 7.2 2.5Example 9 -- 10.2 2.5Example 10 0.08 16.9 2.0Example 11 -- 5.5 2.5Example 12 -- 6.0 2.5______________________________________ Coating treatment Iron oxide particles or iron oxide hydroxide particles Heat treatment Residual Squaric acid water Amount Temp. content added (.degree.C.) (%) Kind (%)______________________________________Example 1 85 0.11 -- --Example 2 90 0.08 -- --Example 3 90 0.09 -- --Example 4 80 0.13 -- --Example 5 85 0.10 -- --Example 6 100 0.07 -- --Example 7 110 0.07 A 1.0Example 8 85 0.10 A 3.0Example 9 120 0.05 A 5.0Example 10 80 0.16 A 1.0Example 11 90 0.10 A 0.5Example 12 85 0.13 A 1.0______________________________________ Coating treatment Specific modified polysiloxane Amount Mixing added temperature Kind (%) (.degree.C.)______________________________________Example 1 Polyether-modified 1.0 85 polysiloxane BYK-080Example 2 Polyether-modified 0.5 110 polysiloxane BYK-080Example 3 Polyether-modified 2.0 95 polysiloxane BYK-080Example 4 Polyether-modified 5.0 85 polysiloxane BYK-325Example 5 Polyether-modified 1.0 95 polysiloxane BYK-310Example 6 Polyether-modified 7.0 95 polysiloxane BYK-322Example 7 Polyether-modified 2.0 100 polysiloxane BYK-080Example 8 Polyether-modified 0.1 90 polysiloxane BYK-322Example 9 Polyether-modified 4.0 90 polysiloxane BYK-320Example 10 Polyether-modified 0.5 80 polysiloxane BYK-310Example 11 Polyether-modified 3.0 85 polysiloxane BYK-080Example 12 Polyether-modified 1.0 90 polysiloxane BYK-080______________________________________ A: 3,4dihydroxy-3-cyclobutene-1,2-dione (produced by Tokyo Kasei Kogyo CO., LTD.)
TABLE 2______________________________________ Coating treatment Iron oxide particles or iron oxide hydroxide particles Major axial Kind Shape diameter (.mu.m)______________________________________Comp. Red iron oxide Granular 0.25Example 1Comp. Red iron oxide Granular 0.20Example 2Comp. Yellow iron oxide Acicular 0.41Example 3Comp. Black iron oxide Granular 0.30Example 4Comp. Brown iron oxide Granular 0.28Example 5Comp. Red iron oxide Granular 0.25Example 6Comp. Red iron oxide Granular 0.25Example 7Comp. Red iron oxide Granular 0.25Example 8Comp. Red iron oxide Granular 0.25Example 9Comp. Red iron oxide Granular 0.25Example 10Comp. Red iron oxide Granular 0.25Example 11Comp. Red iron oxide Granular 0.25Example 12Comp. Red iron oxide Granular 0.25Example 13Comp. Red iron oxide Granular 0.25Example 14______________________________________Coating treatmentIron oxide particles oriron oxide hydroxide particles Minor axial BET specific diameter (.mu.m) surface area (m.sup.2 /g) Amount (kg)______________________________________Comp. -- 7.2 --Example 1Comp. -- 10.2 --Example 2Comp. 0.08 16.9 --Example 3Comp. -- 5.5 --Example 4Comp. -- 6.0 --Example 5Comp. -- 7.2 2.5Example 6Comp. -- 7.2 2.5Example 7Comp. -- 7.2 2.5Example 8Comp. -- 7.2 2.5Example 9Comp. -- 7.2 2.5Example 10Comp. -- 7.2 2.5Example 11Comp. -- 7.2 2.5Example 12Comp. -- 7.2 2.5Example 13Comp. -- 7.2 --Example 14______________________________________ Coating treatment Iron oxide particles or iron oxide hydroxide particles Heat treatment Squaric acid Residual Amount Temp. water added (.degree.C.) content (%) Kind (%)______________________________________Comp. -- -- -- --Example 1Comp. -- -- -- --Example 2Comp. -- -- -- --Example 3Comp. -- -- -- --Example 4Comp. -- -- -- --Example 5Comp. 80 0.11 -- --Example 6Comp. 85 0.12 -- --Example 7Comp. 85 0.10 -- --Example 8Comp. 85 0.10 -- --Example 9Comp. 85 0.11 -- --Example 10Comp. 85 0.11 -- --Example 11Comp. 85 0.13 -- --Example 12Comp. 85 0.12 -- --Example 13Comp. -- -- A 1.0Example 14______________________________________ Coating treatment Specific modified polysiloxane Amount Mixing added temperature Kind (%) (.degree.C.)______________________________________Comp. -- -- --Example 1Comp. -- -- --Example 2Comp. -- -- --Example 3Comp. -- -- --Example 4Comp. -- -- --Example 5Comp. Polyether-modified 0.005 90Example 6 polysiloxane BYK-080Comp. Polydimethylsiloxane 1.0 85Example 7Comp. Methyl 2.0 85Example 8 hydrogensiloxaneComp. Alkoxypolysiloxane 1.0 85Example 9Comp. Methylphenyl- 4.0 85Example 10 polysiloxaneComp. Dimethylpolysiloxy 5.0 85Example 11 chlorideComp. .gamma.-glycidoxypropyl- 0.5 80Example 12 trimethoxysilaneComp. Amino group end 1.0 80Example 13 modified polysiloxaneComp. -- -- --Example 14______________________________________ A: 3,4dihydroxy-3-cyclobutene-1,2-dione (produced by Tokyo Lasei Kogyo CO., LTD.)
Example 7
Water was added to a squaric acid solution prepared previously by adding 5 litres of pure water to 30 g of squaric acid (3,4-dihydroxy-3-cyclobutene-1,2-dione) (produced by Tokyo Kasei Kogyo CO., LTD.) to make the total amount 25 litres, and the mixture was stirred well by a stirrer. The squaric acid concentration in the resulting solution was 1.2 g/litre.
To this squaric acid solution, 3 kg of granular red iron oxide (.alpha.-Fe.sub.2 O.sub.3) particles having an average diameter of 0.25 .mu.m were added gradually, and after mixing and stirring for 30 minutes by a homomixer, the resultant mixture was filtered, dried and pulverized to obtain the red iron oxide particles having their surfaces coated with squaric acid.
The squaric acid coat of the thus obtained red iron oxide particles was 0.41% by weight, calculated as C, based on the particles.
2.5 kg of the said squaric acid-coated red iron oxide particles were mixed in a 110.degree. C. Henschel mixer (10-litre capacity) operated at 1,200 r.p.m. for 10 minutes to remove water, reducing the water content of the red iron oxide particles to 0.07% by weight.
With the Henschel mixer temperature maintained at 100.degree. C., 50 g of a polyether-modified polysiloxane BYK-080 (active ingredient: 100%) was added at a rate of 2.5 g/min over a period of 20 minutes, followed by mixing for 20 minutes to coat the red iron oxide particle surfaces with the said polyether-modified polysiloxane.
Then the Henschel mixer, with mixing continued, was cooled to room temperature to obtain the red iron oxide particles having their surfaces coated with the said polyether-modified polysiloxane.
The coating amount of the polyether-modified polysiloxane on the red iron oxide particles was 1.10%, calculated as C, based on the particles.
Examples 8-12 & Comparative Example 14
The same procedure as in Example 7 was carried out except that the kind, amount, heat treatment (whether conducted or not) and temperature of the iron oxide particles or iron oxide hydroxide particles, the kind, amount and mixing temperature of the modified polysiloxane, treatment therewith (whether conducted or not), and the kind and amount of squaric acid were varied to obtain the treated iron oxide particles or iron oxide hydroxide particles. The treating conditions in these Examples are shown in Table 1.
Production of solvent-type paints containing colored iron oxide particles
Example 13
Using 10 g of the inorganic colored particles obtained in Example 1, the following materials were blended in the specified ratios in a 140 ml glass pot and then mixed and dispersed together with 90 g of 3 mm.phi. glass beads for 45 minutes or 90 minutes by a paint shaker to prepare a mill base:
______________________________________Iron oxide particles obtained 12.2 parts byin Example 1 weightAminoalkyd resin (ARAMIC 19.5 parts byNo. 1026, produced by weightKansai Paint Co., Ltd.)Thinner 7.3 parts by weight______________________________________
This mill base was blended with an aminoalkyd resin in the ratios specified below and then further mixed and dispersed for 15 minutes by a paint shaker to obtain a solvent-type paint:
______________________________________Mill base 39.0 parts by weightAminoalkyd resin (ARAMIC 61.0 parts byNo. 1026 produced by Kansai weightPaint Co., Ltd.)______________________________________
By way of comparison, a paint was produced in the same procedure as Example 13 except that the red iron oxide particles were not coated with the polyether-modified polysiloxane BYK-080 and added in the coating composition in the course of preparation of the solvent-type paint (the method same as disclosed in the afore-mentioned Japanese Patent Application Laid-open (KOKAI) 62-187772). Gloss of the coating film formed by using this coating material was 77% when the dispersion time was 45 minutes and 83% when the dispersion time was 90 minutes, with the reduction percentage of gloss being 10%.
