JPS6224467B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an aqueous dispersion composition capable of irreversibly forming a coherent film, and in particular comprising a film-forming non-asphaltic oily material as an internal phase and at least one flocculant as an external phase. The present invention relates to a composition comprising a clay thickened aqueous slurry. The invention also includes processes for producing such compositions, coherent coatings obtained from such compositions, and products whose metal surfaces are at least partially covered by such coatings. Furthermore, a method of preventing corrosion of a metal surface using the composition is also within the scope of the present invention. Conventionally, oil-based and water-based clay thickening compositions are known. For example, U.S. Patent Nos. 3763042, 3449248, 3250735 and 3247011
See issue. Overbased non-Newtonian, colloidal dispersions are also known. For example, US Pat. No. 3,384,586,
Same No. 3242079, Same No. 3372114, Same No. 3376222
No. 3377283, No. 3422013, and No. 3422013.
See No. 3492231. Regarding the above-mentioned non-Newtonian dispersion system, further, U.S. Pat.
See No. 3746643 and No. 3671012. Clay thickened aqueous asphalt emulsions are known in the art. For example, U.S. Pat.
See No. 3095339, No. 2652341 and No. 1398201. Asphalt emulsions containing sulfonate salts are also known and are described in US Pat. No. 2,503,246. It is an object of this invention to provide an aqueous dispersion composition capable of irreversibly forming a coherent film. Another object of the present invention is to provide a method for producing the above aqueous dispersion composition. Furthermore, it is an object of the present invention to provide a coherent film obtained by substantially removing water from the above aqueous dispersion composition. Furthermore, it is an object of the present invention to provide a method for preventing corrosion of a metal surface by spraying the aqueous dispersion composition onto the metal surface to substantially remove water and form a film. . Other objects of the invention will become apparent from the following description. The aqueous dispersion composition of the present invention is capable of irreversibly forming a coherent film on, for example, a metal surface, and comprises at least one film-forming non-asphaltic oil substance (A). an external phase; and () an aqueous slurry (B-1) thickened with clay, comprising water and at least one
In addition to the seed clay (B-2), it contains at least one flocculant (C). The slurry in this aqueous dispersion composition exhibits a PH value within the range of about 6 to about 9. "Coherent" as used in this specification
The term is used in the sense that the coatings obtained according to this invention have sufficient adhesion properties and yet resist separation, such as separation from the substrate over which such coatings are covered. As will be appreciated by those skilled in the art, such coherent coatings are particularly useful in preventing corrosion and/or wear since they form a strong surface after substantial removal of moisture. . The terms "external phase" and "internal phase" are used in their art-recognized meanings and refer to the "discontinuous phase" and "continuous phase" of the emulsion, respectively. The film-forming non-asphaltic oily substances (A) used in this invention are typically carboxylate salts and oil solutions/dispersions of carboxylate salts. Organic resins having acid groups that can react with carbonates and bicarbonates to produce carbon dioxide are also used. Such acid groups include sulfonic acid groups, phosphoric acid groups, sulfuric acid groups, and boric acid groups. Since such materials are non-asphaltic, they are preferred over asphaltic materials from environmental and other points of view. Typical carboxylate salts include (D) at least one carboxylic acid or reactive equivalent thereof (e.g. anhydride);
(E) with at least one organic acid overbased salt, usually converted into a non-Newtonian colloidal dispersion. carboxylic acid
(D) is obtained by oxidation of petroleum fractions, such as petroleum wax fractions. General formula R(COOH) _x formula (1) (where R is at least one of C ₂ to C ₈ olefins
Substantially hydrocarbyl groups having from about 12 to about 300 carbon atoms derived from the polymerization of a species, and where x is 1, 2 or 3), are also used. A mixture of this carboxylic acid and the oxidized wax may also be used. The carboxylic acid represented by formula () can be obtained by reacting an olefin (e.g., polyalkylene such as polybutene, polypropylene, etc.) or a derivative thereof (e.g., a halogenated derivative) with a low molecular weight unsaturated carboxylic acid or a derivative thereof. . Typical examples of such unsaturated carboxylic acids (and derivatives thereof) include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, and fumaric acid. The method for producing carboxylic acid represented by formula () is described in, for example, a US patent.
No. 3024237, No. 3087936, No. 3172892, No. 3215707, No. 3219666, No. 3231587,
Same No. 3245910, Same No. 3272746, Same No. 3288714
No. 3312619, No. 3341542, No. 3341542, No. 3312619, No. 3341542, No.
No. 3367943, No. 3381022, No. 3454607, No. 3470098, No. 3630902, No. 3652616,
Same No. 3755169, Same No. 3868330, and Same No.
3912764, and British Patent No. 944136;
No. 1085903, No. 1162436 and No. 1440219
No. 956397 and Canadian Patent No. 956397. More typically, carboxylic acid (D) is produced by oxidation of petroleum wax fractions for reasons of economy and availability. Various types of wax can be used, such as paraffin wax, microcrystalline wax, or slug wax, but a particularly suitable wax is petrolatum. Oxidation of these waxes can be carried out in many ways known to those skilled in the art. This oxidation is usually carried out by blowing air through the wax in the presence of a metallic catalyst such as a copper, cobalt or manganese salt. For more information on wax oxidation, see K. Ellis, Chemistry of Petroleum Derivatives, especially pages 962-979 (Reinhold Publishing, 1937).
year). A particularly preferred petrolatum oxide used to prepare the film-forming oily substance (A) used in this invention is commercially available from Asshuland Oil Company under the trade name Tectyl 3050.
Other commercially available petrolatum oxides can also be used alone or in combination with Tectyl 3050. The film-forming non-asphaltic oily substance (A) used to produce the dispersion composition of this invention is:
It is typically obtained by reacting at least one of the carboxylic acids (D) with at least one overbased salt of an organic acid (E). Such salt is 100%
(i.e., such salts have a conversion rate that exceeds the theoretical amount of metal required to convert the acid to the neutral salt).
