GB2174999A

GB2174999A - Resin composition comprising barium sulphate

Info

Publication number: GB2174999A
Application number: GB08613141A
Authority: GB
Inventors: Kiyoshi Shinozuka; Koihi Otsu; Hiroshi Fukumoto
Original assignee: Onahama Sakai Kagaku KK
Current assignee: Onahama Sakai Kagaku KK
Priority date: 1982-12-28
Filing date: 1986-05-30
Publication date: 1986-11-19
Also published as: GB2174999B; DE3347191A1; GB2134094B; GB8613141D0; GB2134094A; GB8334361D0; DE3347191C2; DE3348108C2

Abstract

Resin compositions comprise a resin and barium sulphate in platelet form in an amount of not more than 50% by weight of the resin. The BaSO4 platelets have specified dimensions. A method of producing surface-treated barium sulfate is disclosed which has an improved dispersability in resins and coating compositions. The method comprises adding an aqueous solution of an alkali silicate to an aqueous slurry of barium sulfate which contains barium ions in excess to deposit barium silicate on the surface of barium sulfate, and then adding to the slurry a mineral acid to decompose the barium silicate to hydrous silica. The thus surface-treated barium sulfate may be further coated with hydrous metal oxides such as alumina or with a silane coupling agent so as to have a more improved dispersability.

Description

1 GB 2 174 999 A 1

SPECIFICATION

A resin composition including surface-treated barium sulfate The present invention relates to resin compositions including surface- treated barium sulfate which has an 5 improved dispersability in resins and organic vehicles.

In general, barium sulfate is produced by the reaction of a barium salt such as sulfide, choloricle or nitrate with sulfuric acid or its salts such as sodium sulphate in an aqueous solution. This reaction generally provides spherical barium sulfate which is usually from 0.3 to 2 microns in the primary particle size. The barium sulfate thus produced is filtered off, washed with water, dried and pulverized for various uses. It is 10 well known in the art that the barium sulfate particles aggregate to larger secondary particles of several microns to several tens of microns in the course of drying and pulverizing, and the smaller the primary particle size, the larger the secondary particle size on account of a larger cohesive force between the particles. In particular, the primary particles not more than 0.1 microns in particle size form a hard dried cake after filtering and drying, and the cake provides large secondary particles several tens to several hundreds of 15 microns in particle size when pulverized by a usual pulverizer, for example, a hammer mill. Such large particles of barium sulfate are lacking in dispersability in resins and organic vehicles. Accordingly, when being used in resin moldings, the particles are clearly perceived as aggregates by the naked eye, and when being used in coating compositions, the particles cause the turbidity in the resulting coating. The primary particles of about 0.05 microns or less in particle size form a much harder cake, and the secondary particles 20 therefrom are too large to use as an extender pigment. Even the pulverizing of the cake by a powerful jet mill using high pressure air or steam results only in a stronger cohesion of secondary particles.

The use of barium sulfate as an extender or filler is based upon its chemical and physical stability which makes the surface thereof inactive. Therefore, as another difficulty in using barium sulfate as an extender, barium sulfate is by nature not well dispersable in resins and organic vehicles.

An improved method of producing surface-treated barium sulphate is the subject of our copending UK patent application no. 84 34361.

The present invention provides improved resin compositions, such as resin mouldings, coating compositions and ink compositions, which contain surface treated barium sulfate in plateletform.

According to the invention there is provided a resin composition which includes surface-treated barium 30 sulfate particles therein, the barium sulfate particles being produced by a method which comprises:

(a) adding an aqueous solution of an alkali silicate to an aqueous feed slurry of barium sulfate which contains barium ions in excess, the alkali silicate being added in amounts of 0.1-30% by weight in terms of silicate based on the weight of barium sulfate in the slurry, to deposit barium sulfate on the surface of barium sulfate in the slurry; and then, (b) adding a mineral acid to the resultant slurry and adjusting it to a pH of not greater than about 7 to decompose the barium silicate to hydrous silica.

Other objects and features of the invention will appear in the course of the description thereof which follows.