Examples 14-24 and Comparative Examples 15-28
The same procedure as in Example 13 was carried out except that the kind of iron oxide particles or iron oxide hydroxide particles was varied to produce the solvent-type paints.
The properties of the obtained solvent-type paint are shown in Table 3 and Table 4.
TABLE 3______________________________________Treated iron oxide pigment particles Coating weight Coating weight of modified Kind of iron of squaric acid, polysiloxane, oxide pigment calcd. as C calcd. as C particles (wt %) (wt %)______________________________________Example 13 Example 1 -- 0.54Example 14 Example 2 -- 0.28Example 15 Example 3 -- 1.05Example 16 Example 4 -- 1.40Example 17 Example 5 -- 0.14Example 18 Example 6 -- 3.66Example 19 Example 7 0.41 1.10Example 20 Example 8 1.25 0.06Example 21 Example 9 2.05 1.10Example 22 Example 10 0.42 0.07Example 23 Example 11 0.20 1.65Example 24 Example 12 0.40 0.55______________________________________Solvent-type paintGloss Mill base Mill base Gloss dispersion time dispersion time reduction 45 minutes 90 minutes percentage (%) (%) (%)______________________________________Example 13 90 95 5Example 14 88 93 6Example 15 93 96 5Example 16 82 87 8Example 17 82 85 6Example 18 81 86 7Example 19 98 99 0Example 20 85 90 3Example 21 101 105 1Example 22 88 92 3Example 23 88 91 1Example 24 82 86 4______________________________________
TABLE 4______________________________________Treated iron oxide pigment particles Coating weight Coating weight of modified Kind of iron of squaric acid, polysiloxane, oxide pigment calcd. as C calcd. as C particles (wt %) (wt %)______________________________________Comp. Comp. -- --Example 15 Example 1Comp. Comp. -- --Example 16 Example 2Comp. Comp. -- --Example 17 Example 3Comp. Comp. -- --Example 18 Example 4Comp. Comp. -- --Example 19 Example 5Comp. Comp. -- 0.003Example 20 Example 6Comp. Comp. -- 0.33Example 21 Example 7Comp. Comp. -- 0.43Example 22 Example 8Comp. Comp. -- 0.61Example 23 Example 9Comp. Comp. -- 1.67Example 24 Example 10Comp. Comp. -- 0.69Example 25 Example 11Comp. Comp. -- 0.15Example 26 Example 12Comp. Comp. -- 0.34Example 27 Example 13Comp. Comp. 0.41 --Example 28 Example 14______________________________________Solvent-type paintGloss Mill base Mill base Gloss dispersion time dispersion time reduction 45 minutes 90 minutes percentage (%) (%) (%)______________________________________Comp. 75 82 10Example 15Comp. 73 83 10Example 16Comp. 70 80 10Example 17Comp. 70 81 10Example 18Comp. 72 83 12Example 19Comp. 78 81 9Example 20Comp. 79 84 8Example 21Comp. 70 80 12Example 22Comp. 75 81 6Example 23Comp. 77 83 10Example 24Comp. 70 79 8Example 25Comp. 65 72 12Example 26Comp. 74 80 15Example 27Comp. 82 86 5Example 28______________________________________
Production of water-based paints containing colored iron oxide particles
Example 25
Using 7.62 g of the inorganic colored particles obtained in Example 1, the following materials were blended in the specified ratios in a 140 ml glass pot, and then mixed and dispersed with 90 g of 3 mm.phi. glass beads for 45 minutes or 90 minutes by a paint shaker to prepare a mill base:
______________________________________Iron oxide particles 12.4 parts byobtained in Example 1 weightWater-soluble alkyl resin 9.0 parts by(trade name: S-118, produced weightby Dai-Nippon Ink ChemicalIndustries Co., Ltd.)Defoaming agent (trade name: 0.1 part byNopco 8034, produced by weightSannopco Ltd.)Water 4.8 parts by weightButyl cellosolve 4.1 parts by weight______________________________________
Using this mill base, the following materials were blended in the specified ratios and further mixed and dispersed by a paint shaker to obtain a water-based paint:
______________________________________Mill base 30.4 parts by weightWater-soluble alkyl resin 46.2 parts by(trade name: S-118, produced weightby Dai-Nippon Ink ChemicalIndustries Co., ltd.)Water-soluble melamine resin 12.6 parts by(trade name: S-695, produced weightby Dai-Nippon Ink ChemicalIndustries Co., Ltd.)Defoaming agent (trade 0.1 parts byname: Nopco 8034, produced weightby Sannopco Ltd.)Water 9.1 parts by weightButyl cellosolve 1.6 part by weight______________________________________
For the purpose of comparison, a paint was produced by following the same procedure as Example 25 except that the red iron oxide particles were not coated with the polyether-modified polysiloxane BYK-080 and added in the coating composition in the course of preparation of the water-based paint (the method same as disclosed in the afore-mentioned Japanese Patent Application Laid-open (KOKAI) 62-187772). Gloss of the coating film formed by using this paint was 68% when the dispersion time was 45 minutes and 74% when the dispersion time was 90 minutes, with the reduction percentage of gloss being 13%.
Examples 26-36 and Comparative Examples 29-42
The same procedure as in Example 25 was carried out except that the kind of iron oxide particles or iron oxide hydroxide particles was varied to produce the water-based paints.
The properties of the obtained water-based paints are shown in Tables 5 and 6.
TABLE 5______________________________________Treated iron oxide pigment particles Coating weight Coating weight of modified Kind of iron of squaric acid, polysiloxane, oxide pigment calcd. as C calcd. as C particles (wt %) (wt %)______________________________________Example 25 Example 1 -- 0.54Example 26 Example 2 -- 0.28Example 27 Example 3 -- 1.05Example 28 Example 4 -- 1.40Example 29 Example 5 -- 0.14Example 30 Example 6 -- 3.66Example 31 Example 7 0.41 1.10Example 32 Example 8 1.25 0.06Example 33 Example 9 2.05 1.10Example 34 Example 10 0.42 0.07Example 35 Example 11 0.20 1.65Example 36 Example 12 0.40 0.55______________________________________ Water-based paint Gloss Mill base dispersion Mill base dispersion time 45 minutes time 90 minutes (%) (%)______________________________________Example 25 86 89Example 26 81 86Example 27 88 93Example 28 85 88Example 29 76 80Example 30 72 78Example 31 101 103Example 32 82 86Example 33 98 100Example 34 85 89Example 35 86 89Example 36 83 86______________________________________Water-based paint Gloss reduction Storage percentage stability Zeta potential (%) (%) (mV)______________________________________Example 25 8 82 -50.9Example 26 10 78 -47.8Example 27 6 90 -53.6Example 28 8 85 -43.3Example 29 10 76 -37.4Example 30 12 72 -35.6Example 31 1 101 -55.2Example 32 5 80 -41.6Example 33 3 95 -47.6Example 34 3 86 -40.6Example 35 3 86 -41.2Example 36 4 81 -45.2______________________________________
TABLE 6______________________________________Treated iron oxide pigment particles Coating weight Coating weight of modified Kind of iron of squaric acid, polysiloxane, oxide pigment calcd. as C calcd. as C particles (wt %) (wt %)______________________________________Comp. Comp. -- --Example 29 Example 1Comp. Comp. -- --Example 30 Example 2Comp. Comp. -- --Example 31 Example 3Comp. Comp. -- --Example 32 Example 4Comp. Comp. -- --Example 33 Example 5Comp. Comp. -- 0.003Example 34 Example 6Comp. Comp. -- 0.33Example 35 Example 7Comp. Comp. -- 0.43Example 36 Example 8Comp. Comp. -- 0.61Example 37 Example 9Comp. Comp. -- 1.67Example 38 Example 10Comp. Comp. -- 0.69Example 39 Example 11Comp. Comp. -- 0.15Example 40 Example 12Comp. Comp. -- 0.34Example 41 Example 13Comp. Comp. 0.41 --Example 42 Example 14______________________________________ Water-based paint Gloss Mill base dispersion Mill base dispersion time 45 minutes time 90 minutes (%) (%)______________________________________Comp. 65 73Example 29Comp. 66 76Example 30Comp. 58 69Example 31Comp. 56 73Example 32Comp. 43 70Example 33Comp. 67 75Example 34Comp. 69 74Example 35Comp. 62 73Example 36Comp. 64 69Example 37Comp. 70 78Example 38Comp. 68 78Example 39Comp. 58 67Example 40Comp. 60 70Example 41Comp. 76 80Example 42______________________________________Water-based paint Gloss reduction Storage percentage stability Zeta potential (%) (%) (mV)______________________________________Comp. 12 60 -17.8Example 29Comp. 15 60 -17.2Example 30Comp. 12 58 -10.5Example 31Comp. 18 46 -11.2Example 32Comp. 28 43 -7.6Example 33Comp. 10 63 -22.5Example 34Comp. 8 63 -24.6Example 35Comp. 10 65 -19.5Example 36Comp. 17 58 -18.6Example 37Comp. 15 68 -23.2Example 38Comp. 13 65 -21.6Example 39Comp. 18 55 -16.9Example 40Comp. 16 62 -18.6Example 41Comp. 7 76 -29.1Example 42______________________________________
Production of inorganic colored particles other than iron oxide-based particles
Example 37
2.5 kg of granular titanium oxide particles having an average diameter of 0.27 .mu.m were mixed in an 85.degree. C. Henschel mixer (10-litre capacity) operated at 1,200 r.p.m. for 10 minutes to remove water, reducing the water content of the titanium oxide particles to 0.13% by weight.