Contains more than 100% metal). Salts of this type are also said to have metal ratios greater than 1 (i.e., the ratio of metal equivalents to organic acid equivalents present in the salt requires only a stoichiometric ratio of 1:1) to provide a neutral salt. is also large). These salts are also called overbased salts or superbased salts, and are usually salts of organic sulfur acids, organic phosphorus-containing acids, carboxylic acids, phenols, or a mixture of two or more of these. Mixtures of such overbased salts may also be used. The term "metal ratio" refers to the total chemical equivalent and chemical reactivity of the metal in the overbased salt and the reaction of the base-reactive metal compound with the organic acid to be overbased according to the stoichiometry. is the ratio of the expected chemical equivalent of the metal in the salt. Therefore,
In neutral salts the metal ratio is 1 and in overbased salts the metal ratio is greater than 1. The overbased salt used as component (E) in this invention usually has a metal ratio of at least about 3:1, typically at least about 12:1. Typically, the metal ratio will not exceed about 40:1. A typical salt is about
It has a metal ratio of 12:1 to about 20:1. The base-reactive metal compounds used to make these overbased salts are typically alkali metal compounds or alkaline earth metal compounds (i.e. excluding francium and radium (typically excluding rubicium, cesium and beryllium)). ) metal compounds of Groups A, A and B of the Periodic Table, although other base-reactive metal compounds can also be used: Ca, Ba, Mg, Na and Li.
Base-reactive compounds such as hydroxides and alkoxides are commonly used as base-reactive compounds used to prepare overbased salts, but
Other compounds may also be used. Overbased salts containing mixtures of ions of two or more of the above metals can also be used. These overbased salts include oil-soluble organic sulfur acids such as sulfonic acid, sulfamic acid, thiosulfonic acid,
It may be sulfinic acid, sulfenic acid, partial ester sulfate, sulfite and thiosulfate. Generally, these overbased salts are of carboxylic acids or aliphatic sulfonic acids. The carboxylic acids and sulfonic acids include mononuclear or polynuclear aromatic or alicyclic acids. Most of the oil-soluble sulfonates can be represented by the formula [R _x -T-( _SO3 ) _y ] _z Mb formula () [R'-( _SO3 ) _a ] _d Mb formula (). In each of the above formulas, M is the aforementioned metal cation or hydrogen, and T is, for example, benzene, naphthalene, anthracene, phenanthrene, diphenylene oxide, thianthrene, phenothioxine, diphenylene sulfide, phenothiazine, diphenyl oxide, diphenyl sulfide. cyclic nucleus such as ide, diphenylamine, cyclohexane, petroleum naphthene, decahydronaphthalene, cyclopentane, R in formula () is an alkyl group,
Aliphatic groups such as alkenyl, alkoxy, alkoxyalkyl, carbalkoxyalkyl, x is at least 1, and R _x +T contains at least about 15 carbon atoms in total. R' in formula () is an aliphatic group containing at least about 15 carbon atoms and M is a metal cation or hydrogen. Examples of R′ include alkyl group,
These include alkenyl groups, alkoxyalkyl groups, carbalkoxyalkyl groups, and the like. Specific examples of R' include petrolatum, saturated or unsaturated paraffin waxes or polyolefins (polymerized C ₂ , C ₃ , C ₄ , C ₅ , C ₆ etc. having about 15 to 7000 or more carbon atoms). (including olefins). T, R in each of the above formulas
In addition to the above-mentioned substituents, R′ may contain other inorganic or organic substituents such as hydroxy group, mercapto group, halo group, nitro group, amino group, nitroso group, sulfide group, disulfide group, etc. do not have. In formula (), x, y,
z and b are at least 1, and in formula (), a, b and d are at least 1. Specific examples of sulfonic acids useful in this invention include mahogany sulfonic acid, brightst sulfonic acid, Saybold clay at 100° (37.8°C) and Saybold clay at 210° (98.9°C). Sulfonic acids derived from lubricating oil fractions of about 200 seconds, petrolatum sulfonic acids, mono- and polywax-substituted sulfonic acids such as benzene, naphthalene, phenol, diphenyl ether, naphthalene disulfide, diphenylamine, thiophene, alphachlornaphthalene, etc. and polysulfonic acids, other substituted sulfonic acids such as alkylbenzenesulfonic acids (the alkyl group has 8 or more carbon atoms), cetylphenol monosulfide sulfonic acid, dicetylthianenedisulfonic acid, dilauryl beta naphthylsulfonic acid, dicapryl nitro naphthalene sulfonic acid, and alkaryl sulfonic acid (eg dodecylbenzene bottoms sulfonic acid). The latter acid can be alkylated with propylene tetramer or isobutene trimer to form a branched _C12 substituent.
It is derived from benzene into which 1, 2, 3 or more benzenes are introduced. Dodecylbenzene bottoms (primarily a mixture of mono- and didodecylbenzene) are obtained as a by-product during the manufacture of household detergents. Similar products obtained from alkylated bottoms produced during the production of linear alkyl sulfonates (LAS) are also useful in producing the sulfonates used in this invention. It is well known in the art to produce sulfonate salts from detergent manufacturing by-products, for example by reaction with SO ₃ . For example, ``Encyclopedia of Chemical Technology'' by Kirk Osmar, 2nd edition (Jon Willey)
and Sons, 1969), Vol. 19, p. 291 et seq., "Sulfonates". Descriptions and methods for producing overbased sulfonates are disclosed in U.S. Patent Nos. 2174110, 2174506, and
No. 2174508, No. 2193824, No. 2197800, No. 2202781, No. 2212786, No. 2213360,
Same No. 2228598, Same No. 2233676, Same No. 2239974
No. 2263312, No. 2276090, No. 2276090, No. 2263312, No. 2276090, No.
2276097, 2315514, 2319121, 2321022, 2333568, 2333788,
Same No. 2335259, Same No. 2337552, Same No. 2346568
No. 2366027, No. 2374193, No. 2374193, No. 2366027, No. 2374193, No.
2383319, 3312618, 3471403, 3488284, 3595790, and
It can also be found in No. 3798012. Furthermore, those that are similarly used include paraffin wax sulfonic acid, unsaturated paraffin wax sulfonic acid, hydroxy-substituted paraffin wax sulfonic acid, hexapropylene sulfonic acid, tetraamylene sulfonic acid, and the polyisobutene
aliphatic sulfonic acids, such as polyisobutene sulfonic acid, chloro-substituted paraffin wax sulfonic acid, nitroparaffin wax sulfonic acid, containing from 1 to 7000 carbon atoms or more;
and alicyclic sulfonic acids such as petroleum naphthenesulfonic acid, cetylcyclopentylsulfonic acid, laurylcyclohexylsulfonic acid, and bis(diisobutyl)cyclohexylsulfonic acid. "Petroleum sulfonic acids" or "petroleum sulfonates" as referred to in this specification and claims include all sulfonic acids or salts thereof derived from petroleum products. A particularly valuable petroleum sulfonic acid is mahogany sulfonic acid (so-called because of its reddish brown color), which is obtained as a by-product during the production of white oil using the sulfuric acid process.
