DE3103460A1 - Process for complexing metal oxide particles in an organic medium - Google Patents

Abstract

The process disclosed is notable for the medium having worked into it an effective amount of a complexant of the formula (1st formula), in which R1 is selected from alkyl and alkenyl groups having from 4 to 22 carbon atoms, aryl groups having from 4 to 10 carbon atoms, alkyl and alkenyl groups having from 4 to 22 carbon atoms, substituted with one or more aryl groups having from 4 to 10 carbon atoms, and aryl groups having from 4 to 10 carbon atoms, substituted by one or more alkyl or alkenyl groups having from 1 to 22 carbon atoms, R2 is selected from hydrogen, -(CH2CH2O)nH, where n is an integer from 1 to 10, alkyl and alkenyl groups having from 1 to 22 carbon atoms, aryl groups having from 4 to 10 carbon atoms, alkyl and alkenyl groups having from 1 to 22 carbon atoms and substituted by one or more aryl groups having from 4 to 10 carbon atoms, and aryl groups having from 4 to 10 carbon atoms and substituted by one or more alkyl or alkenyl groups having from 1 to 22 carbon atoms, R3 and R4, independently of one another, are selected from hydrogen, -CH3 and -CH2CH3, and R5 and R6, independently of one another, are selected from hydrogen, -CH3, -CH2CH3 and -(CH2CH2O)nH, where n is an integer from 1 to 10. <IMAGE>

Description

description

The invention relates to a method for complexing Metal oxide particles in an organic medium as well as dispersing or flaking of metal oxide particles in an organic medium. It also refers to a magnetic recording medium comprising a magnetic carrier and an improved, magnetizable coating provided on the carrier.

Many end uses require that certain metal oxide particles are complexed to achieve a desired effect such as dispersing of the particles in an organic medium. For example is for the recording industry to achieve a useful magnetizable coating on a non-magnetic one Carrier necessary, magnetic pigments fine in a carrier with the help of a binder to distribute. Also in the plastics industry it is often necessary to have a lot of one finely divided metal oxide, such as antimony trioxide or antimony pentoxide, via a Distribute plastic compound evenly. To ensure uniform stable dispersions To achieve such metal oxides in organic media, there must be an effective amount of one Complexing agent can be used, which acts as a dispersing agent in this application Means works. Dispersants used in the past are e.g. N-acylsarcosine derivatives, See U.S. Patent 4,153,754.

It is also disclosed for purposes similar to that in the cited patent the use of compounds such as N-tallow-1,3-diamino-propane, especially in Form of the dioleate, known.

The object of the invention is to provide improved complexing agents for use in dispersing or flaking finely divided metal oxide particles in organic media.

These and other tasks, advantages and features emerge from the following description of the invention.

A process has now been found for complexing finely divided metal oxide particles in an organic medium which is characterized in that an effective amount of a complexing agent of the formula ## STR3 ## is added to the medium wherein R1 is selected from alkyl and alkenyl groups with 4 to 22 carbon atoms, aryl groups with 4 to 10 carbon atoms, alkyl and alkenyl groups with 4 to 22 carbon atoms, substituted with one or more aryl groups with 4 to 10 carbon atoms, and aryl groups with 4 to 10 carbon atoms, substituted with one or more alkyl or alkenyl groups with 1 to 22 carbon atoms, R2 under hydrogen, - (CH2CH2O) H, where n is an integer from 1 to 10, alkyl and alkenyl groups with 1 to 22 carbon atoms, aryl groups with 4 to 10 carbon atoms, alkyl and alkenyl groups with 1 to 22 carbon atoms, substituted with one or more aryl groups with 4 to 10 carbon atoms, and aryl groups with 4 to 10 carbon atoms, substituted with one or more alkyl or alkenyl groups with 1 to 22 carbon atoms, R3 and R4 independently of one another under hydrogen, -CH3 and -CH2CH3 and R5 and R6 independently of one another under hydrogen, -CEl3, -CH2C H3 and - (CH2CH2O) nTi, where n is an integer from 1 to 10, are selected.

