FI74888B - VATTENFRI, FLYTANDE KOMPOSITION SOM OMFATTAR EN ORGANOFIL REOLOGISK LERBLANDNING OCH FAERGBLANDNING SOM BASERAR SIG PAO DEN. - Google Patents

Description

j 74888

The present invention relates to a suspension of pigments and other particles in anhydrous flowable compositions. Anhydrous flowable compositions may broadly be characterized by lubricating greases, oil-based sludges, oil-based sealants, paint-varnish removers, paints, varnishes, enamels, old, epoxies, casting sand binders, adhesives and putties, inks, polyester .

These flowable systems often contain finely divided suspended substances such as pigments and the like. A rheological excipient is added to thicken the system to provide a thixotropic runoff behavior at high viscosity at low shear rates. Various organically adapted clays and other inorganic and organic compounds have been used in the past to produce these Theological effects.

Previously available theological and suspending agents have had various shortcomings which are overcome by the agents of this invention. Thus, aluminum stearate is remarkably deficient in its ability to keep pigments in suspension in most organic binders and the ease with which pigments can be redispersed after settling out of such suspensions over long aging periods. The gel formed by the addition of aluminum stearate to organic binders is of a rubbery type rather than the desired thixotropic type of gel effective to maintain stable suspensions. The presence of aluminum stearate in pigment suspensions, such as paints, has no beneficial effect on the brushing properties of such suspensions.

2 74888

Organic derivatives of montmorillonite have also been used as suspending agents. However, such derivatives are generally effective only in the presence of aromatic and polar solvents and are therefore ineffective when added to currently popular odorless, aliphatic hydrocarbon solvents.

In particular, organophilic clays previously used in the art require the use of a polar solvent activator, which must be added to the composition to produce a rheological effect. If polar solvent activators are not used, the desired theological properties, viscosity structure, pigment deposition control, and shrinkage control are not fully achieved, i.e., only a portion of the clay thickening capacity is used. In addition, if polar solvent activators are omitted, the viscosity of currently known organocarbon-containing mixtures increases during storage, thus having a detrimental effect on the Theological properties originally intended for the system.

20 Some of these polar additives, such as acetone, alcohols and the like, have low flash points and should therefore be avoided if possible. In addition, these polar additives must be added as a separate step in the preparation of the compositions.

25 This separate step increases the cost of composition. In addition, some polar additives may react with other ingredients of the composition to remove essential theological properties.

Hydrogenated castor oil is a much more effective suspending agent than the disclosed montmorillonite derivatives and is suitable for use in aliphatic hydrocarbon solvents. However, hydrogenated castor oil has the disadvantage of being unstable at elevated temperatures used in the treatment of suspensions, e.g. paint mills, with the result that bubble formation or the formation of small grains occurs in such suspensions;

II

3 74888 This lack of smoothness is detrimental to most suspensions, including those used in the field of protective coatings and inks. Polyethylene has also been tried as a suspending agent, but it also has 5 drawbacks in this respect. For example, polyethylene-containing paints as a suspending agent are characterized by settling of the pigment they contain within a few days, have poor runoff properties, and show little or no swelling during or after the initial grinding of the paint-10 parts. good dispersion, and resembles whipped cream in appearance. Thus, it is apparent that no prior Theological Auxiliary in the art has fully satisfied or enhanced a wide variety of anhydrous flowable systems.

In contrast to prior art compositions, the present invention provides a Theological organophilic clay additive that does not require the addition of a polar solvent activator while maintaining a wide range of gelling ability without varying dispersion structure and viscosity properties. Certain rheological additives disclosed herein are defined in more detail in co-pending patent application 813617 of the same applicant.

A self-activating organophilic clay gelling agent with improved dispersibility in anhydrous flowable compositions is prepared by combining a smectite-type clay and an organic at least one long chain alkyl group and at least one group selected from a C 1-6 unsaturated alkyl group or 2 to 6 carbon atoms. from a hydroxyalkyl group, a reaction product of a cationic compound.

4,74888

The anhydrous fluid composition of the invention contains, as a theological aid, an organophilic clay gelling agent which is a reaction product of a quaternary ammonium compound of an organic cationic compound and a smectite-type clay having a cation exchange capacity of at least 75 milliequivalents per 100 g of said clay. a) a first member which is a N, N-unsaturated alkyl group or a hydroxyalkyl group having 2 to 6 carbon atoms or a mixture thereof, b) a second member which is a long chain alkyl group having 12 to 60 carbon atoms, and c) a third and a fourth member. a member selected from the groups listed in a) above, aralkyl groups, or alkyl groups having 1 to 22 carbon atoms, or mixtures thereof; and the amount of said organic cationic compound is between 90 and 140 milliequivalents per 100 g of said clay based on 100% of the active clay.

The clays used to prepare the organophilic clay gelling agents of this invention are smectite-type clays having a cation exchange capacity of at least 75 milliequivalents per 100 g of clay. Particularly preferred clay types are the naturally occurring Wyoming subspecies of 25 expandable clay bentonite and the like, and hectorite, expandable magnesium lithium silicate clay.

The cation exchange capacity of smectite-type clays can be determined by a well-known ammonium acetate method.

Clays, especially bentonite-type clays, are preferably converted to the sodium form, unless they are already in this form. This can be conveniently done by preparing an aqueous clay slurry and passing the slurry through a sodium cation exchange bed. Alternatively, the clay may be mixed with water and a soluble sodium compound such as sodium carbonate, sodium hydroxide and the like, followed by cutting the mixture with a clay mill or press.

Il 5 74888

Naturally or synthetically, smectite-type clays prepared by a pneumatolytic or, preferably, hydrothermal synthetic method can also be used to prepare the clays of the organophilic compounds of the present invention. Representatives of such clays include montmorillonite, bentonite, beidellite, hecto-rite, saponite and stevensite. Synthetic clays can be synthesized hydrothermally by forming an aqueous reaction mixture in the form of a slurry containing a mixture of aqueous oxides or hydroxides of the desired metal with or without sodium fluoride (or alternatively a variable cation or mixture thereof) as may be appropriate for a particular synthetic smectite. The slurry is then placed in an autoclave and heated under autogenous pressure to a temperature in the range of about 100 to 325 ° C, preferably 274 to 300 ° C, for a time sufficient to form the desired product.

The organic cationic compounds useful in the present invention can be selected from a wide variety of agents capable of forming an organophilic clay by exchanging cations with a smectite-type clay. The organic cationic compound must have a positive charge located on one atom or a small group of atoms within the compound.

The &, Y '' - unsaturated alkyl group contained in the organic cationic compound can be selected from a wide variety. They may be cyclic or acyclic, unsubstituted or substituted by aliphatic groups containing up to 3 carbon atoms, so that the total number of aliphatic carbons in the β, β-unsaturated group is 6 or less. The β, β-unsaturated alkyl group may be substituted by an aromatic ring which is likewise conjugated to a double bond of the β, β, group, or the β group is substituted by both an aliphatic group and an aromatic ring.