It is. In general, the synthetic and overbased Group A, Group A, and Group B metal salts of petroleum sulfonic acids described above are typically useful in preparing the film-forming materials (A) used in this invention. Carboxylic acids from which suitable overbased salts can be derived for use in this invention include aliphatic, cycloaliphatic and aromatic-basic acids such as naphthenic acid, alkyl- or alkenyl-substituted cyclohexanoic acid, alkyl- or alkenyl-substituted aromatic carboxylic acids, etc. and polybasic carboxylic acids. Aliphatic carboxylic acids are generally those having at least 8, preferably at least 12 carbon atoms. Aliphatic carboxylic acids usually have up to about 400 carbon atoms. Generally, the acid is more oil soluble if the aliphatic carbon chain is branched. Alicyclic and aliphatic carboxylic acids may be saturated or unsaturated. Specific examples include 2-ethylhexanoic acid, α
-linolenic acid, propylene tetramer-substituted maleic acid, behenic acid, isostearic acid, pelargonic acid, capric acid, palmitoleic acid, linoleic acid, lauric acid, oleic acid, ricinoleic acid,
These include undecylic acid, dioctylcyclopentanecarboxylic acid, myristic acid, dilauryldecahydronaphthalenecarboxylic acid, stearyloctahydroindenecarboxylic acid, palmitic acid, and commercially available mixtures of two or more carboxylic acids, such as tall oil acid and roseic acid. Typical oil-soluble carboxylic acids useful in preparing the overbased salts used in this invention are oil-soluble aromatic carboxylic acids. This aromatic carboxylic acid has the general formula (where R <sup>*</sup> is an aliphatic hydrocarbon group having at least 4 carbon atoms and up to about 400 aliphatic carbon atoms, a is an integer from 1 to 4, and A <sub>r</sub> <sup>*</sup> is up to about 14 a polyvalent aromatic hydrocarbon nucleus having carbon atoms, each X is independently a sulfur atom or an oxygen atom, m is an integer from 1 to 4, where R <sup>*</sup> and a are each acid molecule represented by the formula () such that on average there are at least 8 aliphatic carbon atoms provided by the R <sup>*</sup> groups. A <sub>r</sub>
Examples of the aromatic nucleus indicated by <sup>*</sup> are polyvalent aromatic groups derived from benzene, naphthalene, anthracene, phenanthrene, indene, fluorene, biphenyl, etc. In general, A <sub>r</sub> <sup>*</sup>
The group represented by is a polyvalent nucleus derived from benzene or naphthalene such as phenylenes and naphthylenes, such as methylphenylene, epoxyphenylene, nitrophenylene, isopropylphenylene, hydroxyphenylene, mercaptophenylene, N/N-diethylamino Phenylene, chlorphenylene, dipropoxynaphthylene, triethylnaphthylene, and similar trivalent compounds,
These include tetravalent and pentavalent nuclei. The R <sup>*</sup> group is usually a pure hydrocarbyl group, preferably a group such as an alkyl or alkenyl group. However, the R <sup>*</sup> group may contain a small number of substituents such as phenyl, cycloalkyl (e.g., cyclohexyl, cyclopentyl, etc.) and non-hydrocarbon groups such as nitro, amino, halo, etc., as long as its predominant hydrocarbon character is maintained. groups (e.g.
chloro group, bromo group, etc.), lower alkoxy group, lower alkylmercapto group, oxo group (=O), thio group (=S), intervening group (e.g. -NH-, -O-,
-S-) etc. may be included. The above hydrocarbon character is maintained as long as the non-carbon atoms present in the R <sup>*</sup> group do not exceed about 10% of the total weight of the R <sup>*</sup> group. Examples of R <sup>*</sup> groups include butyl group, isobutyl group, pentyl group, octyl group, nonyl group, dodecyl group, tetracontyl group, 5-cyclohexyl group, 4-epoxypentyl group, 4-hexenyl group, 3-cyclohexyl octyl group. group, 4(p-chlorophenyl)octyl group, 2,3,5-trimethylheptyl group, 4-ethyl-5-methyloctyl group, and polychloroprene, polyethylene,
Polypropylene, polyisobutylene, ethylene-
Propylene copolymer, chlorinated olefin polymer,
It is a substituent derived from polymerized olefin such as ethylene oxide-propylene copolymer. Similarly, A
<sub>The r</sub> <sup>*</sup> group also includes various substituents including non-hydrocarbon groups, such as lower alkoxy groups, lower alkylmercapto groups,
It may contain a nitro group, a halo group, an alkyl or alkenyl group having less than 4 carbon atoms, a hydroxy group, a mercapto group, and the like. Other useful carboxylic acids have the formula (Here, R <sup>*</sup> , X, A <sub>r</sub> <sup>*</sup> , m and a are the same as in formula (), and p is an integer from 1 to 4, usually 1 or 2). Among this class of carboxylic acids, particularly preferred oil-soluble carboxylic acids have the formula (wherein R <sup>**</sup> is an aliphatic hydrocarbon group containing from at least 4 to about 400 carbon atoms, a
is an integer from 1 to 3, b is 1 or 2, c is 0,
1 or 2 preferably 1. However, <sup>**</sup> and a satisfy a relationship such that the number of carbon atoms in the aliphatic hydrocarbon group per acid molecule is at least about 12 on average. ). Among this class of oil-soluble carboxylic acids are aliphatic hydrocarbon-substituted salicylic acids in which each aliphatic hydrocarbon substituent has an average of at least about 16
Particularly useful are those having 1 to 3 carbon atoms and 1 to 3 substituents per molecule. such salicylic acids in which the hydrocarbon substituents are derived from polymerized olefins, particularly polyethylene, polypropylene, polyisobutylene, ethylene/propylene copolymers, etc., and having an average of about 30 to about 400 carbon atoms; Preference is given to salts prepared from Carboxylic acids of the formula and are well known and can be prepared by methods known in the art. Processes for the preparation of carboxylic acids of the type described above and their overbased metal salts are well known, for example in US Pat. No. 2,197,832.