With the above Henschel mixer temperature maintained 95.degree. C., 25 g of a polyether-modified polysiloxane BYK-080 (active ingredient: 100%) (corresponding to 1.0% by weight based on the titanium oxide particles) was added at a rate of 2.5 g/min over a period of 10 minutes, and mixed for 20 minutes to coat the said titanium oxide particle surfaces with the said polyether-modified polysiloxane.
Then the Henschel mixer, with mixing continued, was cooled to room temperature to obtain the titanium oxide particles having their surfaces coated with a polyether-modified polysiloxane.
The obtained titanium oxide particles had a 0.55 wt % coat of the polyether-modified polysiloxane.
Examples 38-42 and Comparative Examples 48-55
The same procedure as in Example 37 was carried out except that the kind, amount and heat treatment temperature of the colored particles, the kind, amount and mixing temperature of the modified polysiloxane were varied to obtain the treated colored particles.
The treating conditions are shown in Tables 7 and 8.
Comparative Examples 43-47
For comparison, there were prepared the non-treated colored particles. The properties of these colored particles are shown in Table 8.
TABLE 7______________________________________ Coating treatment Inorganic colored particles Major axial diameter Kind Shape (.mu.m)______________________________________Example 37 Titanium oxide Ganular 0.27Example 38 Titanium oxide Granular 0.25Example 39 Chrome yellow Granular 0.36Example 40 Chrome yellow Granular 0.33Example 41 Chrome oxide Granular 0.30Example 42 Chrome oxide Granular 0.30Example 43 Titanium oxide Granular 0.27Example 44 Titanium oxide Granular 0.25Example 45 Chrome yellow Granular 0.36Example 46 Chrome yellow Granular 0.33Example 47 Chrome oxide Granular 0.30Example 48 Chrome oxide Granular 0.30______________________________________Coating treatmentInorganic colored particles Minor axial BET specific diameter surface area Amount (.mu.m) (m.sup.2 /g) (kg)______________________________________Example 37 -- 11.6 2.5Example 38 -- 16.5 2.5Example 39 -- 6.6 3.0Example 40 -- 9.1 3.0Example 41 -- 7.3 3.0Example 42 -- 7.3 3.0Example 43 -- 11.6 2.5Example 44 -- 16.5 2.5Example 45 -- 6.6 3.0Example 46 -- 9.1 3.0Example 47 -- 7.3 3.0Example 48 -- 7.3 3.0______________________________________ Coating treatment Inorganic colored particles Heat treatment Residual Squaric acid water Amount Temp. content added (.degree.C.) (%) Kind (%)______________________________________Example 37 85 0.13 -- --Example 38 85 0.08 -- --Example 39 85 0.10 -- --Example 40 85 0.15 -- --Example 41 85 0.08 -- --Example 42 85 0.07 -- --Example 43 90 0.08 A 1.0Example 44 90 0.06 A 3.0Example 45 85 0.12 A 5.0Example 46 85 0.13 A 1.0Example 47 100 0.02 A 0.5Example 48 100 0.02 A 1.0______________________________________ Coating treatment Specific modified polysiloxane Amount Mixing added temperature Kind (%) (.degree.C.)______________________________________Example 37 Polyether-modofoed 1.0 95 polysiloxane BYK-080Example 38 Polyether-modified 2.0 95 polysiloxane BYK-080Example 39 Polyether-modified 3.0 85 polysiloxane BYK-080Example 40 Polyether-modified 2.0 85 polysiloxane BYK-080Example 41 Polyester-modified 0.7 100 polysiloxane BYK-310Example 42 Aralkyl-modified 0.5 105 polysiloxane BYK-322Example 43 Polyether-modified 5.0 85 polysiloxane BYK-080Example 44 Polyether-modified 5.0 90 polysiloxane BYK-325Example 45 Aralkyl-modified 7.0 100 polysiloxane BYK-322Example 46 Polyether-modified 0.1 80 polysiloxane BYK-080Example 47 Polyester-modified 2.0 80 polysiloxane BYK-310Example 48 Polyether-modified 1.0 90 polysiloxane BYK-080______________________________________ A: 3,4dihydroxy-3-cyclobutene-1,2-dione (produced by Tokyo Kasei Kogyo CO., LTD.)
TABLE 8______________________________________ Coating treatment Inorganic colored particles Major axial diameter Kind Shape (.mu.m)______________________________________Comp. Titanium oxide Granular 0.27Example 43Comp. Titanium oxide Granular 0.25Example 44Comp. Chrome yellow Granular 0.36Example 45Comp. Chrome yellow Granular 0.33Example 46Comp. Chrome oxide Granular 0.30Example 47Comp. Titanium oxide Granular 0.27Example 48Comp. Titanium oxide Granular 0.27Example 49Comp. Titanium oxide Granular 0.27Example 50Comp. Titanium oxide Granular 0.27Example 51Comp. Titanium oxide Granular 0.27Example 52Comp. Titanium oxide Granular 0.27Example 53Comp. Titanium oxide Granular 0.27Example 54Comp. Titanium oxide Granular 0.27Example 55Comp. Titanium oxide Granular 0.27Example 56______________________________________ Coating treatment Inorganic colored particles Minor axial BET specific diameter surface area Amount (.mu.m) (m.sup.2 /g) (kg)______________________________________Comp. -- 11.6 --Example 43Comp. -- 16.5 --Example 44Comp. -- 6.6 --Example 45Comp. -- 9.1 --Example 46Comp. -- 7.3 --Example 47Comp. -- 11.6 2.5Example 48Comp. -- 11.6 2.5Example 49Comp. -- 11.6 2.5Example 50Comp. -- 11.6 2.5Example 51Comp. -- 11.6 2.5Example 52Comp. -- 11.6 2.5Example 53Comp. -- 11.6 2.5Example 54Comp. -- 11.6 2.5Example 55Comp. -- 11.6 --Example 56______________________________________ Coating treatment Inorganic colored particles Squartic acid Heat treatment Amount Temp. Residual water added (.degree.C.) content (%) Kind (%)______________________________________Comp. -- -- -- --Example 43Comp. -- -- -- --Example 44Comp. -- -- -- --Example 45Comp. -- -- -- --Example 46Comp. -- -- -- --Example 47Comp. 85 0.12 -- --Example 48Comp. 85 0.13 -- --Example 49Comp. 85 0.11 -- --Example 50Comp. 85 0.13 -- --Example 51Comp. 85 0.13 -- --Example 52Comp. 85 0.14 -- --Example 53Comp. 85 0.12 -- --Example 54Comp. 85 0.12 -- --Example 55Comp. -- -- A 1.0Example 56______________________________________ Coating treatment Specific modified polysiloxane Mixing Amount temperature Kind added (%) (.degree.C.)______________________________________Comp. -- -- --Example 43Comp. -- -- --Example 44Comp. -- -- --Example 45Comp. -- -- --Example 46Comp. -- -- --Example 47Comp. Polyether-modified 0.005 80Example 48 polysiloxane BYK-080Comp. Polydimethylsiloxane 1.0 85Example 49Comp. Methyl 2.0 85Example 50 hydrogensiloxaneComp. Alkoxypolysiloxane 1.0 85Example 51Comp. Methylphenyl- 4.0 95Example 52 polysiloxaneComp. Dimethylpolysiloxy 5.0 95Example 53 chlorideComp. .gamma.-glycidoxypropyl- 0.5 80Example 54 trimethoxysilaneComp. Amino group end 1.0 85Example 55 modified polysiloxaneComp. -- -- --Example 56______________________________________ A: 3,4dihydroxy-3-cyclobutene-1,2-dione (produced by Tokyo Kasei Kogyo CO., LTD.)