6 74888

Representative examples of cyclic β, γ-unsaturated alkyl groups include 2-cyclohexenyl and 2-cyclopentenyl groups.

Representative examples of acyclic β, β-unsaturated alkyl groups containing 6 carbon atoms or less include propargyl, allyl (2-propenyl), crotyl (2-butenyl), 2-pentenyl, 2-hexenyl, 3-methyl-2-butenyl, 3-methyl-2-pentenyl, 2,3-dimethyl-2-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 2,4-pentadienyl and 2,4-hexadienyl.

Representative examples of acycloaromatic substituted groups include cinnamyl, (3-phenyl-2-propenyl), 2-phenyl-2-propenyl, and 3- (4-methoxy-phenyl) -2-propenyl.

Representative examples of aromatic and aliphatic substituted groups include 3-phenyl-2-cyclohexenyl, 3-phenyl-2-cyclopentenyl, 1,1-dimethyl-3-phenyl-2-propenyl, 1,1,2-trimethyl- 3-phenyl-2H-2-propenyl, 2,3-dimethyl-3-phenyl-2-propenyl, 3,3-dimethyl-2-phenyl-2-propenyl and 3-phenyl-2-butenyl.

The hydroxyalkyl group is selected from hydroxyl-substituted aliphatic groups in which the hydroxyl group is not substituted on the carbon adjacent to the positively charged atom and in which 2 to 6 aliphatic carbons are present. The alkyl group may be substituted by an aromatic ring. These include 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxypentyl, 6-hydroxyhexyl, 2-hydroxy-propyl, 2-hydroxybutyl, 2-hydroxypentyl, 2-hydroxyhexyl, 2-hydroxycyclohexyl, 3-hydroxycyclohexyl , 4-hydroxycyclohexyl, 2-hydroxycyclopentyl, 3-hydroxycyclopentyl, 2-methyl-2-hydroxypropyl, 1,1,2-trimethyl-2-hydroxypropyl, 2-phenyl-2-hydroxy-35-ethyl, 3-methyl- 2-hydroxybutyl and 5-hydroxy-2-pentenyl.

il 7 74888

Long chain alkyl groups may be branched or unbranched, saturated or unsaturated, substituted or unsubstituted, and the group-straight chain moiety should have from 12 to 60 carbon atoms.

5 Long chain alkyl groups may be derived from naturally occurring oils, including various vegetable oils such as corn oil, coconut oil, soybean oil, cottonseed oil, castor oil and the like, as well as various animal oils and fats such as tallow. Alkyl groups may likewise be petrochemical derivatives, such as those derived from alpha-olefins.

Representative examples of useful branched, saturated groups include 12-methylstearyl and 12-ethylstearyl groups.

Representative examples of useful branched unsaturated groups include 12-methyloleyl and 12-ethyloleyl groups.

Preferred examples of unbranched saturated groups include lauryl, stearyl, tridecyl, myristal (tetradecyl), pentadecyl, hexadecyl, hydrogenated tallow and docosonyl.

Representative examples of unbranched unsaturated and unsubstituted groups include oleyl, linoleyl, linolenyl, soy, and tallow groups.

The remaining groups on the positively charged atom are selected from a) a member of a group selected from a β, β-unsaturated alkyl group and a hydroxyalkyl group having 2 to 6 carbon atoms; both described above, b) an alkyl group having 1 to 22 carbon atoms, cyclic and acyclic, and c) an aralkyl group, i.e., benzyl and substituted benzyl groups having fused ring groups having 1 to 22 carbon atoms in the alkyl moiety. atom linearly or branched.

8 74888

Representative examples of the aralkyl group, i.e., benzyl or substituted benzyl groups, include a benzyl group and groups derived from, e.g., benzyl halides, benzhydryl halides, trityl halides, 1-halo-1-phenylalkanes such as 1-halo -1-phenylethane, 1-halo-1-phenylpropane and 1-halo-1-phenyloctadecane; substituted benzyl groups derivable from ortho-, meta- and para-chlorobenzyl halides, para-methoxybenzyl halides, ortho-, meta- and para-nitrilobenzyl halides and ortho-, meta- and para-alkylbenzyl halides in which the alkyl chain contains 1-22 carbon atoms; and fusion ring benzyl-type groups derivable from 2-halomethylnaphthalene, 9-halomethylanthracene and 9-halomethylphenentren, wherein the halogen group is chlorine, bromine, iodine or any other such group which acts as a leaving group in the group of the benzyl nitrogen , so that the nucleophile replaces the leaving group of the benzyl-type group.

Representative examples of useful alkyl groups, which may be linear or branched, cyclic or acyclic, include methyl, ethyl, propyl, 2-propyl, iso-butyl, cyclopentyl and cyclohexyl groups.

Alkyl groups can also be derived from other natural oils, both substituted and unsubstituted, as described above, including various vegetable oils such as tallow oil, corn oil, soybean oil, cottonseed oil, castor oil and the like, as well as various animal oils and fats.

Il 9 74888

Many methods for preparing organic cationic salts are known. For example, in preparing a quaternary ammonium salt, one skilled in the art would prepare a secondary dialkylamine, e.g., nitrile-5, by hydrogenation (U.S. Patent 2,355,356), and then form a tertiary methyldilacylamine by reductive alkylation using formaldehyde as the methyl group source. UG Patent 3,136,819 discloses the formation of quaternary amine halides by the addition of benzyl chloride, or by the addition of benzyl bromide to a tertiary amine (U.S. Patent 2,776,617).

The salt anion is preferably selected from the group consisting of chloride and bromide and mixtures thereof, and is preferably chloride. Other anions such as acetate-15, hydroxide, nitrite, etc. may be present in the organic cationic compound to neutralize the cation. The representative formula is' f 1

20 R.-X + -R- M

R 3 wherein R 1 is selected from the group consisting of a Γ-25 unsaturated alkyl group or a hydroxyalkyl group having 2 to 6 carbon atoms, R 2 is a long chain alkyl group having 12 to 60 carbon atoms, R 1 and R 4 are selected from the group consisting of an R 1 group, an aralkyl group or An alkyl group having 1 to 22 carbon atoms, X is nitrogen, and 30 M is selected from the group consisting of Cl, Br ", NO 2", OH "and C 2 H 3 O 2".

The organophilic clays of this invention can be prepared by mixing clay, a quaternary ammonium compound and water, preferably at a temperature in the range of 20 to 100 ° C, and most preferably at 35 to 77 ° C, for a sufficient period of time. the organic compound is covered with clay particles, followed by filtration, washing drying and grinding. When organophilic clays are used in emulsions, the drying and grinding steps can be omitted. When the clay, the quaternary ammonium compound and the water are mixed together in cellular concentrations to prevent sludge formation, the filtration and washing steps can be omitted.