No. 2197835, No. 2252662, No. 2252662, No. 2197835, No. 2252662, No.
It is described in No. 2252664, No. 2714092, No. 3410798, and No. 3595791. Other types of overbased carboxylic acid salts used to produce the film-forming material (A) used in this invention have the general formula (Here, R <sup>*</sup> is the same as in the formula) derived from alkenylsuccinic acid.
Such salts and methods for their production are described in U.S. Patent No.
No. 3271130, No. 3567637, and No. 3632510. Other patent documents that specifically describe methods for producing overbased salts of sulfonic acids, carboxylic acids, and mixtures of two or more of these mentioned above include U.S. Patent No. 2501731 and U.S. Patent No. 2616904. , same no.
No. 2616905, No. 2616906, No. 2616911, No. 2616924, No. 2616925, No. 2617049,
Same No. 2777874, Same No. 3027325, Same No. 3256186
No. 3282835, No. 3384585, No. 3384585, No. 3282835, No. 3384585, No.
No. 3373108, No. 3365396, No. 3342733, No. 3320162, No. 3312618, No. 3318809,
Examples include No. 3471403, No. 3488284, No. 3595790, and No. 3629109. In this invention, phenols are organic acids. Thus, overbased salts of phenyls (commonly known as phenates) are also useful in the preparation of the film-forming material (A) used in this invention, and such salts are well known. . The phenols from which these phenates are derived have the general formula (R <sup>*</sup> -) <sub>o</sub> - (A <sub>r</sub> <sup>*</sup> -) - (XH) <sub>n</sub> formula () (where R <sup>*</sup> , n, A <sub>r</sub> <sup>*</sup> , X and m are of the formula () is exactly the same as the case of (). The same example described for formula () is applicable. The commonly available type of phenate is the general formula (Here, a is an integer from 1 to 3, b is 1 or 2,
z is 0 or 1, R' is a substantially saturated hydrocarbon substituent having an average of 30 to about 400 aliphatic carbon atoms, and R <sub>4</sub> is lower alkyl, lower alkoxyl, nitro, and It is manufactured from phenols represented by a group selected from the group consisting of halo groups. A particularly useful type of phenate for use in this invention is an overbased A phenol obtained by sulfiding a phenol as described above with a sulfiding agent such as sulfur, a sulfur halide, or a sulfide or hydrosulfide salt. Group metal sulfide phenates. Methods for producing such sulfurized phenates are described in US Pat. Nos. 2,680,096, 3,036,971 and 3,775,321. Other useful phenates are those prepared from phenols linked with alkylene (eg, methylene) bridges. Such phenols are obtained by reacting monocyclic or polycyclic phenols with aldehydes or ketones, typically in the presence of acid or base catalysts. This type of cross-linked phenate, sulfurized phenate, and sulfurized phenate are disclosed in U.S. Pat.
Detailed information is provided in columns 8 to 8. Furthermore, suitable acids include phosphorus-containing organic acids, oil-soluble organic acids such as thiophosphoric acid, and their alkali metal salts and alkaline earth metal salts are preferred. U.S. Patent No. 2606904, U.S. Patent No. 2695910, U.S. Patent No.
No. 2767164, No. 2767209, No. 2777874, No. 3147232 and No. 3274135 describe various overbased salts made from various organic acids. Overbased salts in which the acid is a phosphorus-containing acid prepared from a polyolefin, a thiophosphoric acid, a mixture of a phosphorus-containing acid and a sulfuric acid, or a sulfuric acid are disclosed in U.S. Pat.
No. 3001981, No. 3108960, and No. 3232883. A mixture of any two or more of the above-mentioned organic sulfur acids, phosphorus-containing acids, carboxylic acids, and phenols may also be used. Overbased salts and the neutral salts used in their production are typically sodium, lithium,
These include magnesium, calcium, or barium, and mixtures of two or more of these may also be used. A particularly useful type of overbased salts of organic acids useful in preparing the film-forming materials (A) of this invention are "gelling" overbased salts known in the art as non-Newtonian colloidal dispersions. It is a basic salt.
Overbased systems of this type include: (1) solid metal-containing colloidal particles dispersed in at least one diluent dispersion medium (2) having an average unit particle size of at least 20 Å and up to about 5000 Å; and (2) as a third essential component, the metal ratio formed directly in said non-Newtonian colloidal system from a metal-containing material homogeneously dispersed in a single phase Newtonian overbased material is at least 1.1; It has a lipophilic moiety and at least one polar substituent, and contains at least one organic compound soluble in the dispersion medium (2). Such non-Newtonian colloidal dispersions and their components (e.g., diluents, dispersion media, and organic compounds) are described in, for example, U.S. Pat.
Same No. 3372114, Same No. 3411923, Same No. 3372115
No. 3422013, No. 3350308, No. 3350308, No. 3422013, No. 3350308, No.
No. 3312618, No. 3376222, No. 3471403, No. 3453124, No. 3377283, No. 3595790,
It is described in the same No. 3766067, the same No. 3766066, the same No. 3671012, and the same No. 3384586. In the non-Newtonian system, at least some of the dispersed particles are solid metal-containing particles formed therein. The size of the particles is not critical as long as they are dispersed, for example in the form of a colloid or a colloidal solution. Typically, the size of this particle does not exceed 5000 Å. Generally, the maximum unit particle size is less than about 1000 Å, usually less than 400 Å. It has been found that dispersions with unit particle sizes in the range of 30 Å to 200 Å give excellent results. The term "unit particle size" refers to the
Defined in No. 3384586. The solid metal-containing particles are metal salts of organic acids, low molecular weight organic acids (carbonic acid, acetic acid, propionic acid, etc.), hydrates thereof, or mixtures of two or more thereof.