Example 43
A squaric acid solution was prepared by adding 30 g of squaric acid (3,4-dihydroxy-3-cyclobutene-1,2-dione) (available from Tokyo Kasei Kogyo CO., LTD.) to 5 litres of pure water, and water was added to this squaric acid solution to make the total amount 25 litres and stirred well by a stirrer. The squaric acid concentration in the resulting solution was 1.2 g/litre.
3 kg of granular titanium oxide particles having an average diameter of 0.27 .mu.m were added gradually to the said squaric acid solution and mixed with stirring by a homomixer for 30 minutes, followed by filtration, drying and pulverization to obtain the titanium oxide particles coated with squaric acid.
The squaric acid coat of the obtained titanium oxide particles was 0.40% by weight, calculated as C, based on the particles.
2.5 kg of the said squaric acid-coated titanium oxide particles were supplied into a 10-litre Henschel mixer heated to 90.degree. C. and mixed therein at 1,200 r.p.m. for 10 minutes to remove water, thereby reducing the water content of the titanium oxide particles to 0.08% by weight.
With the Henschel mixer temperature maintained at 85.degree. C., 125 g of a polyether-modified polysiloxane BYK-080 (active ingredient: 100%) was added at a rate of 6.25 g/min over a period of 20 minutes, followed by mixing for 20 minutes to coat the said titanium oxide particle surfaces with the said polyether-modified polysiloxane.
Then the Henschel mixer, with mixing continued, was cooled to room temperature to obtain the titanium oxide particles having their surfaces coated with a polyether-modified polysiloxane.
The polyether-modified polysiloxane coat of the obtained titanium oxide particles was 2.56%, calculated as C, based on the particles.
Examples 44-48 & Comparative Example 56
The same procedure as in Example 43 was carried out except that the kind, amount, heat treatment (whether conducted or not) and treatment temperature of the inorganic colored particles, the kind, amount and mixing temperature of the modified polysiloxane, and the kind and mount of squaric acid were varied to obtain the treated inorganic colored particles.
The treating conditions in these Examples are shown in Table 7.
Production of solvent-type paints containing colored particles other than iron oxide-based particles
Example 49
Using 10 g of the titanium oxide particles obtained in Example 37, the following materials were blended in the specified ratios in a 140 ml glass pot, and then mixed and dispersed with 90 g of 3 mm.phi. glass beads for 45 minutes or 90 minutes to make a mill base:
______________________________________Titanium oxide particles 12.2 parts byobtained in Example 37 weightAminoalkyd resin 19.5 parts by(No. 1026, produced by weightKansai Paint Co., Ltd.)Thinner 7.3 parts by weight______________________________________
This mill base was blended with the said aminoalkyd resin in the ratios specified below, and further mixed and dispersed for 15 minutes by a paint shaker to obtain a solvent-type paint:
______________________________________Mill base 39.0 parts by weightAminoalkyd resin 61.0 parts by(No. 1026, Kansai Paint weightCo., Ltd.)______________________________________
By way of comparison, there was produced a paint by the following the same procedure as Example 49 except that the titanium oxide particles were not coated with the polyether-modified polysiloxane BYK-080 and added in the coating composition in the course of production of the paint (the method same as disclosed in Japanese Patent Application Laid-open (KOKAI) 62-187772). Gloss of the coating film formed by using this paint was 76% when the dispersion time was 45 minutes and 78% when the dispersion time was 90 minutes, with the reduction percentage of gloss being 12%.
Examples 50-60 and Comparative Examples 57-70
The same procedure as in Example 49 was carried out except that the kind of the inorganic colored particles was varied to obtain solvent-type paints.
The properties of the obtained solvent-type paints are shown in Table 9 and Table 10.
TABLE 9______________________________________ Treated iron oxide pigment particles Coating weight Coating weight of modified Kind of iron of squaric acid, polysiloxane, oxide pigment calcd. as C calcd. as C particles (wt %) (wt %)______________________________________Example 49 Example 37 -- 0.55Example 50 Example 38 -- 1.10Example 51 Example 39 -- 1.58Example 52 Example 40 -- 1.04Example 53 Example 41 -- 0.10Example 54 Example 42 -- 0.30Example 55 Example 43 0.40 2.56Example 56 Example 44 1.25 1.40Example 58 Example 45 1.97 3.61Example 59 Example 46 0.41 0.05Example 60 Example 47 0.23 0.30Example 61 Example 48 0.42 0.55______________________________________ Solvent-type paint Gloss Mill base Mill base Gloss dispersion time dispersion time reduction 45 minutes 90 minutes percentage (%) (%) (%)______________________________________Example 49 82 86 7Example 50 86 91 4Example 51 78 82 8Example 52 80 85 8Example 53 77 83 9Example 54 78 81 9Example 55 84 88 3Example 56 89 94 1Example 58 83 85 2Example 59 80 84 6Example 60 80 83 10Example 61 83 83 4______________________________________
TABLE 10______________________________________ Treated iron oxide pigment particles Coating weight Coating weight of modified Kind of iron of squaric acid, polysiloxane, oxide pigment calcd. as C calcd. as C particles (wt %) (wt %)______________________________________Comp. Comp. -- --Example 57 Example 43Comp. Comp. -- --Example 58 Example 44Comp. Comp. -- --Example 59 Example 45Comp. Comp. -- --Example 60 Example 46Comp. Comp. -- --Example 61 Example 47Comp. Comp. -- 0.003Example 62 Example 48Comp. Comp. -- 0.32Example 63 Example 49Comp. Comp. -- 0.43Example 64 Example 50Comp. Comp. -- 0.60Example 65 Example 51Comp. Comp. -- 1.71Example 66 Example 52Comp. Comp. -- 0.71Example 67 Example 53Comp. Comp. -- 0.14Example 68 Example 54Comp. Comp. -- 0.33Example 69 Example 55Comp. Comp. 0.39 --Example 70 Example 56______________________________________ Solvent-type paint Gloss Mill base Mill base Gloss dispersion time dispersion time reduction 45 minutes 90 minutes percentage (%) (%) (%)______________________________________Comp. 73 76 15Example 57Comp. 75 78 12Example 58Comp. 69 75 17Example 59Comp. 72 76 15Example 60Comp. 66 71 22Example 61Comp. 76 80 13Example 62Comp. 75 80 12Example 63Comp. 73 76 12Example 64Comp. 76 79 14Example 65Comp. 75 79 16Example 66Comp. 68 68 19Example 67Comp. 70 72 13Example 68Comp. 76 80 12Example 69Comp. 75 80 12Example 70______________________________________
Production of water-based paints containing colored particles other than iron oxide-base particles
Example 61
Using 7.62 g of the titanium oxide particles obtained in Example 37, the following materials were blended in the specified ratios in a 140 ml glass pot, and then mixed and dispersed with 90 g of 3 mm.phi. glass beads for 45 minutes or 90 minutes by a paint shaker to make a mill base:
______________________________________Titanium oxide particles 12.4 parts byobtained in Example 37 weightWater-soluble alkyd resin 9.0 parts by(trade name: S-118, produced weightby Dai Nippon Ink ChemicalCo., Ltd.)Defoaming agent (trade name: 0.1 part byNopco 8043, produced by weightSannopco Ltd.)Water 4.8 parts by weightButyl cellosolve 4.1 parts by weight______________________________________
Using this mill base, the following materials were blended in the specified ratios and then further mixed and dispersed for 15 minutes by a paint shaker to obtain a water-based paint:
______________________________________Mill base 30.4 parts by weightWater-soluble alkyd resin 46.2 parts by(trade name: S-118, produced weightby Dai Nippon Ink ChemicalCo., Ltd.)Water-soluble melamine resin 12.6 parts by(trade name: S-695, produced weightby Dai Nippon Ink ChemicalCo., Ltd.)Defoaming agent (trade name: 0.1 part byNopco 8034, produced by weightSannopco Ltd.)Water 9.1 parts by weightButyl cellosolve 1.6 part by weight______________________________________
For comparison, a paint was produced in the same procedure as Example 61 except that the titanium oxide particles were not coated with the polyether-modified polysiloxane BYK-080 and added in the composition in the course of preparation of the water-based paint (the method same as disclosed in the afore-mentioned Japanese Patent Application Laid-open (KOKAI) 62-187772). Gloss of the coating film formed by using this paint was 64% when the dispersion time was 45 minutes and 73% when the dispersion time was 90 minutes, with the reduction percentage of gloss being 14%.