The clay is preferably dispersed in water at a concentration of about 1 to 80%, most preferably 2 to 7%, the slurry is optionally centrifuged to remove non-clay impurities that make up about 10 to 50% of the starting clay mixture, the slurry is mixed and heated to 35 to 77 ° C. The quaternary ammonium salt is then added in the desired equivalent ratio, preferably as a liquid in isopropanol or dispersed in water, and stirring is continued to complete the reaction.

To facilitate processing, it is preferred that the total organic matter content of the organophilic clay reaction products of this invention be less than about 50% by weight of the organic clay. Although higher concentrations are useful, it is then difficult to filter, dry and grind the reaction product.

The amount of organic cation added to the clay for the purposes of this invention must be sufficient to provide the clay with the desired improved dispersibility property. This amount is defined as the milliequivalence source, which is the number of milliequivalents (M.E.) of organic cation in organic clay per 100 g of clay, calculated on 100% of the active clay. The organophilic clays of this invention should have a milliequivalence ratio of 35 to 140 and preferably 100 to 130.

II

Organophilic clays produced at valence ratios of 11,74888 are not effective gelling agents, although they may be good gelling agents dispersed in the usual manner in polar organic dispersants.

5 At higher milliequivalent ratios, organophilic clays are poor gelling agents. However, it should be noted that the preferred milliequivalence ratio in the range of 90 to 140 varies depending on the properties of the organic composition to be gelled with organophilic clay.

The manner in which the organic cation functions in the organophilic clay reaction products of this invention is not fully known. However, the unique properties associated with the compositions of this invention are presumably due, at least in part, to the electro-releasing and donating moieties of the cation, and in particular to the presence of at least one long-chain unsaturated alkyl group and / or hydroxyalkyl group. Bound to a positively charged atom, the long chain alkyl group appears to act as an electro-20 donor that aids in the localization of the positive charge. More importantly, however, it allows the clay flakes to separate sufficiently to allow further separation under moderate shear conditions. The β, β-unsaturated alkyl group, on the other hand, appears to create a delocalization of the positive charge which may result from the resonance and / or inductive effect manifested by the unsaturated alkyl group. This effect is not significantly seen with other prior art saturated alkyl groups. The enhanced effect of the lower hydroxyalkyl group appears to be related to an internally covalently bonded polar activating group, namely a hydroxyl group, when not adjacent to a positively charged atom.

12 7 4 8 8 8 This effect is reversed when the hydroxyl group is located on the carbon atom adjacent to the positively charged atom or on the carbon of an aliphatic alkyl group longer than 6 carbon atoms.

The compositions of the invention discussed above have a wide range of uses as theological additives in anhydrous flowable systems. Anhydrous, flowable compositions in which self-activating organophilic clays are useful include paints, varnishes, enamels, yahas, epoxies, putties, adhesives, cosmetics, inks, polyester lamination resins, polyester gel coatings, and the like. These liquids can be prepared by any conventional method, as described in U.S. Patent No. 4,208,218, including colloid mills, rollers, ball mills, and high speed dispersion mixers in which the pigments are well dispersed in the organic binder by the high shears used in the treatment. Although the present invention has been defined with reference to anhydrous liquids, it may be contemplated that such compositions may contain minor amounts, such as up to 10% by weight of water in the anhydrous liquid, and are still within the scope of the invention.

The organophilic clay gel core is used in such mixtures in amounts sufficient to provide the desired Theological properties, such as high viscosity at low shear rates, control of fluid film runoff, and prevention of settling and packaging of pigments present in anhydrous liquid mixtures. The amounts of organophilic clay gelling agents used in anhydrous flowable systems should preferably be between about 0.1% and about 15% by weight of the treated anhydrous flowable system, and preferably between 0.3% and 5.0% to obtain the desired theological effects.

Il 13 74888 The thickener of this invention is characterized by several advantages over previously used suspending agents. Such advantages are evidenced by the improved behavioral properties that occur in a number of certain species that fall within the general description of the compounds of the invention. In general, the suspending agents of this invention do not become granular, bubbly, or undergo other deleterious changes at high handling or storage temperatures; 10 they behave as effective gelling agents in the absence of solvent activators; they are effective in both aliphatic and aromatic solvents as well as moderately polar solvents; their use allows complete control of Theological properties and 15 produces consistent results. In addition, depending on the product properties and the desired end uses, they are non-yellowing and can be used without fear of color defects, providing uniform suspension properties that allow excellent suspension and non-flow properties of the pigment sus-20.

A particular embodiment of the present invention involves the formation of anhydrous flowable systems containing thioxotropic coating compositions.

Coating compositions comprising a film-forming organic and / or inorganic binder, solvents and optionally pigments have been previously described for use as decorative and / or protective agents in, for example, metal, wood, plastic and paper. In practice, these mixtures are applied to the substrate by means of equipment 30 such as a brush, a roller, with air or by spraying or dipping from air. Thixotropic gelling agents which produce a low viscosity high shear coating composition as would be used to coat the coating, but which produce a high viscosity under low shear conditions or without shear, can be used in these compositions.

14 74888

In the past, asbestos, silicic acid, various organic materials, and organophilic clays have been used as effective gelling agents in such coating compositions. However, these materials have suffered from various disadvantages, such as the formation of health hazards, high operating costs and the production of defective coating compositions which lack sufficient gloss and surface smoothness.

The clays of this invention have been used as effective gelling agents for the coating composition without the difficulties associated with prior art materials. Organophilic clays can be dispersed in coating compositions under low or optionally high shear conditions.

In a typical method, an organophilic say gel gel is added to a portion of a coating composition comprising a film-forming organic binder, an organic solvent, and optionally pigments with stirring at a rate of 25.4 m / s. The stirring speed is increased to 76.2 m / s for 15 minutes to ensure complete dispersion of the organophilic clay. As soon as the dispersion has formed, the remaining amount of organic binder and solvent is added under low or moderate shear conditions to finalize the preparation. Although this typical method of addition is acceptable for use with the novel compositions of this invention, such compositions may alternatively be added under low or moderate shear conditions to a previously prepared coating composition. 30 This post-addition method is quite unexpected and is not possible with conventional organophilic clay materials, as they cannot achieve full viscosity levels and dispersion in the absence of large shear.

The Kalyon-forming organic binders of this invention are prepared by conventional methods such as acrylate and methacrylate esters with a polymer; unsaturated polyester resins; 5 and in the reaction of drying oils such as linoleic acid with polymers containing hydroxyl groups. Generally useful are organic binders having molecular weight weights from 200 to several hundred thousand.