These salts are usually alkali metal or alkaline earth metal formates, acetates, carbonates, bicarbonates, hydrosulfides, sulfides, sulfates, hydrogen sulfates or halides. magnesium salt,
Calcium and barium salts are typical examples. That is, typically the metal-containing particles are mainly composed of alkaline earth metal salts,
The particles are further characterized by being formed in situ. The colloidal dispersion used in this invention also includes at least one liquid dispersion medium. Since this dispersion medium mainly acts as a liquid carrier in which solid particles are dispersed, there are no particular restrictions on its type. Usually it consists of one or more substantially inert, non-polar oily liquids. This liquid is therefore chemically substantially inert under the relevant environment. In other words, the liquid does not chemically interact with components of its environment in a manner that substantially alters its chemical properties. The liquid dispersion medium may be substantially volatile or non-volatile under standard temperatures and pressures. Often, non-Newtonian dispersions are prepared using a mixture of the above volatile and non-volatile organic liquids as the dispersion medium, so that all or part of the volatile components can be removed by heating. It's easy. This is an optional and often desirable means of controlling the clay or fluidity of the dispersion. A typical dispersion medium is described in US Pat. No. 3,384,586. Such dispersion media include mineral and synthetic oils as well as organic liquids such as ethers, alkanols, alkylene glycols, ketones, and the like. Liquid hydrocarbons, especially liquid stone liquor fractions, are particularly useful dispersion media because of their availability, cost, and performance. Dispersion media of this type include alkylated benzenes, naphthenic petroleum fractions, paraffinic petroleum fractions, petroleum ethers, petroleum naphtha, mineral oils, Stottard solvents and mixtures thereof. Typically, the dispersion medium is mineral oil or at least about 25% of the total dispersion medium is mineral oil. Often at least about 50% of the dispersion medium is mineral oil. As is clear from this, mineral oil may be used by itself as a dispersion medium, or it may be used in combination with a non-mineral oil-based organic liquid, such as the fluidizing agent described below. Preferably, the overbased non-Newtonian system (E) is derived from one or more alkali metal, alkaline earth metal or mixed metal overbased salts thereof of organic sulfonic acids, carboxylic acids or mixtures thereof. Particularly preferred is U.S. Pat.
3492231, non-Newtonian overbased aluminum salts of alkylbenzene sulfonic acids. Clays (B-2) useful in the compositions of this invention are those capable of thickening aqueous slurries containing them. Many such clays are known. For example, ``Applied Clay Mineralology'' by Ralph E. Grimm (McGraw & Hill Books, 1962), as well as U.S. Pat.
See No. 1398201. Typically, montmorillonite type clays are useful. Montmorillonite type clays include bentonite, hechlorite and mixtures thereof. An important component of the composition of this invention is a clay flocculant (C)
, which interacts with the clay to increase its ability to thicken aqueous slurries. The flocculant also acts as a film stabilizer to stabilize the film obtained by removing water from the dispersion composition of this invention. Such flocculants are generally polyvalent metal salts of metals such as copper, aluminum, etc., and are derived from sulfuric acid, chromic acid, formic acid, acetic acid, and mixtures thereof. McBain's ``Colloid Science'' on useful flocculants
(Heath Publishing, 1950), page 396.
Copper salts are particularly useful flocculants, and a typically useful copper salt is cupric sulfate. Usually, when the above-mentioned montmorillonite clay is used together with a clay flocculant, a thixotropic aqueous dispersion composition can be obtained. As is well known, this thixotropic property is desirable when the composition is used in certain coating applications. The compositions of this invention may also contain one or more auxiliary additives. Such auxiliary additives prevent metal corrosion and provide freeze/freeze-thaw stability against temperature changes. Buffers that maintain the pH of the overall aqueous dispersion composition, particularly the slurry that serves as its external phase, are in the desired range of about 6 to about 9. The compositions of this invention may also include one or more clay modifiers. It may be a thickener or a thinner. These are added at various stages of manufacturing the compositions of this invention. For example, it may be desirable to reduce the clay content of the composition during its manufacture and to thicken it after manufacture.
Such techniques are well known to those skilled in the art. Useful thinning agents include the dispersion media described above, such as inert liquid organic solvents/diluents. As a thickener,
There are fillers such as talc, silica, and calcium carbonate. Mixtures of various clay modifiers may also be used. Auxiliary additives that are generally desirable in the compositions of this invention when the compositions are used in the application of ferrous materials.
is a flash rust prevention agent. This rust preventive agent prevents rust on metal surfaces immediately after application using the aqueous dispersion composition of the present invention. The film formed by removing water from the composition of this invention prevents corrosion on metal surfaces once formed, whereas flash rust inhibitors are used to prevent rust before the film is formed. . A typical flash rust inhibitor is a phosphate ester neutralized with tetraethylenepentamine. This ester is well known to those skilled in the art. Typical buffering agents used in the compositions of this invention include a combination of potassium dichromate and acetic acid and a combination of potassium dichromate and phosphoric acid. Acetic acid also acts as a thinning agent. It has been found that the combination of a phosphate-based flash rust inhibitor and a dichromate/acetate buffer or a dichromate/phosphate buffer imparts desirable freeze/thaw stability to the aqueous dispersion compositions of this invention. . The aqueous dispersion compositions of this invention generally contain from about 5 to about 50% of the total dispersion composition.
% by weight, typically from about 10 to about 40% by weight, and from about 1 to about 10% by weight, typically from about 2 to about 6% by weight, of the dispersion composition on a non-hydrate basis. It is included in percentage. Flocculant (C) is present in an amount of from about 1 to about 40% by weight of the amount of clay (B-2), typically from about 2 to about 25%. Auxiliary additives, when used, are used at the concentrations normally used. For example, corrosion inhibitors are about 1 to about 15% by weight, flash rust inhibitors are about 1 to about 10% by weight, buffering agents are about 0.01 to about 1% by weight, and viscosity modifiers are about 0.1 to about 10% by weight.
It is. The compositions of this invention are aqueous and therefore contain water, usually in an amount of at least about 10% by weight, and often at least about 25% by weight. Generally, the compositions of this invention contain oily film-forming substances.