The invention also leads to a magnetic recording medium with a non-magnetic carrier and a magnetizable one provided thereon Coating, the magnetizable coating having a binder and therein with the aid of a dispersing agent having finely divided magnetic pigments and the dispersing agent Agent is a compound of the formula given above.

According to preferred embodiments, in the given formula R1 can be selected from alkyl and alkenyl groups having 4 to 22 carbon atoms. Preferably, R1 is a long chain alkyl group having from about 8 to about 18 carbon atoms. Thus, R1 can be any long chain alkyl group, e.g.

those that differ from naturally occurring fats and oils, such as cocoa, Sebum and soy. The group R1 can also be an aryl group with about 4 to about 10 carbon atoms or an alkyl or alkenyl group as defined above, substituted with one or more such aryl groups as a phenylstearyl group. Likewise, the aforementioned aryl group with an alkyl or alkenyl group with 1 up to 22 carbon atoms. Group R2 is selected independently under hydrogen, - (CH2CH2O) nH, where n is an integer from 1 to 10, and the same group as given for R1, but with the alkyl and alkenyl groups 1 can contain up to 22 carbon atoms.

Where reference is made herein to an aryl group, the The term should be understood to include any aromatic system which the meets the specified criteria, e.g. has 4 to 10 carbon atoms. The aryl group can therefore use heteroatoms, such as nitrogen, sulfur and oxygen, as part of the aromatic Group include.

The groups R3 and R3 are independently selected from Hydrogen, -CH3 and -CH2CH3. Both groups R3 and R4 are preferably methyl. Groups R5 and R6 are independent chosen from each other among Hydrogen, -CH3, -CH2CH3 and - (CH2CH2O) nH, where n is an integer from 1 to 11 is.

Preferably R5 and R6 are hydrogen.

The most preferred class of compounds is given by the above formula reproduced, wherein R1 is an alkyl group having from about 4 to about 22 carbon atoms, is preferably from about 8 to about 18 carbon atoms, and is particularly preferred is derived from tallow, R2 is hydrogen, R3 and R4 are both methyl, and R5 and R6 are both hydrogen are. The most preferred compound is therefore 1- (N-tallowamino-2-amino-2-methylpropane.

Other compounds useful in practicing the invention are e.g. 1- (N-dodecylamino) -2-amino-2-methyl-propane, 1- (N-phenylstearylamino) -2-amino-2-methylpropane, 1- (benzyl-N-tallowamino) -2-amino-2-methyl-propane, 1 - (N-morpholino) -2-amino-2-methyl-propane, 1- (N-di-n-butylamino) -2-amino-2-methyl-propane, 1- (tallow-N-ethanolamino) -2-diethanolamino-2-methyl -propane, 1- (methyl-N-octadecyl-amino) -2-amino-2-methyl-propane, 1 - (N-n-butylamino) -2-amino-2-methyl-propane and 1- (N-eicosylamino) -2-amino-2-methylpropane.

The compounds according to the invention can be known to those skilled in the art chemical techniques are synthesized. For example, an editorial is that of A. G. Johnson, JACS. 68, 14 (1946).

For the production of the N-tallow-2-methyl-1,2-propane-diamine used according to the invention you can e.g. 393 g of primary tallow amine with 147 g of nitropropane in a 1 l Parr autoclave made of stainless steel with stirrer, heated to 900C, to react.

121 g formalin (37%) can be added under pressure and the reaction mixture heated to 90 ° C. for about 6 hours in order to obtain 95% of the desired nitro intermediate obtain. 500 g of the intermediate can then with hydrogen in the presence of 22.5 g of nickel catalyst and 35 g of filter aid in a 1 liter Parr autoclave made of stainless steel can be implemented with a stirrer. The hydrogenation can take place at 600C and 1000 psig (69 bar) hydrogen pressure for several hours. The product may contain about 83% of the desired diamine and 15% of the corresponding monoamine.