10 Organic solvents for such coatings can be broadly classified into five categories that include aliphatic, aromatic, relatively polar, polar, and chlorinated solvents. Aliphatic solvents include normal and branched chain aliphatic hydrocarbons containing from about 5 to about 12 carbon atoms and cycloaliphatic compounds. Aromatic solvents include substances such as benzene, toluene, xylene and ethylbenzene. Relatively polar solvents include ketone and ester solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, ethoxyethyl acetate and the like, Polar solvents such as minor ethanol, propanol, 2-propanol, butanol, 2-butanol and ethoxyethanol. Chlorinated hydrocarbon solvents include substances such as methylene chloride, chloroform, carbon tetrachloride, chloroethane and 1,1,1-trichloroethane.

The coating compositions of this invention may contain conventional additives such as finely divided solids, particles, suspending agents of the present invention. Certain additives used, such as pigments, extenders, inert materials, fillers, diluents, and so forth, are all known in the art. well known and do not form part of this invention.

The amounts of organophilic clay gel used in the coating compositions may range from 0.25% to 10% and preferably from 0.5% to 5% by weight. Amounts greater than 10% can be used, but are difficult to handle due to high viscosities. The organic binder can be conveniently used in amounts of 10% to 80% based on the liquid portion of the coating composition. Sufficient amounts of organic solvent are used to reduce the viscosity of the coating composition to useful levels depending on the method of use, but in any case to produce no more than 100% of the total composition. Supplementary additives, including pigments, can be used in amounts ranging from 0.5 to 50% of the total coating composition.

20 The particular Theological Additive and the amount of it used to produce satisfactory behavior in a given coating composition will vary depending on a number of factors. In general, it has been found that acceptable behavior in highly polar solvent systems is achieved using organophilic clay reaction products prepared from quaternary compounds containing two or three long chain alkyl groups. In contrast, quaternary compounds containing only one long chain alkyl group have been found to be acceptable in moderately polar and low polar solvent systems. As such, the most suitable Organic Theological Additive would depend on the required Theology of the coating, the type of solvent,

II

17 74 88 8 on processing temperature control and manufacturing equipment. Although the efficacy of a particular Theological Additive will vary depending on these factors, the compositions disclosed herein have been found to produce excellent behavior when ingested with conventional additives. Unlike such prior art materials, the present compositions do not require heat treatment during manufacture, are less sensitive to heat during use and storage, do not necessarily require the presence of a polar activator, and provide excellent viscosity structure, settling, and shrinkage prevention.

examples

The following examples are provided to more fully illustrate the present invention. All percentages given are based on weight, unless otherwise indicated. The ingredients and amounts used to prepare each coating composition are listed in Table IA (Aliphatic Pigmented Solvent System), Table IIA (Aliphatic Clear Solvent System), Table IIIA 20 (Aromatic Pigmented Solvent System), Table IVA (Aromatic Clear Solvent System), and Table VA (Relatively Polar Solvent System). ).

The results in the tables show that the cumbersome mixture of the invention added afterwards to the prefabricated coating system with relatively little shear gives the system superior viscosity and flow control and disperses at almost the same level as conventionally used materials added to the system under significantly higher shear conditions. Also, the reference substances added to the system under lower shear conditions are clearly inferior in dispersibility, viscosity structure and flow resistance properties compared to the substance of the invention added to the system in the same shear.

ib 74888 The organophilic clays of this invention having a composition in accordance with the tables were subsequently added under low shear conditions to the coating composition without a polar solvent activator. For comparison, various organosils were also added to the coating mixture afterwards under the same shear conditions as the test organophilic clay, however, in this case a mixture containing 95% methanol and 5% water was used as the polar solvent activator for the organoclay.

In particular, 600 g of a previously prepared coating composition without the Theological Additive was weighed into a rimless round quarter-gallon vessel measuring 10 cm in diameter and 11.6 cm high. The system was mixed using a 1HP Premier disperser equipped with a 3.1 cm diameter sawtooth Cowles blade: The blade was placed in the center of the system in a vessel at a height such that the bottom of the blade is 1.3 cm above the bottom surface of the vessel. The shaft speed is kept constant at 3000 min. 5.1 g of the organophilic clay of this invention are slowly screened into a vortex system.

3

In the case of reference substances, 1.7 g (2.1 cm) of a mixture containing 95% methanol and 5% water are also added to the system exactly one minute after the addition of organoclay is complete. This polar solvent activator is injected into the system using a 5 cm glass pipette.

In the case of the system as well as the organophilic clay of the system and the organoclay, as well as the activator 30, are allowed to mix at a shaft speed of 3000 rpm for a total of 15 minutes. At this time, without stopping the disperser, take a small sample of the solution from the vessel using a narrow 100 cm stainless steel spatula. This sample

II

19 74888 is used to measure the roughness of a solution dispersion. The measurement is made using a Hecpnjan ^ roughness meter on a scale ranging from 0 to 8, where 0 corresponds to a film thickness of 0f025 mm and 8 corresponds to a film thickness of 0 mm.

5 The roughness gauge is a stainless steel rod with a channel of varying depth cut into it. The test solution is placed in the channel at its deepest end and is then drawn along the entire length of the channel. # The grinding roughness of the system is determined at the point in the channel where the pigment particles first appear above the surface of the film solution. This measurement was made after a stirring time of 15 minutes. The systems are then transferred to a tin can and allowed to equilibrate overnight at 20 ° C before examining their viscosity and shrinkage.

The dispersion ease test is performed as discussed above using a Brookfielt RVT viscometer equipped with a ^ * 4 spindle at a spindle speed of 10 1 / min. Leak measurements are made with a Leneta anti-run blade.

20 Drip strips are provided on Leneta 7B cards with a mechanically operated film applicator equipped with a perforated vacuum plate. Complete cards are placed in a vertical position with the paint strips horizontal, the thinnest strip at the top. The run is read, after the film has dried, as the thickest strip that does not flow enough to cross the next strip below it. The flow units are mil units (0.025 mm).

The data in Tables IB and IIB show the preparation of coating systems with easier dispersion and / or higher viscosity structure under moderate shear conditions compared to conventional additives.

In Tables IIIB and IVB, the data show the overall increase in the viscosity structure of the organophilic clays of this invention and the generally improved anti-runoff properties compared to conventionally prepared additives.

20 7 4 8 8 8

In Table y & a data, the organophilic says of the invention present substantially equivalent results to prior art additives, with a limited amount of viscosity structure.

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Table II A

Aliphatic clear solder system 1, Add 388 g of Aroplaz 1266-M70 to a borderless quarter-balloon container.

5. Stir at 100 ° 1 / min in a 0.736 kW disperser using a 41.3 mm Hi ^ Vis blade.

3. Add 12 g of Theological Additive with stirring.

4. Increase the agitator blade speed to 3000 l per minute.

5. After 1 minute, add 2 g of ethylene glycol to 10 portions of silicic acid alone.

6. Check the roughness of the grind after 15 minutes of mixing.

7. Transfer the gel to a borderless 0.5 liter can.

8. Brookfield viscosity is measured at 15 rpm for 5 minutes.

9. The viscosity is checked the next day.

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Table IVA,

Aromatic Mixed Solvent System 1, Add 39.2 g of Duraplex 12 ^ 08 to a borderless four-nes balloon jar.