Examples 62-72 and Comparative Examples 71-84
The same procedure as in Example 61 was carried out except that the kind of the inorganic colored particles was varied to produce water-based paints. The properties of the obtained water-based paints are shown in Table 11 and Table 12.
TABLE 11______________________________________ Treated inorganic colored pigment particles Coating weight Coating weight of modified Kind of iron of squaric acid, polysiloxane, oxide pigment calcd. as C calcd. as C particles (wt %) (wt %)______________________________________Example 61 Example 37 -- 0.55Example 62 Example 38 -- 1.10Example 63 Example 39 -- 1.58Example 64 Example 40 -- 1.04Example 65 Example 41 -- 0.10Example 66 Example 42 -- 0.30Example 67 Example 43 0.40 2.56Example 68 Example 44 1.25 1.40Example 69 Example 45 1.97 3.61Example 70 Example 46 0.41 0.05Example 71 Example 47 0.23 0.30Example 72 Example 48 0.42 0.55______________________________________ Water-based paint Gloss Mill base dispersion Mill base dispersion time 45 minutes time 90 minutes (%) (%)______________________________________Example 61 83 86Example 62 87 91Example 63 81 86Example 64 82 88Example 65 76 80Example 66 78 82Example 67 86 93Example 68 90 96Example 69 86 89Example 70 82 88Example 71 80 85Example 72 85 89______________________________________ Water-based paint Gloss reduction Storage percentage stability Zeta potential (%) (%) (mV)______________________________________Example 61 8 76 -46.1Example 62 5 83 -50.6Example 63 7 77 -46.2Example 64 6 79 -53.6Example 65 10 72 -35.2Example 66 10 78 -33.1Example 67 5 81 -48.6Example 68 3 93 -54.6Example 69 5 86 -53.0Example 70 5 80 -50.0Example 71 8 80 -42.1Example 72 8 86 -41.6______________________________________
TABLE 12______________________________________ Treated inorganic colored pigment particles Coating weight Coating weight of modified Kind of iron of squaric acid, polysiloxane, oxide pigment calcd. as C calcd. as C particles (wt %) (wt %)______________________________________Comp. Comp. -- --Example 71 Example 43Comp. Comp. -- --Example 72 Example 44Comp. Comp. -- --Example 73 Example 45Comp. Comp. -- --Example 74 Example 46Comp. Comp. -- --Example 75 Example 47Comp. Comp. -- 0.003Example 76 Example 48Comp. Comp. -- 0.32Example 77 Example 49Comp. Comp. -- 0.43Example 78 Example 50Comp. Comp. -- 0.60Example 79 Example 51Comp. Comp. -- 1.71Example 80 Example 52Comp. Comp. -- 0.71Example 81 Example 53Comp. Comp. -- 0.14Example 82 Example 54Comp. Comp. -- 0.33Example 83 Example 55Comp. Comp. 0.39 --Example 84 Example 56______________________________________ Water-based paint Gloss Mill base dispersion Mill base dispersion time 45 minutes time 90 minutes (%) (%)______________________________________Comp. 59 67Example 71Comp. 68 74Example 72Comp. 63 70Example 73Comp. 63 72Example 74Comp. 38 51Example 75Comp. 66 72Example 76Comp. 65 73Example 77Comp. 63 69Example 78Comp. 59 66Example 79Comp. 65 70Example 80Comp. 63 68Example 81Comp. 45 61Example 82Comp. 68 72Example 83Comp. 73 78Example 84______________________________________ Water-based paint Gloss reduction Storage percentage stability Zeta potential (%) (%) (mV)______________________________________Comp. 19 65 -21.6Example 71Comp. 15 70 -23.8Example 72Comp. 16 65 -13.8Example 73Comp. 15 68 -15.6Example 74Comp. 26 40 -6.5Example 75Comp. 15 70 -24.8Example 76Comp. 17 68 -20.0Example 77Comp. 20 63 -10.6Example 78Comp. 21 60 -11.3Example 79Comp. 15 60 -21.6Example 80Comp. 18 63 -15.0Example 81Comp. 19 52 -18.2Example 82Comp. 15 68 -21.3Example 83Comp. 13 72 -29.6Example 84______________________________________
Production of magnetic particles
Example 73
3.0 kg of granular barium ferrite particles having an average diameter of 0.65 .mu.m, a BET specific surface area of 4.6 m.sup.2 /g, a coercive force Hc of 2,753 Oe, a saturation magnetization .sigma..sub.s of 55.6 emu/g, a pH value of 9.5 and a water content of 0.17% by weight were mixed in an 85.degree. C. Henschel mixer (10-litre capacity) operated at 1,200 r.p.m. for 10 minutes to reduce the water content of the barium ferrite particles to 0.06% by weight.
With the Henschel mixer temperature maintained at 85.degree. C., 30 g of a polyether-modified polysiloxane BYK-080 (trade name, produced by BYK Chemie Co., Ltd.) (active ingredient: 100%) (corresponding to 1.0% by weight based on barium ferrite particles) was added at a rate of 3.0 g/min over a period of 10 minutes and mixed for 20 minutes to coat the barium ferrite particle surfaces with the said polyether-modified polysiloxane.
Then the Henschel mixer, with mixing continued, was cooled to room temperature to obtain the barium ferrite particles having their surfaces coated with a polyether-modified polysiloxane.
The polyether-modified polysiloxane coat of the obtained barium ferrite particles was 0.52% by weight, calculated as C, based on the particles.
Examples 74-78 and Comparative Examples 90-98
The same procedure as in Example 73 was carried out except that the type, amount and heat treatment temperature of the magnetic particles, the kind, amount of squaric acid, the type, amount and mixing temperature of the modified polysiloxane were varied to obtain magnetic particles. The treating conditions are shown in Table 13 and Table 14.
Comparative Examples 85-89
By way of comparison, there were prepared the non-treated magnetic particles. The properties of these magnetic particles are shown in Table 14.
Example 79
A squaric acid solution was prepared by adding 35 g of squaric acid (3,4-dihydroxy-3-cyclobutene-1,2-dione) (available from Tokyo Kasei Kogyo CO., LTD.) to 5 litres of pure water, and water was added to this squaric acid solution to make the total amount 35 litres and stirred well. The squaric acid concentration in the resulting solution was 1.0 g/l.
To this squaric acid solution were gradually added 3.5 kg of granular barium ferrite particles having an average diameter of 0.65 .mu.m, a BET specific surface area of 4.6 m2/g, a coercive force Hc of 2,753 Oe, a saturation magnetization .sigma..sub.s of 55.6 emu/g, a pH value of 9.5 and a water content of 0.17% by weight, and the suspension was mixed with stirring by a homomixer for 30 minutes, followed by filtration, drying and pulverization to coat the said barium ferrite particle surfaces with squaric acid.
The obtained barium ferrite particles had a squaric acid coat of 0.40% by weight, calculated as C, based on the particles.
3.0 kg of the said squaric acid-coated barium ferrite particles were mixed in a 85.degree. C. 10-litre Henschel mixer operated at 1,200 r.p.m. for 10 minutes to reduce the water content of the barium ferrite particles to 0.03% by weight.
With the Henschel mixer temperature maintained at 85.degree. C., 60 g of a polyether-modified polysiloxane BYK-080 (active ingredient: 100%) was added at a rate of 3.0 g/min over a period of 20 minutes, followed by mixing for 20 minutes to coat the barium ferrite particle surfaces with the said polyether-modified polysiloxane.
Then the Henschel mixer, with mixing continued, was cooled to room temperature to obtain the barium ferrite particles having a squaric acid coat on which a polyether-modified polysiloxane coat was formed.
The polyether-modified polysiloxane coat of the obtained barium ferrite particles was 1.05% by weight, calculated as C, based on the particles.
Examples 80-84
The same procedure as in Example 79 was carried out except that the kind, amount, heat treatment (conducted or not) and treatment temperature of the magnetic particles, and the kind, the amount of squaric acid, the amount and mixing temperature of the modified polysiloxane were varied to obtain the treated magnetic particles. The treating conditions and the properties of the obtained magnetic particles are shown in Table 13.