The term complexing used here is used here in the meaning any chemical, physical or other interaction between the complexing agent used according to the invention and the metal oxide to be complexed, the a chemical, physical, or other association between the complexing agent and allows the metal oxide particle to enter. The formation of real organometallic Complex is therefore not necessary.

As used herein, the term "dispersing" is the metal oxide particles against settling in the case of liquid suspensions or migration in the case of Metal oxides distributed in a polymeric material, physically stabilizing meant. The term flake "or flocculation is used here to mean precipitation, Agglomeration or other physical association of the metal oxide particles with the formation of a markedly increased density of the metal oxide particles.

The organic medium used in the process of the invention can vary widely and includes liquid and solid organic substances in which finely divided metal oxide particles are incorporated. So can usable organic Media organic liquids such as mineral oil, synthetic oils, derived from petroleum Oils and typical organic solvents, like methyl ethyl ketone, Methyl isobutyl ketone and toluene. Of course, mixtures of different of organic materials as an organic medium for the purpose of practical implementation of the invention can be used. For example, a 1: 1: 1 mixture of methyl ethyl ketone, Methyl isobutyl ketone and toluene can be used.

As for the finely divided metal oxide particles that are useful for practical use Typically, particles with sizes are useful in practicing the invention from about 0.01 to about 100 µm is practically useful when dispersing the particles is desired. Such particles can be of any shape, either regular or irregular to have. Such particles can be spherical or needle-shaped, such as Fe203- and CrO2 particles, which are generally about 0.1 to 1.0 µm in length and one From about 0.01 to about 0.2 µm thick. The type of metal oxide particles used is not critical. For example, the metal oxide particles can be any of the well known Oxides of iron, nickel, copper, vanadium, molybdenum, uranium, mercury, chromium, Magnesium, titans and antimony as well as others.

In the practice of the invention, the complexing agent exist exclusively in the form indicated by the above formula. The complexing agent can also be in a completely or partially neutralized form. So can the complexing agents according to the invention, being diamines, in whole or in part neutralized with acids, preferably fatty acids such as oleic acid.

Thus the complexing agent can be used for every mole of diamine present present either as a mono- or as a disalt. A particularly useful dispersant appears to be N-tallow-2-lbathyl-1,2-propane-diamine-dioleate.

If the complexing agent is to act as a dispersant, depends the actual amount of finely divided metal oxide needed to disperse in any one particular organic medium used dispersant strongly depends on many factors, such as the size, type, amount of metal oxide particles present, and nature the organic medium in which the metal oxide particles are to be dispersed.

In any case, the amount of dispersant present should be be an effective amount. This means a lot of dispersants, which is sufficient to at least partially counteract the metal oxide particles in the medium to stabilize sitting down or walking. The amount doesn't have to be enough to cover the finely divided metal oxide particles dispersed indefinitely throughout the organic medium to keep, but just enough to keep the system stable beyond that that would otherwise be obtained without the presence of the dispersant.

If the complexing agent is to act as a flocculant, depends again the amount used of the factors listed above for the dispersant away. The amount employed should be an "effective amount" which refers to an amount should, which is sufficient to at least an increased degree of flocculation of the metal oxide particles to effect that which would otherwise occur in the absence of the flocculant would.