5 2. Stir at 1QQ0 rpm in a 0.736 kW disperser using a 41.3 m Hi-Vis blade.

3. Add 12 g of Theological Additive while mixing.

4. Increase the agitator blade speed to 30001 in min.

5. Check the roughness of the grind after 15 minutes of mixing.

6. Transfer the gel to a borderless 0.5 liter jar.

7. Measure the Brookfield viscosity at 10 rpm for 5 minutes.

9. Check the viscosity the next day *.

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Another particular embodiment of the present invention involves the formation of anhydrous flowable systems containing ink mixtures.

Fine pigments, i.e. dispersing the ink color-5 substance in organic ink binders to produce a substance suitable as a printing ink is a very complex skill. The quality of the surface used for printing, the particular printing machine used, the working speed and the drying time are all basic factors that determine satisfactory essential working requirements for the ink.

The greatly expanded circulation of existing newspapers has brought with it the development and use of high speed printing machines in the printing industry. This has required 15 fast drying printing inks. Resin-based systems that can be dried with water, steam, or hot air are gradually replacing conventionally used drying oils. Current high-speed presses require inks that dry in as little as 20 seconds rather than minutes.

In fast printing, inks must maintain proper adhesion balance, permeability, and fullness control. Excessive adhesion can cause paper to tear or ink to cloud at high speeds.

25 Insufficient ink does not transfer properly during printing. If the ink permeability is too high, the ink will appear on the opposite side of the paper or cause smudges on the patterns. Poorly controlled permeation can cause clutter when the liquid is tolerably dry. The ink must have a mass that prevents it from splashing out at high speeds due to its centrifugal force. On the contrary, too much viscous ink does not spread properly from the tanks to the rollers.

These variations and the conditions of 35 that are necessarily encountered make inkiness dependent on a large amount of product. U.S. Patent No. 2,750,296 discloses a printing ink containing a dye dispersion.

II

33,74888 perched in a binder formed by a soluble resinous binder dissolved in a mineral oil and containing a long-chain aliphatic amine-bentonite containing 34 carbon atoms in the aliphatic chain. On the other hand, U.S. Patent No. 2,754,219 discloses the formation of an anti-fog ink prepared by adding to a ink having a hydrocarbon containing an aromatic component, a finely divided organic derivative of montmoril-10one having a chain of at least 12 carbon atoms. In addition to these patents, U.S. Patent No. 2,739,067 discloses a printing ink containing adapted clay which forms a gel in an organic binder and has an essential gel property therein. However, prior art compounds in the art have suffered from various shortcomings. For example, some require the use of harmful polar dispersion additives that can react with other ink formulation components to destroy unavoidable ink properties, while others require numerous shear operations through the roller to produce a stable viscosity stop-25 from.

In contrast to these prior art methods, U.S. Patent 4,193,806 discloses the preparation of a storage-stable ink comprising an organic ink binder and an organophilic clay gel core comprising 30 smectite-type clays having a cation exchange capacity of at least 75 milliequivalents per 100 g of clay, and 34 7 4 And a reaction product of a methylbenzyldialkylammonium compound or a dibenzyldialkylammonium compound in which the alkyl groups contain 14 to 22 carbon atoms. The printing inks of this U.S. patent are shown to be capable of maintaining full viscosity levels following one revolution on a tricycle, in contrast to prior art comparable gelling agents, which have a steadily increasing viscosity. Although this patented printing ink has significantly improved the state of the art, the development and improvement of li-10 is necessary so that the ink does not have to be subjected to high shear forces to achieve acceptable viscosity levels first.

Surprisingly, a printing ink has now been invented which contains a viscosity-increasing additive formed by an organic ink binder dispersed in an ink dye and an organophilic clay gel formed by an organic cationic quaternary ammonium compound and a smectite-type clay having a cation exchange capacity of at least 75 millimeters. g per said clay, a reaction product wherein said organic cationic compound contains a) a first member selected from the group consisting of a -unsaturated alkyl group or a hydroxyalkyl group having 2 to 6 carbon atoms or mixtures thereof, b) a second member consisting of a long chain 12 - an alkyl group having 60 carbon atoms, and c) a third and fourth member selected from the groups listed in a), aralkyl groups having 30 and 1 to 22 carbon atoms, and a mixture thereof; and wherein the amount of said organic cationic compound is between 90 and 140 milliequivalents per 100 g of said clay, based on 100% of the active clay.

The printing inks of the present invention contain an organic ink binder in which an ink dye and a new organophilic say gel are dispersed. The organic ink carrier contains a solvent and a binder.

5 Conventional solvents such as high boiling hydrocarbon as well as other conventional solvents may be used. The solvent is preferably a high boiling aliphatic solvent or a mixture thereof that is economical to use and process to prepare acceptable systems. Conventional binders, such as synthetic or natural resins, having film-forming properties can be used. These binders also act as pigment carriers. The type of binder used depends on the particular application and can be selected from drying oil varnish, alkyd resins, polyester binders and urethane alkyds. Ink dyes include pigments or pre-dispersed pastes. The pre-dispersed pastes may contain a pigment, a binder and a solvent. Other additives may be included in the printing ink to modify the properties of the ink for special purposes. These additives may include bedding, dispersants, pigment extenders and antioxidants.

The printing ink is prepared in an economical and practical manner simply by incorporating organophilic clay gels into an ink masterbatch containing an ink dye and an organic ink binder.

The ink blends prepared using the blends of this invention achieve high viscosity levels so that they are only mixed with the ink preparation and do not require tricycle passage or other similar systems to provide an increase in viscosity.

36 7 4 8 8 8

The product can be easily dispersed as a theological additive to the producer by the maximum viscosity structure by conventional means of dispersing in the absence of triple alcohols. The oxganophilic clays of this invention produce an ink mixture which, when properly dispersed, is of a sufficiently fine particle size so that neither filtration nor milling is required to make a ready-to-use preparation.

Although the tricycle can be used to help disperse the ink pigments or substances of the ink 10 so that the ink is printed satisfactorily on a printing press, a procedure generally required, such delivery is not required to increase the viscosity.

Loose passage through the tricycle may be necessary in some cases where oxidation occurs in the ink systems so that the air trapped in the hatch from dispersion does not cause the formation of small cured ink particles.

The invention can also be practiced by adding an organophilic clay gel core to the final printing ink prepared in advance. These inks can be prepared by any conventional method, such as colloid mills, rollers, ball mills, etc., in which the ink pigment is well dispersed in the organic ink binder in the large shears used in the work. This dispersion of the pigment in the binder forms an ordinary ink and has a conventional tendency to cloud.