TABLE 13______________________________________ Coating treatment Magnetoplumbite ferrite particles or magnetic iron oxide particles Major axial diameter Kind Shape (.mu.m)______________________________________Example 73 Barium Granular 0.65 ferriteExample 74 Barium Granular 0.65 ferriteExample 75 Barium Granular 0.68 ferriteExample 76 Strontium Granular 0.70 ferriteExample 77 Maghemite Acicular 0.40Example 78 Magnetite Acicular 0.42Example 79 Barium Granular 0.65 ferriteExample 80 Barium Granular 0.65 ferriteExample 81 Barium Granular 0.68 ferriteExample 82 Strontium Granular 0.70 ferriteExample 83 Maghemite Acicular 0.40Example 84 Magnetite Acicular 0.42______________________________________ Coating treatment Magnetoplumbite ferrite particles or magnetic iron oxide particles Minor axial BET Specific diameter surface area Hc (.mu.m) (m.sup.2 /g) (Oe)______________________________________Example 73 -- 4.6 2753Example 74 -- 4.6 2753Example 75 -- 4.3 1768Example 76 -- 3.8 2560Example 77 0.050 16.4 310Example 78 0.052 14.8 334Example 79 -- 4.6 2753Example 80 -- 4.6 2753Example 81 -- 4.3 1768Example 82 -- 3.8 2560Example 83 0.050 16.4 310Example 84 0.052 14.8 334______________________________________ Coating treatment Magnetoplumbite ferrite particles or magnetic iron oxide particles .sigma.s Amount Heat treatment (emu/g) (kg) Temp. (.degree.C.)______________________________________Example 73 55.6 3.0 85Example 74 55.6 3.0 85Example 75 56.2 3.0 90Example 76 53.9 3.0 100Example 77 75.8 2.5 110Example 78 81.6 2.5 80Example 79 55.6 3.0 85Example 80 55.6 3.0 85Example 81 56.2 3.0 120Example 82 53.9 3.0 100Example 83 75.8 2.5 85Example 84 81.6 2.5 80______________________________________ Coating treatment Magnetoplumbite ferrite particles or magnetic iron oxide particles Heat treatment Squaric acid Residual water Amount added content (%) Kind (%)______________________________________Example 73 0.06 -- --Example 74 0.05 -- --Example 75 0.03 -- --Example 76 0 -- --Example 77 0.02 -- --Example 78 0.08 -- --Example 79 0.03 A 1.0Example 80 0.05 A 3.0Example 81 0 A 5.0Example 82 0.02 A 1.0Example 83 0.05 A 0.5Example 84 0.09 A 1.0______________________________________ Coating treatment Specific modified polysiloxane Mixing Amount temperature Kind added (%) (.degree.C.)______________________________________Example 73 Polyether-modified 1.0 85 polysiloxane BYK-080Example 74 Polyether-modified 0.5 85 polysiloxane BYK-080Example 75 Polyether-modified 2.0 90 polysiloxane BYK-080Example 76 Polyether-modified 5.0 100 polysiloxane BYK-325Example 77 Polyester-modified 3.0 105 polysiloxane BYK-310Example 78 Aralkyl-modified 3.5 85 polysiloxane BYK-322Example 79 Polyether-modified 2.0 85 polysiloxane BYK-080Example 80 Aralkyl-modified 0.1 90 polysiloxane BYK-322Example 81 Polyether-modified 8.0 110 polysiloxane BYK-320Example 82 Polyester-modified 1.0 100 polysiloxane BYK-310Example 83 Polyether-modified 3.0 85 polysiloxane BYK-080Example 84 Polyether-modified 1.0 80 polysiloxane BYK-080______________________________________ A: 3,4dihydroxy-3-cyclobutene-1,2-dione (produced by Tokyo Kasei Kogyo CO., LTD.)
TABLE 14______________________________________ Coating treatment Magnetoplumbite ferrite particles or magnetic iron oxide particles Major axial diameter Kind Shape (.mu.m)______________________________________Comp. Barium Granular 0.65Example 85 ferriteComp. Barium Granular 0.68Example 86 ferriteComp. Strontium Granular 0.70Example 87 ferriteComp. Maghemite Acicular 0.40Example 88Comp. Magnetite Acicular 0.42Example 89Comp. Barium Granular 0.65Example 90 ferriteComp. Barium Granular 0.65Example 91 ferriteComp. Barium Granular 0.65Example 92 ferriteComp. Barium Granular 0.65Example 93 ferriteComp. Barium Granular 0.65Example 94 ferriteComp. Barium Granular 0.65Example 95 ferriteComp. Barium Granular 0.65Example 96 ferriteComp. Barium Granular 0.65Example 97 ferriteComp. Barium Granular 0.65Example 98 ferrite______________________________________ Coating treatment Magnetoplumbite ferrite particles or magnetic iron oxide particles Minor axial BET Specific diameter surface area Hc (.mu.m) (m.sup.2 /g) (Oe)______________________________________Comp. -- 4.6 2753Example 85Comp. -- 4.3 1768Example 86Comp. -- 3.8 2560Example 87Comp. 0.050 16.4 310Example 88Comp. 0.052 14.8 334Example 89Comp. -- 4.6 2753Example 90Comp. -- 4.6 2753Example 91Comp. -- 4.6 2753Example 92Comp. -- 4.6 2753Example 93Comp. -- 4.6 2753Example 94Comp. -- 4.6 2753Example 95Comp. -- 4.6 2753Example 96Comp. -- 4.6 2753Example 97Comp. -- 4.6 2753Example 98______________________________________ Coating treatment Magnetoplumbite ferrite particles or magnetic iron oxide particles .sigma.s Amount Heat treatment (emu/g) (kg) Temp. (.degree.C.)______________________________________Comp. 55.6 3.0 --Example 85Comp. 56.2 3.0 --Example 86Comp. 53.9 3.0 --Example 87Comp. 75.8 2.5 --Example 88Comp. 81.6 2.5 --Example 89Comp. 55.6 3.0 85Example 90Comp. 55.6 3.0 85Example 91Comp. 55.6 3.0 85Example 92Comp. 55.6 3.0 85Example 93Comp. 55.6 3.0 85Example 94Comp. 55.6 3.0 85Example 95Comp. 55.6 3.0 85Example 96Comp. 55.6 3.0 85Example 97Comp. 55.6 3.0 --Example 98______________________________________ Coating treatment Magnetoplumbite ferrite particles or magnetic iron oxide particles Heat treatment Residual water Squaric acid content Amount added (%) Kind (%)______________________________________Comp. -- -- --Example 85Comp. -- -- --Example 86Comp. -- -- --Example 87Comp. -- -- --Example 88Comp. -- -- --Example 89Comp. 0.06 -- --Example 90Comp. 0.06 -- --Example 91Comp. 0.07 -- --Example 92Comp. 0.06 -- --Example 93Comp. 0.06 -- --Example 94Comp. 0.07 -- --Example 95Comp. 0.06 -- --Example 96Comp. 0.06 -- --Example 97Comp. -- A 0.25Example 98______________________________________Coating treatmentSpecific modified polysiloxane Mixing Amount temperature Kind added (%) (.degree.C.)______________________________________Comp. -- -- --Example 85Comp. -- -- --Example 86Comp. -- -- --Example 87Comp. -- -- --Example 88Comp. -- -- --Example 89Comp. Polyether-modified 0.005 90Example 90 polysiloxane BYK-080Comp. Polydimethylsiloxane 1.0 85Example 91Comp. Methylhydrogensiloxane 2.0 85Example 92Comp. Alkoxypolysiloxane 1.0 85Example 93Comp. Methyphenylpolysiloxane 4.0 85Example 94Comp. Dimethylpolysiloxychloride 5.0 85Example 95Comp. .gamma.-glycidoxypropyl- 0.5 80Example 96 trimethoxysilaneComp. Amino group end modified 1.0 80Example 97 polysiloxaneComp. -- -- --Example 98______________________________________
Production of solvent-type paints
Example 85
Using 18 g of the treated magnetic particles obtained in Example 73, they were blended with a lecithin solution in the specified ratios in a 140 ml glass pot and then mixed and dispersed with 100 g of 1.5 mm.phi. glass beads for 15 minutes by a paint shaker to obtain a mill base (1). Mill base (1) composition:
______________________________________Treated magnetic particles 37.5 parts by weightobtained in Example 73Lecithin solution (2.5 wt % 7.5 parts by weightcyclohexanone solution)______________________________________
Using this mill base (1), the following materials were blended in the specified ratios and further mixed and dispersed by a paint shaker to obtain a mill base (2). There were prepared two types of mill base (2), one being prepared with a dispersion time of 60 minutes and the other with a dispersion time of 120 minutes. Mill base (2) composition:
______________________________________Mill base (1) 45.0 parts by weightVinyl chloride-vinyl 12.5 parts by weightacetate copolymer resinsolution (30 wt % cyclohexanonesolution of VAGF, produced byUnion Carbide Corp.)Methyl ethyl ketone 16.3 parts by weight______________________________________
Using the thus obtained mill base (2), the following materials were blended in the specified ratios and further mixed and dispersed for 30 minutes by a paint shaker to obtain a solvent-type paint.