When the invention is in the field of magnetic recording media is used, useful results are obtained. In such a field of application it is common to use a magnetic recording medium with a non-magnetic To use carrier and a magnetizable coating on the carrier. The magnetizable Coating comprises a binder as well as a magnetic pigment that is contained therein with the help of of a dispersant is kept finely divided. A typical carrier will made of a synthetic resin such as polyester or polyvinyl chloride, but can on the other hand paper, Be glass or metal. The wearer can use the In the form of a tape, a plate, a disk or the like. Have. For dispersing of a magnetic pigment in a binder is a suitable amount of dispersant according to the invention about 1 to about 10% by weight, calculated on the weight of the magnetic Pigments, preferably from about 2 to about 5% by weight. Typical binders that can be used are polyvinyl chloride, Polyvinyl acetate, polyacrylate, polyesters, polyester amides, polyurethanes and copolymers of at least two monomers from the group vinyl chloride, vinyl acetate, acrylonitrile, Vinyl alcohol, vinyl butyral and vinylidene chloride. Particularly useful binders are Polyurethane and partially hydrolyzed polymers of vinyl chloride and vinyl acetate.

The magnetizable particles present in the binder are conventional and typically, for example, iron powder, Fe2O3 particles, and CrO2 particles.

To practice the invention one can use the magnetizable Particles, the dispersant according to the invention and part of the binder in Mix thoroughly a solvent for the binder using a ball mill.

The remainder of the binder dissolved in a suitable solvent and A lubricant can then be added and the whole thing further in the ball mill some Be ground for hours. Typical solvents for the binder are, for example, organic Liquids such as esters, e.g. ethyl acetate, ethers, e.g. tetrahydrofuran, ketones, e.g. methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, hydrocarbons, e.g. toluene and chlorinated hydrocarbons, e.g. 1,2-dichloroethane. The mixing the materials can certainly also be done in a stage in which all components be fed to the ball mill at the same time. The amount of magnetizable particles (Pigment) is about 60 to 85% by weight, calculated on the total amount of the magnetizable Coating. After thorough chopping the dispersion in the ball mill the larger magnetizable particles can be screened out and the magnetizable one obtained Coating can be applied to the support in a uniform layer. The whole structure can then be dried and the solvent evaporated and a recording layer can be formed with a thickness of, for example, about 2 to about 10 μm remain on the carrier. The layer can, if desired, be hardened or subjected to a calendering process in which the surface of the layer becomes smoother.

The invention is described in more detail below in the non-restrictive Examples described.

Example I This example illustrates the utility of a Compound, 1 - (N-tallowamino) -2-amino-2-methyl-propane, as a suspending agent for Iron oxide (Fe2O3) in a mineral oil of cosmetic quality demonstrated and with the usefulness of a previously known suspending agent, Sarkosyl-NL, which chemically Sodium Lauryl Sarcosinate is compared. Since the Sarkosyl-NL material as a 30% aqueous solution is available, two known means were used in the comparison used, one material in the form of the available 30% solution and the other Sarkosyl-NL which was first dried to produce 100% mg active material.

The components in these systems were as follows: (1) 1% Fe 2 O 3 (0.074-0.037 mm or (2) 1% Fe203 200-400 mesh) 3.33% Sarkosyl NL (30%) 1% Sarkosyl NL (dried) 95.67% mineral oil 98% mineral oil (3) 1% Fe203 (0.074-0.037 mm or 200-400 mesh) 1% 1- (N-tallowamino) -2-amino-2-methyl-propane 98% mineral oil suspensions were first made with a polytetrafluoroethylene for 48 h (Teflon) coated stir bar and magnetic stirrer. The suspensions were then kept in tightly closed vessels and not disturbed for the duration. After one day about 90% of the Fe203 had settled in both samples 1 and 2, while sample 3 was still in suspension.

After 4 weeks, about 60% of the 203 each had settled in sample 3. Even after a period of 8 weeks, no more than 90% of the Fe 2 O 3 of sample 3 had remained discontinued, which contained the complexing agent according to the invention.

Example II Following the procedure of Example I, various other complexing agents according to the invention in combination with 0.1% Fe 2 O 3 in Mineral oil used. The complexing agents used and the settling rates are shown in Table I. In this table are the settling speeds given in days and corresponding to the time required to settle 10, 50 or 90% of the Fe203 divided into the time required in the dispersion.