The organophilic clay gel core is used in amounts sufficient to obtain the desired viscosity value and to adhere to the printing ink. If necessary, the viscosity can be further controlled by increasing the viscosity 11 37 74888 to reduce the substance, for example naphthenic oil or solvent. In general, amounts of between 0.1% and 15% by weight of the printing ink are sufficient to greatly reduce the tendency of the liquid to cloud when used in high speed newspaper printing, with preferred amounts being between 0.5% and 4% and most preferably between 1% and = 3%. by weight. When the gel core is used at concentrations less than 0.1% or greater than 10% by weight of the printing ink, the structure, flow and other properties affecting the critical properties of the ink 10 are severely degraded, and the desired increase in viscosity and adhesion is not achieved.

The printing inks of the invention may contain conventional ink additives used in such printing inks. For example, oil-soluble toners used to overcome the brownish tinge of mineral oil and carbon black pigment can be used, as well as small amounts of waxes or fats to impart special properties to the printing ink.

Printing inks for use with the gelling agents of the present invention include, but are not limited to, heat drying or news printing ink, water or steam drying ink, or lithographic printing ink.

News printing inks dry mainly by permeation and absorption, although some heat is used to accelerate drying and stain intimate to prevent it. By properly controlling the viscosity, adhesion, and yield strength of such inks, the organophilic clays of the invention achieve proper permeation in an efficient manner without centrifugal displacement or turbidity.

When the organophilic clays of the invention are used in other heat-drying printing inks, such as 33 748 8 8 high-grade magazine inks, which contain additives such as binders and solvents, the inks are highly flexible, stain-free, print well and dry quickly at high temperatures.

5 The use of a gelling agent in steam or water-drying inks greatly affects viscosity and adhesion by providing the characteristic shortness of the ink.

On the other hand, lithographic printing inks are very similar in structure to printing inks, except that the fullness is slightly higher and the pigment concentration is higher. The advantages of using organophilic clays given above also apply here.

The following examples are provided to illustrate the invention but are not intended to limit it.

15 All percentages given are by weight unless otherwise indicated.

The following test methods were used in the examples:

Dlspergointi

The test ink was drawn into both channels of the NPIRI G-1 grin-20 dometer and checked for grinding roughness (small particles) and scratches. Scale readings range from "10" to "O". A reading of 10 corresponds to a depth of 0.0254 mm and a reading of 0 is the zero depth. The samples were drawn so that the readings of at least four different measurements were taken and averaged. Complete readings of the test sample would be "O" for both grinding roughness and scratches.

Viscosity

Viscosity was measured using a Thving-Albert falling rod viscometer at a column temperature of 25 ° C.

30 air was removed from the ink simply by stirring and then the rod was completely covered with the ink sample. Three weights were used to obtain fall time values: 700, 500, 200 g. These weights were repeated and the data were run on a Hewlett-Packard computer to obtain the predicted viscosity of Bingham-35 in boys at 1000, the viscosity value selected in the tables was taken using the data, I! 39 7 4 8 8 8 which contained a standard deviation from a straight wire calculated from the Bingham equation fB ^ -DgMg, which is the point of intersection on the shear stress axis at a shear rate of zero.

5 fQ = is the elastic value T is the shear stress D_, is the shear rate

O

M „is the viscosity

O

Example 10 A roll offset, heat-drying red base ink preparation containing the ingredients listed in Table VI was prepared and passed once through a tricycle to achieve good ink dispersion. The rheological additive was then slowly added to the base ink 15 using as little agitation as possible to prevent spillage. Dispersion was then achieved at 3000 rpm with a 0.368 kW Premier dispersing unit using a Cowles blade. The appropriate speed was maintained for 15 minutes. Viscosity measurements were performed after 20 seconds of dispersion and after 24 hours.

Separate ink samples were treated with different organophilic clay derivatives and a reference substance at a level of 2% by weight.

The comparative run BB used fine-particle silica, commercially known as Aerosil R972 (DeGussa Inc.). The comparative CC used an organophilic clay known as benzyl trihydrated tallow ammonium benzonite. The mixtures according to the invention are shown in Table VII.

The results show that the substance of the invention prepared from the quaternary compound of the invention achieved good dispersion and potency under low shear mixing conditions.

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Another particular embodiment of the present invention involves the systemic formation of anhydrous fluxes, including fat preparations,

In the past, lubricating greases have consisted mostly of hydrocarbon oils thickened with soap. In recent years, a number of non-soap thickeners have been identified which are remarkably inexpensive compared to soaps used to date.

Also, the range of useful lubricating binders 10 has been expanded to include liquids other than hydrocarbon oils, such as various esters, silicone oil, and the like. The newer types of fats just mentioned are generally known as non-soap thickened fats.

An important subgroup of these are those thickened with clay minerals, such as montmorillonite and hectorite, which have been rendered organophilic by complexing with a long chain compound. Fats of this type are described in Jordan's Patent No. 2,531,440 and in various articles in the technical literature, such as "BENTONE Greases," C.M. Finlayson et al., The Institute Spokesman, May 1950, pp. 13-23; and in paragraph 17 of Lubricating Greases, C.J., Boner, New York, 1954. Such greases, in conjunction with other greases, may contain other additives, such as corrosion inhibitors, high pressure additives, finely divided solid lubricants, fluorescent additives, and the like.

It has been found that fats of the type described in the general case are not always ideal for behavioral prolonged work at elevated temperatures. Such action can cause structural changes that manifest in laboratory experiments as increased permeability. This should not always be such as to render the fat inoperable, but it is clearly desirable to

II

43 74888 tayaa to obtain xaayaf which retains its physical properties unchanged during use.

It has unexpectedly been found that the use of the organolytic clays according to the present invention makes it possible to produce a lubricating grease which has improved stability at prolonged working at high temperatures and which does not suffer from adverse effects on other grease properties such as corrosion, water pollution reaction and the like.

The lubricating oil which forms the basis of the grease to which the invention applies may be any of those commonly used in the manufacture of lubricating greases in which the thickener is an organophilic clay. This truly covers the full and wide range of liquid lubricants 15 and includes, by way of example, but not limited to, petroleum-derived lubricating oils, sometimes referred to as mineral lubricating oils; lubricating oils derived from petroleum by various polymerization and remodeling routes, such as Fischer-Tropsch, Synthol, Synthine and the like; Lubricating oils produced by the Bergius method, applied to the hydrogenation of coal, peat and the like, and asphalts, petroleum residues and the like; synthetic lubricants produced by an evaporation process from, for example, fatty oils, petroleum hydrocarbons and the like; so-called ester lubricants, which may be alkyl esters of organic acids, such as dioctyl phthalate, ethyl castor oleate and the like, or which may be alkyl or alkylaryl esters, such as tricresyl phosphate; synthetic lubricants made in the polymerization of alkylene oxides and glycols such as pentamethylene glycol; and silicone polymers 44 74 888, commonly known as silicone oils,

The organophilic clay reaction product may be added to the fat blend at any desired stage of preparation. Since the clay reaction products do not require the presence of a polar-5 activator, prior dispersion with conventional activators is not necessary. In general, amounts of thickener in the range of 0.5 to 10% by weight of fat have been found to be effective.