Solvent-type paint composition
______________________________________Mill base (2) 73.8 parts by weightPolyurethane resin 12.5 parts by weightsolution (30 wt % methylethyl ketone/toluene (1/1)solution of NIPPORAN 2301available from Nippon PolyurethaneIndustry Co., Ltd.)Methyl ethyl ketone 3.4 parts by weightCyclohexanone 10.3 parts by weight______________________________________
The thus obtained solvent-type paint was filtered by a stainless steel mesh with an opening size of 44 .mu.m, then coated on a PET base film to a thickness of 50 .mu.m, oriented in a 2,800 G orienting magnetic field and dried to form a coating film. The properties of this coating film are show in Table 15 and Table 16.
By way of comparison, a paint was produced by following the procedure of Example 85 except that the barium ferrite particles were not coated with the polyether-modified polysiloxane BYK-080 and added in the coating composition in the course of production of the solvent-type paint (the method same as disclosed in the afore-mentioned JAPANESE PATENT APPLICATION LAID-OPEN (KOKAI) 62-187772). The coating film formed with this paint using the mill base (2) prepared with dispersion time of 120 minutes had a coercive force Hc of 2,703 Oe, RS of 0.85, Ra of 0.47 .mu.m, RMS of 0.56 .mu.m and Ra changing percentage after dilution of 11.4%.
Examples 86-96 and Comparative Examples 99-112
The same procedure as in Example 85 was carried out except for variation of the kind of the magnetic particles used to produce solvent-type paints. The properties of the obtained solvent-type paints are shown in Table 15 and Table 16.
TABLE 15______________________________________Treated magnetic particles Coating weight of Coating weight of modified Kind of squaric acid, polysiloxane, magnetic calcd. as C calcd. as C particles (wt %) (wt %)______________________________________Example 85 Example 73 -- 0.52Example 86 Example 74 -- 0.27Example 87 Example 75 -- 1.08Example 88 Example 76 -- 1.43Example 89 Example 77 -- 0.40Example 90 Example 78 -- 1.83Example 91 Example 79 0.40 1.05Example 92 Example 80 1.19 0.06Example 93 Example 81 1.98 2.30Example 94 Example 82 0.39 0.15Example 95 Example 83 0.20 1.66Example 96 Example 84 0.39 0.54______________________________________Properties of the coating using solvent-typepaintWhen using mill base (2) prepared withdispersion time of 60 minutes Hc RS Ra (Oe) (-) (.mu.m)______________________________________Example 85 2713 0.90 0.32Example 86 2726 0.91 0.31Example 87 1750 0.91 0.29Example 88 2516 0.90 0.35Example 89 350 0.88 0.27Example 90 373 0.87 0.28Example 91 2710 0.91 0.28Example 92 2731 0.91 0.35Example 93 1756 0.92 0.26Example 94 2530 0.91 0.34Example 95 354 0.89 0.30Example 96 368 0.89 0.30______________________________________Properties of the coating using solvent-typepaintWhen using millbase (2) prepared When using mill base (2)with dispersion prepared with dispersiontime of 60 minutes time of 120 minutes RMS Hc RS (.mu.m) (Oe) (-)______________________________________Example 85 0.38 2720 0.91Example 86 0.38 2725 0.92Example 87 0.36 1746 0.92Example 88 0.42 2510 0.92Example 89 0.33 355 0.88Example 90 0.34 372 0.88Example 91 0.33 2716 0.92Example 92 0.42 2721 0.92Example 93 0.34 1748 0.92Example 94 0.38 2514 0.93Example 95 0.38 351 0.89Example 96 0.37 370 0.89______________________________________ Properties of the coating using solvent-type paint When using mill base (2) Dispersion prepared with dispersion time stability of 120 minutes (Ra change rate Ra RMS after dilution) (.mu.m) (.mu.m) (%)______________________________________Example 85 0.30 0.36 6.3Example 86 0.30 0.35 8.3Example 87 0.26 0.32 4.6Example 88 0.32 0.38 7.1Example 89 0.25 0.31 5.6Example 90 0.25 0.30 2.7Example 91 0.24 0.30 4.3Example 92 0.33 0.39 5.6Example 93 0.23 0.29 2.6Example 94 0.31 0.35 7.2Example 95 0.26 0.31 3.8Example 96 0.24 0.30 6.6______________________________________
TABLE 16______________________________________Treated magnetic particles Coating weight of Coating weight of modified Kind of squaric acid, polysiloxane, magnetic calcd. as C calcd. as C particles (wt %) (wt %)______________________________________Comp. Comp. -- --Example Example 85Comp. Comp. -- --Example 100 Example 86Comp. Comp. -- --Example 101 Example 87CFomp. Comp. -- --Example 102 Example 88Comp. Comp. -- --Example 103 Example 89Comp. Comp. -- 0.003Example 104 Example 90Comp. Comp. -- 0.32Example 105 Example 91Comp. Comp. -- 0.41Example 106 Example 92Comp. Comp. -- 0.60Example 107 Example 93Comp. Comp. -- 1.69Example 108 Example 94Comp. Comp. -- 0.78Example 109 Example 95Comp. Comp. -- 0.15Example 110 Example 96Comp. Comp. -- 0.31Example 111 Example 97Comp. Comp. 0.11 --Example 112 Example 98______________________________________Properties of the coating using solvent-typepaintWhen using mill base (2) prepared withdispersion time of 60 minutes Hc RS Ra (Oe) (-) (.mu.m)______________________________________Comp. 2703 0.82 0.49Example 99Comp. 1731 0.81 0.48Example 100Comp. 2501 0.77 0.48Example 101Comp. 321 0.75 0.38Example 102Comp. 339 0.73 0.38Example 103Comp. 2715 0.84 0.47Example 104Comp. 2703 0.83 0.45Example 105Comp. 2716 0.83 0.42Example 106Comp. 2717 0.83 0.40Example 107Comp. 2726 0.85 0.38Example 108Comp. 2715 0.83 0.40Example 109comp. 2689 0.83 0.43Example 110Comp. 2698 0.84 0.48Example 111Comp. 2698 0.86 0.40Example 112______________________________________Properties of the coating using solvent-typepaintWhen using millbase (2) prepared When using mill base (2)with dispersion prepared with dispersiontime of 60 minutes time of 120 minutes RMS Hc RS (.mu.m) (Oe) (-)______________________________________Comp. 0.58 2696 0.85Example 99Comp. 0.59 1724 0.83Example 100Comp. 0.58 2516 0.79Example 101Comp. 0.47 325 0.81Example 102Comp. 0.46 346 0.79Example 103Comp. 0.56 2709 0.85Example 104Comp. 0.54 2712 0.86Example 105Comp. 0.52 2731 0.86Example 106Comp. 0.47 2713 0.85Example 107Comp. 0.45 2726 0.87Example 108Comp. 0.48 2713 0.85Example 109Comp. 0.53 2706 0.83Example 110Comp. 0.56 2721 0.87Example 111Comp. 0.48 2715 0.87Example 112______________________________________Properties of the coating using solvent-typepaintWhen using mill base (2) Dispersionprepared with dispersion stabilitytime of 120 minutes (Ra change rate Ra RMS after dilution) (.mu.m) (.mu.m) (%)______________________________________Comp. 0.45 0.54 16.8Example 99Comp. 0.45 0.52 12.9Example 100Comp. 0.46 0.51 20.5Example 101Comp. 0.36 0.43 9.3Example 102Comp. 0.36 0.41 9.0Example 103Comp. 0.42 0.50 13.6Example 104Comp. 0.41 0.51 13.2Example 105Comp. 0.39 0.47 11.6Example 106Comp. 0.39 0.49 15.2Example 107Comp. 0.37 0.47 11.6Example 108Comp. 0.40 0.48 13.8Example 109Comp. 0.41 0.48 19.6Example 110Comp. 0.41 0.48 17.3Example 111Comp. 0.38 0.46 12.5Example 112______________________________________
Production of water-based paints
Example 97
Using 20.0 g of barium ferrite particles obtained in Example 73, the following materials were blended in the specified ratios in a 140 ml glass pot and mixed and dispersed with 100 g of 1.5 mm.phi. glass beads by a paint shaker to make a mill base. There were prepared two types of mill base, one prepared with a dispersion time of 30 minutes and the other with a dispersion time of 60 minutes. Mill base composition:
______________________________________Barium ferrite particles 44.4 parts by weightobtained in Example 73Dispersing agent (trade 0.5 part by weightname: POIZ 521 (40%aqueous solution) produced by Kao Corp.)Defoaming agent (trade 0.3 part by weightname: Nopco 8034, produced by Sannopco Ltd.)Water 18.4 parts by weightButyl cellosolve 7.9 parts by weight______________________________________
The mill base was blended with a water-soluble acrylic emulsion specified below in the ratios shown below, and mixed and dispersed for 15 minutes by a paint shaker to obtain a water-based paint.