(A) and a clay slurry (B-1) containing viscosity (B-2) and flocculant (C). In this aqueous dispersion composition, the film forming agent (A) forms the internal phase, and the clay slurry (B-
1) forms the external phase. Care must be taken to adjust the PH of this composition to within the desired range. A typical method for producing an aqueous dispersion composition includes: () viscosity of at least one of the increasing amounts (B-2);
a step of hydrating the aqueous clay slurry (B-1) to produce an aqueous clay slurry (B-1);
-1) with an auxiliary additive selected from the group consisting of metal corrosion inhibitors, buffers, freeze/freeze stabilizers and viscosity modifiers to produce an additive aqueous clay slurry (B-3). () treating the aqueous clay slurry (B-1) or the added aqueous clay slurry (B-3) with at least one flocculant (C) to form a treated aqueous clay slurry or a treated aqueous clay slurry; (a) forming at least one carboxylic acid (D) into at least one organic acid overbased salt (E), typically (a) at least one liquid dispersion medium (2); solid metal-containing colloidal particles dispersed in at least 20
formed in situ in the dispersion composition from a metal-containing material homogeneously dispersed in a single-phase Newtonian overbased material having an average unit particle size of Å to about 5000 Å and a metal ratio of at least 1.1; and (b) react with an overbased non-Newtonian colloid system comprising at least one organic compound having a lipophilic moiety and at least one polar group and soluble in the dispersion medium (2) to form a film. a step of producing a film-forming oily substance (A); () optionally a step of fluidizing the film-forming oily substance (A) to produce a fluid substance (F); () optionally, The aqueous clay slurry (B
-1) and (or) a step of adding at least one resin to the film-forming oily substance (A) or the fluid substance (F); and () the film-forming oily substance (A) or the fluid substance.
An aqueous dispersion composition in which (F) is combined with the aqueous clay slurry (B-1) to have the oily substance (A) or fluid substance (F) as an internal phase and the aqueous clay slurry (B-1) as an external phase. It consists of the process of producing something. Typically, the hydration step and each processing step are conducted at a temperature of about 15°C to about 85°C, typically about 70°C to about 80°C. Carboxylic acids and overbased colloid systems (E)
The reaction with is usually carried out at about 20°C to about 120°C. The fluidization step, which is carried out when it is desired to reduce the clay content of the composition below that provided by the oily substance (A) itself, is carried out at a temperature that fluidizes the oily substance (A), usually about 20°C. It is carried out at a temperature of about 150°C. The resin addition step takes place within this same temperature range. The step of combining the film-forming oily substance (A) with the aqueous clay slurry (B-1) is generally carried out at a temperature of about 15°C to about 75°C. In each of the above steps, mixing is usually performed by stirring. Generally, each of the above steps will each be about 0.15 to about
It is held 24 hours a day. In some cases, it is convenient for the hydration step () and the binding step () to each take place for about 2 hours to about 18 hours. As mentioned above, the method for producing the aqueous dispersion composition of the present invention may optionally include the step of adding at least one type of resin. Resins useful here are commercially available polymers such as polyethylene, ethylene/propylene copolymers, polyvinyl acetate, polyvinyl chloride, polybutadiene, and the like. Hydrocarbon resins, typically synthetic waxes, are particularly useful in producing rust-resistant coatings. Microcrystalline waxes are also used. Whatever their individual properties, the resins may provide desirable properties such as adhesion, corrosion protection, thermal stability, etc. to the compositions of this invention by forming coherent films and/or by removing water. This assists in providing a film having a One of the features of this invention is that the dispersion composition is capable of irreversibly forming a coherent film. This means that as water is removed from the composition (eg, by drying), a coherent film is irreversibly formed. Once a film is formed by substantially removing water, it is not possible to add water to restore the original dispersion composition. The aqueous dispersion compositions of this invention are useful in forming corrosion-resistant and corrosion-inhibiting coatings on metal surfaces, such as ferrous metals, plated metals, aluminum or magnesium surfaces. This composition is particularly useful for internally rust-proofing automobile bodies and the like and for base coating. The composition of this invention may be used alone or together with the above-mentioned auxiliary additives. Other additives for such corrosion inhibiting coatings may also be used, such as the resins mentioned above and many petroleum and synthetic waxes. These substances are used in various proportions,
Generally, the amount will be a small amount, typically about 0.5 to about 5% by weight of the composition of this invention.
U.S. Pat. Nos. 3,453,124 and 3,671,072 describe additives useful with the aqueous dispersion compositions of this invention. When intended for corrosion protection, the compositions of this invention are generally applied to the surface to be protected and then substantially removed by evaporating the water present in the composition at ambient or elevated temperatures. to form a coherent film. Typically, about 80 to about 99% water is removed. The coatings thus obtained and products partially or completely coated with such coatings also fall within the scope of the present invention. For the purpose of corrosion prevention, the aqueous dispersion composition of this invention can be applied to metal surfaces by conventional methods such as brushing, spraying, dipping, flow coating, roller coating, etc. Depending on the application method used, the clay of the composition can be adjusted, if necessary, by the addition of substantially inert, normally liquid organic diluents or other clay modifiers as described above. Since the compositions of this invention are thixotropic, the clay can also be modified by mechanical shearing. This shearing can be accomplished by stirring or by forcing through a device such as a pump (eg, a gear pump) or a nozzle. The viscosity can also be adjusted by the amount of water present in the aqueous dispersion composition. By exposing the coated metal surface to the outside air,
Or it can be dried by baking. There is no particular limit to the thickness of the film formed, but
Approximately 50 to 2000 mg per ton ² of coated surface is sufficient for adequate corrosion protection. However, thicker coatings may be used, especially when the metal surface is subjected to severe corrosive conditions or wear, or is stored for a long period of time. Examples of this invention will be described below. All “departments”
and "%" are by weight. Example 1 A hydrated clay slurry was prepared by slowly adding 240 parts of Bentonite 200 (NL clay) to 3750 parts of water with mixing at ambient temperature. The above mixing was performed using a Cowles type mixer until the slurry was smooth and no lumps were observed. The slurry was filtered through a 60 mesh screen and allowed to hydrate overnight. Example 2 The process of Example 1 was carried out using 651 parts of bentonite 200 and 7550 parts of water. Example 3 50/50 isopropyl alcohol and water at 77°C
(%) A mixture of 821 parts of polypropenyl (n=1000) substituted succinic anhydride and a petroleum sulfonic acid overbased calcium carbonate salt in which the free sulfonic acid has a molecular weight of approximately 430 is gelled in the presence of a water/alcohol mixture. A film-forming material was prepared by adding slowly to a mixture with 2860 parts of the resulting non-Newtonian overbased colloidal dispersion. The metal ratio of the overbased sulfonate was 12 and the mineral oil content was 50%. The overbased calcium petroleum sulfonate itself was manufactured by the method of US Pat. No. 3,350,308. Gelation was performed according to the method of US Pat. No. 3,492,231. The above reaction mixture was heated at 77°C under nitrogen.