In addition to the above-mentioned additives used in the preparation of the fat preparation, it has been found that the incorporation of asbestos helps the thickening effect of the organophilic clay.

The asbestos which may be incorporated into the fats to which the invention applies may be any chrysolite or tremolite which is reasonably free of non-asbestos impurities and which has been mechanically or chemically treated to separate the fibers to such an extent that private fibers are not readily visible to the naked eye. Many methods are available for accomplishing this and need not be described in detail herein. Reference may be made to Asbestos Fundamentals, Berger and Oesper, New York, 1963.

When asbestos is used in accordance with the invention, it is convenient to make a dry mixture by mixing the organophilic clay and asbestos. Considering the relative thickening and stabilizing effects of organophilic clays and asbestos, there is a practical weight range of asbestos relative to the organophilic clay in such a dry blend to about half the amount of said organophilic clay.

Il 45 74888

It is also possible to include the corrosion inhibitor in the grease together with the organophilic Saye, such as sodium nitrite and the like. Generally speaking, when sodium nitronite is used in this manner, its practical concentration range is from about 0.25 to about 1.0 times the weight of the organophilic clay used. Again, if a dry mixture is prepared in advance that lacks only lubricating oil, it is really practical to retain any sodium nitrite as one of its ingredients. In such cases, it will, of course, have the same weight ratio to organophilic clay as just shown for fat.

The following examples are given to illustrate this aspect of the invention, but are not intended to be limiting. All percentages are by weight unless otherwise indicated.

Example

In the examples, different types of organophilic gelling agents prepared were evaluated as fat thickeners at a concentration of 6% by weight in a conventionally refined oil containing 0.4% water. Fats were prepared by mixing the gel core, oil and water together for 30 minutes using a drill press equipped with sweeping blades rotating at 450 rpm.

The resulting batch was then milled through a "Tri-Homo" dispersing device, keeping the rotor and stator free between 0.0254 mm. ASTM permeation of fats after standing overnight was obtained after 60 and 10,000 treatments of fats in an ASTM motorized fat handling machine. The results obtained are given in Table 30 VIII. Conventional reference gelling agents were also evaluated in a conventional heated degreasing method using 2% by weight of acetone as a polar organic dispersant for the gelling agent. fats were prepared by mixing the gel core, oil and acetone together for 30 minutes with heating to 121 ° C with continued stirring to evaporate the acetone, cooling to 82 ° C and adding 0.1% water while continuing to stir and grind as above . The results obtained for these fats, which are not a description of the present invention, are compared with the results for the fats in the table, because these fats have the same composition.

Conventionally refined oil has the following characteristics: 2o Conventionally refined

Density, at 16 ° C 20

Viscosity, at 38 ° C 500

Viscosity, at 99 ° C 53

Viscosity factor 12 15 Refractive index 1.5085

Flash point, ° C 199 ° C

Freezing point, ° C -20 ° C

The results show that the organophilic clays containing the thickener according to the invention were very effective thickeners for this oil at ambient temperatures using only a small, negligible amount of water as a dispersant. The results also show that organophilic clays readily disperse in the absence of a polar organic dispersant, producing fats with a permeability equivalent to that obtained with fats prepared using a dispersant.

Il 74888 47

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Yet another particular embodiment of the present invention involves the preparation of a vinyl-based sealant composition. A "sealant" is broadly taken to act to keep air and water out of contact with the substrate to which it is applied. Typically, sealants are used to bond surfaces or glass and metal layers. to fill spaces and bond glass to glass, metal to metal, forests to glass as well as a number of other substrates. They 10 are also widely used in the manufacture of automobiles for the purpose of joining metal parts, filling wells and leaking valves and the like.

A number of sealant preparations are based on vinyl chloride didipolymers or resins and, depending on the particular sealant preparation, are commonly referred to as plastisols, plastels, organosols and organogels. Although these formulations have generally been effective as sealants, conventional vinyl chloride resin sealants have exhibited a number of detrimental properties when prepared in conjunction with conventional theological excipients such as finely divided asbestos, silicic acid aerogels and organophilic bentonites. For example, several shortcomings include the difficulty of controlling viscosity? toxic waste problems, 25 especially when using asbestos? poor durability? and deterioration of the product during melting together and migration of plasticizers, especially when conventional organophilic benzonites are used.

It has unexpectedly been found that the novel compositions disclosed herein are capable of producing a sealant composition having controllable yet desirable Theological properties and therefore enabling

II

49 74888 sealants for virtually any purpose in which vinyl chloride sealants have been used to date without the difficulty of disposing of toxic waste, and the deterioration properties of the product associated with prior art materials.

The new sealant compositions include a vinyl chloride resin, a plasticizer for the resin, and an improvement therein of about 0.1% to about 10% by weight of the reaction product described above made from an organically cationic quaternary ammonium compound and a smectite-type clay having a cation exchange capacity of at least 75 milliequivalents per 100 g of said clay, wherein said organic cationic compound contains: (a) a first member selected from the group consisting of an unsaturated alkyl group and a hydroxyalkyl group having 2 to 6 carbon atoms and mixtures thereof, (b) a second member, consisting of a long chain alkyl group having 12 to 60 carbon atoms and (c) a third and fourth member selected from a member of group 20 (a), an aralkyl group, an alkyl group having 1 to 22 carbon atoms and a mixture thereof, and wherein the amount of said organic cationic compound is between 90 to 140 milliequivalents per 100 g mentioned a per clay 100% of the active clay.

The terms "vinyl chloride polymer or resins" and "polyvinyl chloride" as used herein are generally emulsion grade polyvinyl chloride resins having molecular weights greater than about 10,000 and average particle sizes less than about 10 microns.

However, these terms apply not only to all types of polyvinyl chloride homopolymers, but also to copolymers of vinyl chloride to a large extent, such as copolymers of vinyl chloride, which are copolymerized with less than 50% by weight of an ethylenically unsaturated comonomer. Ethylenically unsaturated comonomers copolymerizable with vinyl chloride include vinyl acetate, vinylidene chloride, maleic or fumaric acid esters, styrene and acrylonitrile. Smaller batches of other synthetic resins such as chlorinated polyethylene and copolymers of acrylonitrile, butadiene and styrene may be included.