The aqueous feed slurry of barium sulfate which contains barium ions in excess may be prepared preferably by the reaction of barium sulfide with sulfuric acid or its water-soluble salts such as sodium sulfate in an aqueous solution in the presence of excess amounts of barium ions. Therefore, this aqueous solution reaction may be carried out in the presence of excess amounts of barium sulfide in relation to sulfuric acid or its salts. The excess amounts of barium sulfide may be replaced by other water-soluble barium salts such as barium chloride or nitrate. Although not critical, barium ion is usually present in the solution reaction in excess from 0.1 to 20 mole % based on the stoichiometric amount, and preferably from 1 to 10 mole %. As will be apparent, the excess barium ions remain after the reaction to provide an aqueous feed slurrv of barium sulfate which contains barium ions in excess.

On the other hand, when the aqueous solution reaction is carried out stoichiometrically or nearly so, or in the acidic conditions in the presence of excess amounts of sulfuric acid, water-soluble barium compounds 50 such as barium sulfide and barium nitrate are dissolved in the resultant slurry of barium sulfate after the reaction so as to provide a feed slurry containing barium ions in excess.

The aqueous solution reaction is carried out usually at temperatures not lower than 400C, and preferably between 60'C and 90'C. The feed aqueous slurry is so prepared preferably as to contain barium sulfate in amounts of 70-150 g/I from the viewpoint of process economy, although not critical.

When necessary, a feed slurry may be prepared by suspending pulverized barium sulfate in water and then adding thereto a water-soluble barium compound as previously referred to.

As fully described later, in the method employed to produce barium sulphate for use in the invention the excess barium ions in the feed slurry is reacted with an alkali silicate to form barium silicate on the surface of barium sulfate in the slurry. Therefore, when the slurry contains barium ions only in a little excess, it may be 60 than an insufficient amount of barium silicate deposits on the surface of barium sulfate, whereas when the slurry contains too large an excess of barium ions, a large amount of barium sulfate is newly produced in the decomposition reaction of barium silicate by sulfuric acid to hydrous silica, also as will be fully described later, and barium sulfate thus obtained may have a low dispersability as a whole. Therefore, it is preferable that the feed slurry contains barium ions in amounts from 0.1-20 mole %, most preferably 1-10 mole %, 65 2 GB 2174999 A 2 based on the barium sulfate in the slurry.

In one process, an aqueous solution of alkali silicate, preferably of sodium silicate or potassium silicate, is added to the aqueous feed slurry of barium sulfate to deposit barium silicate on the surface of barium sulfate in the slurry. The alkali silicate is used in amounts of 0. 1-30% by weight, preferably 1-20% by weight, in terms Of Silica, Si02, based on the weight of barium sulfate in the slurry so that the excess barium ions in the slurry react with the alkali silicate to form a uniform coating of barium silicate on the surface of barium sulfate in the slurry.

When too small an amount of alkali silicate is used in relation to barium sulfate in the slurry, a uniform coating of barium sulfate with barium silicate is not attained, whereas when too large an amount is used, an excess amount of hydrous silica is produced when barium silicate is decomposed by a mineral acid added to 10 the slurry afterthe decomposition of barium silicate on barium sulfate, and the excess hydrous silica may cause the aggregation of barium sulfate particles to undesired larger particles.

A mineral acid is then added to the aqueous slurry to hydrolyze the barium silicate on the surface of barium sulfate to form a coating of hydrous silica, which may be represented by Si02-nH2O. Among mineral acids are preferably used hydrochloric acid and nitric acid since these acids produce no water-insoluble 15 barium salts in the presence of barium ions in the slurry. However, sulfuric acid may also be used if necessary. Since the hydrolysis reaction of barium silicate occurs at a pH not greater than about 7, the slurry is usually adjusted to a pH of 2-7, and preferably 5-7 in order to provide barium sulfate particles having a pigment pH of about 6-8. The hydrolysis reaction may be carried out at temperatures of about 400C or higher, and preferably at temperatures from 60'C to 90'C.

The barium sulfate particles thus surface-treated are readily filtered, and a cake thereof provides secondary particles small in particle size and excellent in the dispersability in resins and organic vehicles even when the primary particles of barium sulfate prepared in the aqueous solution reaction are 0.5 microns or less in average particle size.

The barium sulfate thus surface-treated may be further coated with hydrous metal oxides such as hydrous 25 alumina and hydrous titania so as to have a more improved dispersability. This coating of barium sulfate with hydrous metal oxides is accomplished according to the invention by adding an aqueous solution of a water-soluble metal compound to the aqueous slurry of barium sulfate having a coating of hydrous silica thereon, and then neutralizing the metal compound with an alkali or an acid, depending on the metal compound used, to water-insoluble hydrous metal oxides. The water-soluble metal compound is used in 30 amounts of 0.1-30% by weight in terms of anhydrous metal oxide thereof based on the weight of barium sulfate in the slurry. The amount of 1-20% by weight in terms of anhydrous metal oxide based on barium sulfate is most preferred.