Heat for 2.5 hours and strip at 150°C under nitrogen. The residue was the desired film forming material. Example 4 452 parts of water and isopropyl alcohol at 77°C
230 parts were slowly added to a mixture of 5000 parts of the non-Newtonian dispersion of Example 3 and 2145 parts of petrolatum oxide (Textyl 3050 manufactured by Assuland Oil). The acid value of the above petrolatum oxide is 57 (ASTM
D-664). The above reaction mixture was heated to 77°C under nitrogen for 2.5 hours, then to 150°C under nitrogen.
I did stripping. The residue was the desired film-forming oily material. Example 5 50/50 (%) of isopropyl alcohol and water
144 parts of the mixture was added to the non-Newtonian dispersion of Example 3.
2176 parts and 700 parts of petrolatum oxide of Example 4 and polypropenyl (n=1000) substituted succinic anhydride
It was slowly and carefully added to the mixture with 233 parts at 77°C. The reaction mixture was heated at 77°C under nitrogen for 2.5 hours and then stripped at 150°C under nitrogen.
The residue was the desired film forming material. Example 6 To 10,368 parts of the hydrated clay slurry prepared in Example 1 was added 8% potassium dichromate and 8% glacial acetic acid at 60°C.
and 30.4 parts of a buffer solution consisting of 84% water, glacial acetic acid
A treated clay slurry was prepared by adding 9.6 parts and 67.2 parts of a 6.4% cupric sulfate aqueous solution. Example 7 To 5192 parts of the hydrated clay slurry prepared in Example 2, 20 parts of a buffer solution consisting of 8% potassium dichromate, 8% glacial acetic acid and 84% water and 45 parts of 6.4% cupric sulfate were added at 60°C. In addition, treated clay slurry was prepared. Example 8 Treated clay slurry 10475 prepared in Example 6
The film-forming material of Example 3 was preheated to 99°C.
4,803 copies were added slowly. This mixture was stirred for 0.5 hour to homogenize the emulsion. At room temperature, 250 parts of water was added to compensate for evaporation losses. Neutralization product of 1 part of commercially available ethoxylated linear alcohol phosphate ester (manufactured by GAF, Antara LK-500) and 2 parts of triethanolamine (rust inhibitor)
394 parts were added to the emulsion. Then, 78 parts of Aqua 100 (a black pigment dispersion manufactured by Borden Chemical) was added to the emulsion. After mixing for 5 minutes, 40 parts of Cab-O-Sil (micro-combusted dried fumed silica, filler manufactured by Cabot Co., Ltd.) was added.
The emulsion was degassed by gentle mixing. Example 9 5263 parts of the treated clay slurry prepared in Example 7 was added with the film-forming material of Example 3 preheated to 99°C.
3210 copies were added slowly. This mixture was stirred for 0.5 hour to homogenize the emulsion. At room temperature, 113 parts of water was added to compensate for evaporation losses. Then,
To this emulsion was added 320 parts of the rust inhibitor of Example 8. Aqua 100 (50 parts) was then added to the emulsion. After mixing for 5 minutes, Cab-O-
Thirty parts of Sil was added and mixed slowly to degas the emulsion. Example 10 To 6540 parts of the treated clay slurry prepared in Example 6 were slowly added 2260 parts of the film-forming material of Example 4, which had been fluidized by reheating to 99°C. This mixture was mixed for 0.5 hours to homogenize the emulsion. At room temperature, 270 parts of the rust preventive agent of Example 8 and 890 parts of a commercially available rust preventive composition were added. Then,
Added Aqua 100 (40 parts). After thorough mixing, the emulsion was degassed by gentle mixing. Example 11 To 6500 parts of the treated clay slurry prepared in Example 6 were slowly added 2320 parts of the film-forming material of Example 5, which had been fluidized by heating to 99°C.
The mixture was stirred for 0.5 hour to homogenize the emulsion. Then, 270 parts of the rust preventive agent of Example 8 and 900 parts of a commercially available rust preventive composition were added at room temperature. After thorough mixing, the emulsion was degassed by gentle mixing. Example 12 The bentonite of Example 1 was prepared in the same manner as in Example 1.
A clay slurry was prepared from 12.63 parts and 145.28 parts water. Example 13 The following components were mixed. Component part 1 Clay slurry (Example 12) 57.44 2 8% K ₂ Cr ₂ O ₇ aqueous solution 0.23 3 10% H ₃ PO ₄ aqueous solution 0.32 4 10% CuSO _{4.5H 2} O aqueous solution 0.50 5 Film-forming substance (implemented) Example 3) 35.48 6 Stoddard Solvent 5.50 7 Water 6.75 8 Black Pigment 0.58 9 Rust Inhibitor (Example 8) 2.9 10 Cab-O-Sil 0.3 Add the above hydrated clay slurry to 30% while mixing with a propeller type steel mixer. It was heated to about 65°C over a period of minutes and water was added to compensate for evaporation losses. Ingredients 2, 3 and 4 were added in order. The film-forming substance was preheated to 100°C and slowly added to the slurry to avoid splattering. The slurry was cooled to about 60°C and ingredients 6 and 7 were added slowly. Ingredient 6
When added, the viscosity increased considerably. Ingredients 8, 9 and 10 were then slowly added in order while stirring the mixture at about 38°C. The resulting product is a highly thixotropic soft gel-like black substance with a solids content of 39% as determined by evaporating a sample at 110°C for 3 hours.
It was hot. Example 14 Regarding the composition of Example 14 of the present invention (containing a flocculant) and the composition of Comparative Example 1 (not containing a flocculant) having the compositions shown in Table 1 below, the results are as follows when these are applied to a steel plate. The properties of the film were tested. The results are shown in Table 2. In Comparative Example 1, the film-forming resin precipitated together with the clay, making it difficult to uniformly disperse it in the aqueous slurry as the continuous phase.