Any of the usual plasticizers for vinyl pastes can be used. Particularly desirable substances are phthalate plasticizers. Exemplary plasticizers include dialkyl phthalates such as dioctyl phthalate (di-2-ethyl-hexyl phthalate) and octyl decyl phthalate; alkyl phthalylalkyl glycolates such as ethyl phthalylethyl glycolate and butyl phthalyl glycolate; dialkyl esters of alkane di-carboxylic acids such as diisobutyl adipate, di-2-ethylhexyl adipate and dibutyl sebacate, acetyltrialkyl citrates such as acetyltributyl citrate and triacyl and triacylphosphate ethylphosphate, 2-octylphosphate, such as trioctylphosphate Other useful plasticizers include alkyl esters of fatty acids such as octyl stearate; epoxidized triglycerides such as epoxidized soybean oil and polymers polyester plasticizers such as polymeric glycol adipate. White oil can also be used as a plasticizer. Preferred plasticizers are di-2-ethylhexyl phthalate and diisodecyl phthalate. Softeners can be used at a level of about 50 to about 300 parts per 100 parts of resin, and preferably about 70 to 200 parts per 100 parts of resin.

Il si 74 88 8

Other conventional additives may also be used, such as fillers, stabilizers and antioxidants. The filler mixture acts primarily as a water-binding agent by isolating the water in the preparation. Representative agents include barium sulfate with either talc or enamel.

Other fillers that can be included in the sealant composition include diatomaceous earth, magnesium silicate, calcium silicate, calcium sulfate, titanium dioxide and zinc carbonate. Calcium stearate coated calcium carbonate can also be used as a filler. The fillers may be added in amounts of about 0 to 200 parts per 100 parts of resin.

Useful stabilizers previously used in the art include zinc, calcium, and aluminum stearates. Other stabilizers include zinc octoate and tin octoate. Commercially available calcium zinc stearate is preferably used in combination with epoxidized soybean oil.

Stabilizers may be included in the mixture in amounts moving at a reasonable level, preferably from 0 to 100 parts and most preferably from 2 to 50 parts per 100 parts of resin.

The sealant compositions can be prepared in any conventional manner, such as in a mixing device commonly used in the preparation of viscous materials. Because the Theological Additive of this invention can be added to the sealant composition without the need for high shear equipment, conventional mixing is sufficient without the need for high shear mixers such as the Cowles mixer or Waring Blendor required for conventional organophilic clay compounds. In this sense, the mixing® can be performed in a planetary mixer, a conventional dough mixer, a melatypical mixer, a press, a Banbury mixer and rollers.

52 7 4 8 8 8

The order in which the ingredients are added is not critical to the practice of the invention. For example, the theological additive may be dispersed in the plasticizer prior to mixing with the resin, or may be added simultaneously or independently of the addition of the remaining ingredients.

The sealant compositions may be in the form of plastic sols, plastic gels, organosols or organogels, and therefore conventional volatile liquids may be used in the manufacture of sealant compositions.

10 The following examples are given to illustrate this aspect of the invention, but are not intended to be limiting. All percentages given are by weight unless otherwise indicated.

Example 15 The following experimental methods were used in the examples.

Drop test Using a stainless steel trowel, a drop channel measuring 152.4 mm x 19.05 mm x 12.7 mm was filled, filled with a sealant preparation (plastic sol) (usually 55 g of sealant). Once filled, the channel was placed vertically on a 50.8 mm extension surface for one hour at 25 ° C. The fall is recorded as the distance in millimeters as the plastisol moves down the extension surface.

25 Color pronunciation

The plastisol preparation is added to an aluminum container having a diameter of 57.15 mm and a depth of 17.46 mm. A spatula is then used to level the surface of the plastisol and the vessel is placed in a compressed air oven at 177 ° C for 30 to 15 minutes. Once the plastisol has cooled to room temperature, its color is recorded.

Il 74888 53

The plastisol sealant is prepared by mixing the ingredients listed below in the order listed. This method is a conventional method introduced in the present invention.

5 PVC Plasma T l iv i s t y sm a s s a diisodecyl phthalate 100 parts PVC resin, Firestone FPC-6338 100 parts

Mix until the resin is completely dispersed, with a dough or similar mixer and add the following ingredients with stirring:

CaCO 2, Camel-wite 160

Stabilizer, TRIBASE 4

Plasticizer, Kodaflex PA-5 26

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Having thus described the invention, it will be apparent that it may be modified in many ways. Such variations are in accordance with the invention and are intended to fall within the scope of the following claims.

Claims (13)

Anhydrous liquid composition comprising an anhydrous liquid mixture and an organophilic rheological clay mixture which is a reaction product of an organic cationic quaternary ammonium compound and a smetite type clay having a cation exchange capacity of at least 75 milliequivalents per 100 g clay, characterized in that the organic cationic compound contains a) a first member which is a /, 7 ~ unsaturated alkyl group or a hydroxyalkyl group having 2-6 carbon atoms or a mixture thereof, b) a second member which is a long chain alkyl group having 12 to 60 carbon atoms, and c) a third and fourth member selected from the groups listed above in a), aralkyl groups and alkyl groups having 1-22 carbon atoms and of these; And the amount of the organic cationic compound is 90-140 milliequivalents per 100 g of clay calculated on 100% active clay. Composition according to claim 1, characterized in that the clay of the smectite type is hectorite or sodium bentonite. Composition according to claim 1, characterized in that the ftt'Y 'unsaturated alkyl group is an unsubstituted or substituted cyclic group, an acyclic alkyl group having less than 7 carbon atoms, a cyclic alkyl group substituted by an aromatic group, or an aromatic group substituted by aliphatic groups. 4. A composition according to claim 1, characterized in that the hydroxyalkyl group is a substituted or unsubstituted cyclic or aliphatic group of 2-6 carbon atoms, wherein the hydroxy substitution is at C2 - Cg. 60 74888 5. A composition according to claim 1, characterized in that the long-chain alkyl group in member b) has 12 to 22 carbon atoms. 6. A composition according to claim 1, characterized in that the long chain alkyl group is a long chain fatty acid group. 7. Composition according to claim 1, characterized in that the amount of the organic cationic compound is 100 - 130 equivalents per 100 g of clay calculated on 100% active clay. 8. A composition according to claim 1, characterized in that the organophilic clay mixture constitutes 0.1-15% of the weight of the anhydrous liquid composition. 9. A composition according to claim 1, characterized in that the organophilic clay mixture comprises 0.3 to 5.0% by weight of the anhydrous liquid composition. 10. A composition according to claim 1, characterized in that the organic cationic compound has the general formula N * ί R.-X-R0 M 4 I 2 In R 3 -, where R 2 is a / 4 P-unsaturated alkyl group or a hydroxy alkyl group of 2-6 carbon atoms or a mixture thereof, R2 is a long chain alkyl group of 12 to 60 carbon atoms, R 2 and R 2 are selected from an R 2 group, aralkyl group, alkyl group having 1-22 carbon atoms and mixtures thereof, X is nitrogen, and M is Cl, Br, NO 2, OH or C 2 H 3 ° 2 'and the amount of the organic cationic compound is 90 - 140 milliequivalents per 100 g of clay calculated on 100% active clay. Il