Water-based paint composition:
______________________________________Mill base 71.5 parts by weightWater-soluble acrylic 28.5 parts by weightemulsion (35 wt %) (tradename: SW-135 produced bySanyo Chemical Co., Ltd.)______________________________________
The obtained water-based paint was filtered through a stainless steel mesh with an opening size of 44 .mu.m, then coated on a paper-made base film to a thickness of 50 .mu.m, oriented in a 3,200 G orienting magnetic field and dried to form a coating film. The properties of the formed coating film are shown in Table 17.
By way of comparison, a water-based paint was produced in the same way as Example 97 except that the polyether-modified polysiloxane BYK-080 was not coated on the ferrite particles and these uncoated particles were added in the coating composition in the course of preparation of the water-based paint (the method same as disclosed in the afore-mentioned Japanese Patent Application Laid-open (KOKAI) 62-187772). The coating film formed by using this paint, with the mill base used therein being the type prepared with a dispersion time of 60 minutes, showed a coercive force Hc of 2,710 Oe, RS of 0.83, Ra of 0.42 .mu.m, RMS of 0.50 .mu.m, Ra changing percentage after dilution of 18.6%, and Ra during storage of 0.56 .mu.m. Zeta potential of the particles in the paint was -21.6 mV.
Example 98-108 and Comparative Examples 113-126
The same procedure as in Example 97 was carried out except for variation of the kind of the magnetic particles used to produce water-based paints. The properties of the obtained water-based paint are shown in Table 17 and Table 18.
TABLE 17______________________________________ Treated magnetic particles Coating weight of Coating weight of modified Kind of squaric acid, polysiloxane, magnetic calcd. as C calcd. as C particles (wt %) (wt %)______________________________________Example 97 Exmple 73 -- 0.52Example 98 Example 74 -- 0.27Example 99 Example 75 -- 1.08Example 100 Example 76 -- 1.43Example 101 Example 77 -- 0.40Example 102 Example 78 -- 1.83Example 103 Example 79 0.40 1.05Example 104 Example 80 1.19 0.06Example 105 Example 81 1.98 2.30Example 106 Example 82 0.39 0.15Example 107 Example 83 0.20 1.66Example 108 Example 84 0.39 0.54______________________________________ Properties of the coating using water-based paint When using mill base prepared with dispersion time of 30 minutes Hc RS Ra RMS (Oe) (-) (.mu.m) (.mu.m)______________________________________Example 97 2730 0.91 0.28 0.33Example 98 2741 0.91 0.28 0.34Example 99 1753 0.92 0.26 0.30Example 100 2555 0.90 0.30 0.35Example 101 348 0.88 0.22 0.28Example 102 372 0.88 0.24 0.29Example 103 2742 0.90 0.26 0.31Example 104 2746 0.90 0.28 0.31Example 105 1740 0.92 0.22 0.25Example 106 2560 0.90 0.28 0.32Example 107 349 0.89 0.25 0.28Example 108 375 0.88 0.25 0.29______________________________________ Properties of the coating using water-based paint When using mill base prepared with dispersion time of 60 minutes Hc RS Ra RMS (Oe) (-) (.mu.m) (.mu.m)______________________________________Example 97 2726 0.91 0.24 0.28Example 98 2746 0.92 0.26 0.30Example 99 1732 0.92 0.22 0.26Example 100 2546 0.91 0.26 0.29Example 101 358 0.91 0.20 0.24Example 102 381 0.89 0.20 0.25Example 103 2738 0.91 0.24 0.26Example 104 2749 0.92 0.25 0.28Example 105 1738 0.94 0.21 0.24Example 106 2556 0.92 0.26 0.29Example 107 357 0.91 0.23 0.26Example 108 381 0.90 0.22 0.26______________________________________ Properties of the coating using water-based paint Dispersion Storage stability stability (Ra change rate (Ra during Zeta after dilution) storage) potential (%) (.mu.m) (mV)______________________________________Example 97 8.3 0.25 -51.5Example 98 9.2 0.28 -46.6Example 99 6.8 0.22 -69.3Example 100 9.6 0.28 -52.5Example 101 8.8 0.24 -46.6Example 102 9.0 0.24 -53.2Example 103 5.6 0.26 -80.6Example 104 7.8 0.29 -58.6Example 105 3.8 0.21 -83.2Example 106 7.8 0.28 -47.9Example 107 4.2 0.24 -51.5Example 108 5.8 0.22 -49.8______________________________________
TABLE 18______________________________________ Treated magnetic particles Coated weight of Coating weight of modified Kind of squaric acid, polysiloxane, magnetic calcd. as C calcd. as C particles (wt %) (wt %)______________________________________Comp. Comp. -- --Example 113 Example 85Comp. Comp. -- --Example 114 Example 86Comp. Comp. -- --Example 115 Example 87Comp. Comp. -- --Example 116 Example 88Comp. Comp. -- --Example 117 Example 89Comp. Comp. -- 0.003Example 118 Example 90Comp. Comp. -- 0.32Example 119 Example 91Comp. Comp. -- 0.41Example 120 Example 92Comp. Comp. -- 0.60Example 121 Example 93Comp. Comp. -- 1.69Example 122 Example 94Comp. Comp. -- 0.70Example 123 Example 95Comp. Comp. -- 0.15Example 124 Example 96Comp. Comp. -- 0.31Example 125 Example 97Comp. Comp. 0.11 --Example 126 Example 98______________________________________ Properties of the coating using water-based paint When using mill base prepared with dispersion time of 30 minutes Hc RS Ra RMS (Oe) (-) (.mu.m) (.mu.m)______________________________________Comp. 2716 0.80 0.55 0.66Example 113Comp. 1756 0.79 0.58 0.71Example 114Comp. 2532 0.76 0.48 0.58Example 115Comp. 331 0.72 0.49 0.58Example 116Comp. 348 0.68 0.80 1.02Example 117Comp. 2718 0.79 0.55 0.67Example 118Comp. 2732 0.80 0.56 0.68Example 119Comp. 2722 0.77 0.53 0.70Example 120Comp. 2715 0.80 0.55 0.66Example 121Comp. 2718 0.81 0.49 0.63Example 122Comp. 2710 0.81 0.52 0.64Example 123Comp. 2710 0.76 0.52 0.62Example 124Comp. 2731 0.77 0.56 0.67Example 125Comp. 2712 0.85 0.36 0.44Example 126______________________________________ Properties of the coating using water-based paint When using mill base prepared with dispersion time of 60 minutes Hc RS Ra RMS (Oe) (-) (.mu.m) (.mu.m)______________________________________Comp. 2723 0.81 0.48 0.58Example 113Comp. 1742 0.79 0.53 0.64Example 114Comp. 2526 0.77 0.46 0.55Example 115Comp. 333 0.72 0.42 0.50Example 116Comp. 356 0.70 0.53 0.64Example 117Comp. 2721 0.82 0.42 0.51Example 118Comp. 2730 0.83 0.45 0.56Example 119Comp. 2725 0.81 0.45 0.55Example 120Comp. 2720 0.80 0.48 0.58Example 121Comp. 2718 0.84 0.43 0.52Example 122Comp. 2712 0.81 0.45 0.58Example 123Comp. 2726 0.80 0.48 0.58Example 124Comp. 2726 0.79 0.44 0.53Example 125Comp. 2700 0.85 0.36 0.43Example 126______________________________________ Properties of the coat using aqueous paint Dispersion Storage stability stability (Ra change rate (Ra during Zeta after dilution) storage) potential (%) (.mu.m) (mV)______________________________________Comp. 31.2 0.55 -9.6Example 113Comp. 21.0 0.65 -8.8Example 114Comp. 24.1 0.53 -6.5Example 115Comp. 20.0 0.48 -21.2Example 116Comp. 25.1 0.55 -6.8Example 117Comp. 17.2 0.48 -16.9Example 118Comp. 19.2 0.51 -18.5Example 119Comp. 15.9 0.53 -16.9Example 120Comp. 18.8 0.54 -21.5Example 121Comp. 15.6 0.51 -26.8Example 122Comp. 18.6 0.51 -17.8Example 123Comp. 24.2 0.61 -12.6Example 124Comp. 19.9 0.49 -15.5Example 125Comp. 16.8 0.46 -32.3Example 126______________________________________

Number	Name	Date
3849152	Mimeault	Nov 1974
4369265	Buxbaum et al.	Jan 1983
4544415	Franz et al.	Oct 1985
5232782	Charmot	Aug 1993
5387467	Hohner et al.	Feb 1995

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Derwent Database WOU Week 9440 AN 94-322377 XP002017552 & JP-A-06 248 217 Sep. 1994.