TABLE I S u b s t a n z% Fe2O3 Settling speeds (days) 10% 50% 90% 1- (N-DODECYLAMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil 2 8> 10 1- (N-PHENYLSTEARYLAMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil 3> 10> 10 1- (BENZYL-N-Tallow- AMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil 3> 10> 10 1- (N-MORPHOLINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil <1 <1 <1 1- (N-di-n-BUTYL-AMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil <1 3 7 1- (TALG-N-ETHANOLAMINO) -2-DIETANOLAMINO-2-METHYL-PROPANE 0.1% mineral oil 2 8> 10 1- (METHYL-N-OCTADECYL-AMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil <1 4> 10 1- (N-n-BUTYL-AMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil <1 4> 10 1- (N-EICOSYLAMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil 2 7> 10 CONTROL 0.1% Mineral oil <1 <1 <1 Example III According to the procedure of Examples I and II were several complexing agents according to the invention for Complexing CrO2 used in mineral oil. Table II contains those in the same Manner as results obtained in Table I.

Example IV Following the procedure of Examples I and II, various Complexing agent according to the invention for complexing So30, in mineral oil used. Table III contains those obtained in the same manner as in Table I. Results.

Example V The same procedure as in Examples I and II was followed used to complex TiO2 in mineral oil. Which in the same way as for Results obtained in Table I are shown in Table III.

TABLE II S u b s t a n z% CrO2 Settling speed (days) 10% 50% 90% 1- (N-DODECYLAMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil <1 3 5 1- (N-PHENYLSTEARYLAMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil <1 3 5 1- (BENZYL-N-TALG-AMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil <1 3 5 1- (N-MORPHOLINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil <1 1 3 1- (N-di-n-BUTYL-AMINO) -2-AMINO-2- METHYL PROPANE 0.1% mineral oil <1 3 5 1- (TALG-N-ETHANOLAMINO) -2-DIÄTHANOLAMINO-2-METHYL-PROPANE 0.1% mineral oil <1 3 4 1- (METHYL-N-OCTADECYL-AMINO) -2-AMINO-2-METHYL-PROPANE 0.1% Mineral oil <1 3 5 1- (N-n-BUTYL-AMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil <1 3 5 1- (N-EICOSYLAMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil <1 2 4 1- (N-TALGAMINO) -2-AMINO-2-AMINO-2-METHYL-PROPANE 0.1% mineral oil <1 2 - CONTROL 0.1% mineral oil <1 3 5 TABEL III S u b s t a n z% Sb2O3 Sitting speeds (days) 10% 50% 90% 1- (N-DODECYLAMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil <1 3 6 1- (N-PHENYLSTEARYLAMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil 1 7> 19 1- (BENZYL-N-Tallow- AMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil <1 3 14 1- (N-MORPHOLINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil <1 <1 5 1- (N-di-n-BUTYL-AMINO) -2-AMINO-2-METHYL -PROPANE 0.1% mineral oil <1 5 18 1- (TALG-N-ETHANOLAMINO) -2-DIÄTHANOLAMINO-2-METHYL-PROPANE 0.1% mineral oil 1 8> 19 1- (METHYL-N-OCTADECYL-AMINO) -2-AMINO-2-METHYL-PROPANE 0.1% Mineral oil 1 8> 19 1- (N-n-BUTYL-AMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil <1 3 6 1- (N-EICOSYLAMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil <1 2 5 1- (N-TALGAMINO) -2-AMINO-2-AMINO-2-METHYL- PROPANE 0.1% mineral oil <1 - CONTROL 0.1% mineral oil <1 3 6 TABEL IV S u b s t a n z% TiO2 Settling speed (days) 10% 50% 90% 1- (N-DODECYLAMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil 1 6 17 1- (N-PHENYLSTEARYLAMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil 1 7> 19 1- (BENZYL-N-Tallow- AMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil 1 5 17 1- (N-MORPHOLINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil <1 3 5 1- (N-di-n-BUTYL-AMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil 1 7 18 1- (TALG-N-ETHANOLAMINO) -2-DIÄTHANOLAMINO-2-METHYL-PROPANE 0.1% Mineral oil 1 8> 19 1- (METHYL-N-OCTADECYL-AMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil 1 8> 19 1- (N-n-BUTYL-AMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil 1 7 15 1- (N-EICOSYLAMINO) -2-AMINO-2-METHYL-PROPANE 0.1% mineral oil 1 6> 19 1- (N-TALGAMINO) -2-AMINO-2-AMINO-2-METHYL-PROPANE 0.1% mineral oil 1 1 1 CHECK 0.1% mineral oil 1 5> 19 Goes out of the tables show that some of the complexing agents according to the invention for increasing the Dispersion stability of Fe203 in mineral oil compared to the system without a dispersant are effective, while others, 1- (N-morpholino) -2-amino-2-methyl-propane, Fe2O3-flocculant are in mineral oil.