【table】

【table】

【table】

【table】

Claims (1)

[Scope of Claims] 1. As an internal phase, (i) a compound of _the general formula R( _{COOH )} substantially hydrocarbyl group, and x is at least one carboxylic acid represented by 1, 2 or 3)
(D) or a reactive equivalent thereof; and (ii) a non-containing overbased salt of an alkali metal, alkaline earth metal, or mixture of organic sulfonic acids, phosphorus-containing acids, carboxylic acids, or mixtures thereof. at least one film-forming non-asphaltic oily substance (A) obtained by reacting a Newtonian dispersion (E); and () a pH of about 6 to about 9 enriched with clay as an external phase. Aqueous slurry (B-1)
and water and at least one clay (B-
An aqueous dispersion composition capable of irreversibly forming a coherent film, which contains at least one flocculant (C) in addition to 2). 2 The oily substance (A) is at least one carboxylic acid
(D) or a reactive equivalent thereof with at least one non-Newtonian dispersion (E) comprising an overbased salt of an organic acid. Composition according to item 1. 3. The composition according to claim 1, wherein the flocculant (C) is a water-soluble salt of a heavy metal. 4. Claim 3 further comprising one or more auxiliary additives selected from the group consisting of metal corrosion inhibitors, film stabilizers, buffers, viscosity modifiers, and fillers. Compositions as described. 5. The composition according to claim 1 or 2, wherein the clay (B-2) is a montmorillonite clay. 6. The composition according to claim 1 or 2, wherein the carboxylic acid (D) is obtained by oxidizing a substantially hydrocarbyl substance. 7. The viscosity (B-2) of claim 4, wherein the viscosity (B-2) is a montmorillonite clay, the flocculant (C) is a copper salt, and the entire aqueous dispersion composition is thixotropic. Composition. 8 The clay (B-2) is bentonite, hectorite or a mixture thereof, the flocculant (C) is a copper salt, the non-Newtonian dispersion (E) is an overbased calcium sulfonate, and a carboxylic acid (D) is obtained by oxidation of petrolatum, and at least one member selected from the group consisting of metal corrosion inhibitors, film stabilizers, buffers, clay modifiers, and fillers. 7. The composition of claim 6 further comprising auxiliary additives. 9. Buffers and flash corrosion inhibitors selected from the group consisting of chromic acids, mineral acids, C1 _{- C4} carboxylic acids and mixtures thereof are present. Compositions as described in Section. 10 The oily substance (A) is about 5 to about 50% of the dispersion composition.
% by weight, the clay (B-2) comprises from about 1 to about 10% by weight of the dispersion composition, and the flocculant (C)
Claim 1, characterized in that the clay (B-2) contains about 1 to about 40% by weight of the clay (B-2);
The composition according to item 4 or item 8. 11 The non-Newtonian dispersion system (E) is (a) at least 1
solid metal-containing colloidal particles dispersed in a liquid dispersion medium (2) of at least 20 Å to about 5000 Å;
formed in situ in said dispersion composition from a metal-containing material homogeneously dispersed in a single-phase Newtonian overbased material having an average unit particle size of Å and a metal ratio of at least 1.1; (b) having a lipophilic moiety and at least one polar group;
The composition according to claim 2, which comprises at least one organic compound soluble in (2). 12 () At least one type of clay (B
-2) to form aqueous clay slurry (B-1)
() treating the aqueous clay slurry (B-1) or the added aqueous clay slurry (B-3) with at least one flocculant (C) to produce a treated aqueous clay slurry or a treated aqueous clay slurry; (i) as an internal phase, (i) having the general formula R(COOH) _x , where R is the number of carbon atoms derived from the polymerization of at least one _C2 - _C8 olefin; about 12 to about
300 substantial hydrocarbyl groups, and x is 1, 2 or 3) at least one carboxylic acid (D) or reactive equivalent thereof; and (ii) an organic sulfonic acid, a phosphorous acid, a carboxylic acid or A film-forming oily substance (A) is produced by reacting a mixture of two or more of these with a non-Newtonian dispersion system (E) which is an overbased salt of an alkali metal, an alkaline earth metal, or a mixture thereof. () the film-forming oily substance (A) or the fluid substance;
(F) combined with the oily clay slurry (B-1) to form an aqueous dispersion having the oily substance (A) or fluid substance (F) as an internal phase and the aqueous clay slurry (B-1) as an external phase. 1. A method for producing an aqueous dispersion composition capable of irreversibly forming a coherent film, the method comprising a step of producing a composition. 13 The overbased salt is (a) solid metal-containing colloidal particles dispersed in at least one liquid dispersion medium (2) having an average unit particle size of at least 20 Å to about 5000 Å, and having a metal ratio of formed in situ in said dispersion composition from a metal-containing material homogeneously dispersed in at least one phase of Newtonian overbased material; and (b) having a lipophilic moiety and at least one polar group. 13. The method of claim 12, wherein the dispersion medium (2) is an overbased non-Newtonian colloidal dispersion comprising at least one organic compound soluble in the dispersion medium (2). 14. The method according to claim 13, wherein the flocculant is a water-soluble polyvalent metal salt of sulfuric acid, chromic acid, formic acid, acetic acid, or a mixture thereof. 15. The method according to claim 14, wherein the clay (B-2) is a montmorillonite type clay. 16. The method of claim 15, wherein the entire aqueous dispersion composition is thixotropic. 17. The method according to claim 16, wherein the carboxylic acid (D) is obtained by oxidizing a substantially hydrocarbyl substance. 18. The method of claim 17, wherein the substantial hydrocarbyl substance is petrolatum. 19 Claim 1 in which the flocculant (C) is a copper salt
The method described in Section 8. 20. The method according to claim 19, wherein the clay (B-2) is bentonite, hectorite or a mixture thereof. 21 The oily substance (A) accounts for about 5 to about 50% of the dispersion composition.
% by weight, the clay (B-2) comprises from about 1 to about 10% by weight of the dispersion composition, and the flocculant (C)
21. A method according to claim 20, characterized in that the clay (B-2) contains about 1 to about 40% by weight of clay (B-2). 22 Between the steps () and (), the aqueous clay slurry (B-1) is treated with a metal corrosion inhibitor,
a step of producing an additional aqueous clay slurry (B-3) by treatment with at least one auxiliary additive selected from the group consisting of a buffering agent, a film stabilizer and a clay modifier; () a step of fluidizing the film-forming oily substance (A) to produce a fluid material (F), and the aqueous clay slurry (B-1) and/or the film-forming oily substance. 13. The method according to claim 12, comprising the step of adding at least one resin to (A) or to the fluid material (F).