Claims (8)

A process for complexing metal oxide particles in an organic medium. Claims 1. A process for complexing metal oxide particles in an organic medium, characterized in that an effective amount of a complexing agent of the formula wherein R1 is selected from alkyl and alkenyl groups with 4 to 22 carbon atoms, aryl groups with 4 to 10 carbon atoms, alkyl and alkenyl groups with 4 to 22 carbon atoms, substituted with one or more aryl groups with 4 to 10 carbon atoms, and aryl groups with 4 to 10 carbon atoms, substituted with one or more alkyl or alkenyl groups with 1 to 22 carbon atoms, R2 under hydrogen, - (CH2CH2O) nH, where n is an integer from 1 to 10, alkyl and alkenyl groups with 1 to 22 carbon atoms, aryl groups with 4 to 10 carbon atoms, alkyl and alkenyl groups with 1 to 22 carbon atoms, substituted with one or more aryl groups with 4 to 10 carbon atoms, and aryl groups with 4 to 10 carbon atoms, substituted with one or more alkyl or alkenyl groups with 1 to 22 carbon atoms, R3 and R4 independently of one another under hydrogen, -CH3 and -CH2CH3 and R5 and R6 independently of one another under hydrogen, -CH3, -CH2CH3 and - (CH2CH2O) n H, where n is an integer from 1 to 10, are selected. 2. The method according to claim 1, characterized in that the complexing agent acts as a dispersing agent. 3. The method according to claim 1, characterized in that the complexing agent acts as a flocculant. 4. The method according to any one of the preceding claims, characterized in that that the complexing agent among 1 - (N-tallowamino) -2-amino-2-methyl-propane, 1- (N-dodecylamino) -2-amino-2-methyl-propane, 1- (N-phenylstearylamino) -2-amino-2-methylpropane, 1- (benzyl-N-tallowamino) -2-amino-2-methyl-propane, 1- (N-morpholino) -2-amino-2-methylpropane, 1- (N-di-n-butylamino) -2-amino-2-methyl-propane, 1- (Tallow-N-ethanolamino) -2-diethanolamino-2-methyl-propane, 1- (methyl-N-octadecylamino) -2-amino-2-methyl-propane, 1- (N-n-butylamino) -2-amino-2-methyl-propane and 1- (N-eicosylamino) -2-amino-2-methyl-propane is selected. 5. The method according to any one of claims 1 to 3, characterized in, that 1- (N-tallowamino) -2-amino-2-methyl-propane is used as a complexing agent. 6. Magnetic recording medium, characterized by a non-magnetic one Carrier and a magnetizable coating applied to it, which is a binder and magnetic particles finely dispersed therein with the aid of a dispersing agent wherein the dispersing agent contains a compound of the formula according to claim 1 is. 7. Magnetic recording medium according to claim 6, characterized in that that the dispersing agent is selected from among the compounds according to claim 4 is. 8. Magnetic recording medium according to claim 6, characterized in that that the dispersing agent is the compound according to claim 5.