The alkali or acid which is used to decompose the water-soluble metal compound is selected depending on the metal compound used, and is not specifically limited. However, alkalis such as sodium hydroxide, 35 potassium hydroxide and ammonia, or acids such as hydrochloric acid and nitric acid are preferably used in amounts sufficient to decompose the water-soluble metal compound to form a water-insoluble coating of hydrous metal oxide on the surface of barium sulfate. Excellent results are usually obtained when the alkali or acid is added to the slurryto adjust itto a pH of 6-8. The decomposition reaction may be also carried out at temperatures of 40'C or higher, and preferably attemperatures of 60C to 90'C, although not critical.

The water-soluble metal compound used in the process includes compounds of magnesium, aluminum, zirconium, titanium and zinc. Typical examples are sulfates, chlorides and nitrates. Water-soluble basic salts such as titanyl sulfate and complex salts such as sodium aluminate may also be preferably used.

Since barium sulfate is an advance coated with hydrous silica, a uniform and tight coating of hydrous metal oxides is formed possibly through the reaction of hydrous silica with the metal oxides formed thereby, 45 to further improve the dispersability of barium sulfate in resins and organic vehicle compositions as well as the filterability from the aqueous slurry. On the other hand, barium sulfate which has no coating of hydrous silica has little affinity with hydrous metal oxides formed so that the metal oxides precipitate independently without depositing on the surface of barium sulfate, thus causing no improvement in the dispersability thereof.

Alternatively, barium sulfate having a coating of hydrous silica thereon may be treated with a silane coupling agent so as to have a more improved dispersability in resins and coating compositions. Preferably a silane coupling agent is added to the aqueous slurry of barium sulfate successively after the decomposition of barium silicate to hydrous silica from the viewpoint of process economy. However, powders of barium sulfate may be directly treated with a silane coupling agent. The silane coupling agent 55 preferably used in amounts of 0.01-5% by weight, most preferably 0.05-2% by weight based on the weight of the barium sulfate.

Silane coupling agents are already known, and most of the agents have the general formula:

X-Si(OR)3 wherein X represents an organic group containing an alky], a vinyl, an acryloxy, a methacryloxy, an amino, an epoxy, a mercapto, a halogen, for example, and R represents an alky]. Therefore, some examples of agent usable in the invention are vinyltrimethoxysilane, -yanilinopropy[trimethoxysilane, methyltrimethoxysilane, 65 -ymethacryloxypropyltrimethoxysilane and ^1-glycydoxytrimethoxysilane.

3 GB 2 174 999 A 3 Since barium sulfate made by the process described herein has a coating of hydrous silica thereon, the silanecoupling agent reacts with hydroxyls of the silica, thereby to provide a uniform and tight coating of the agent. However, barium sulfate having no coating of hydrous silica is little improved in the dispersability by the treatment possibly beause of substantially no formation of binding between the inactive surface of barium sulfate and silane coupling agent.

The barium sulfate thus having a coating of hydrous silica or a further coating either of hydrous oxides of metals or of silane coupling agent is filtered off, dried and pulverized for use. The barium sulfate particle about 0.5 microns in primary particle size or less, and even 0.1 micron or less, is readily filtered but also forms a cake which is pulverizable to finely divided particles by a usual pulverising means such as a jet mill.

Therefore, the particle has an improved disperability in resins and organic vehicles, and resin moldings and coatings including such particles have improved transparency and gloss. A wet cake may be used as it is for aqueous coating compositions, if necessary.

It has been unexpectedly found out that the barium sulfate particle in the form of plate, when being surface-treated as above, improves physical properties of resin compositions. In more detail, a resin molding formed of a resin composition which contains the surface-treated barium sulfate in platelet form has improved mechanical strength, especially bending strength. A coating composition and an ink composition which contain such barium sulfate are greatly improved in physical and chemical properties such as anti-abrasion, anti-chipping, adhesion to substrates and anti-cracking properties. These improvements are attainable in particular when the platelet barium sulfate is about 0.2-20 microns in the maximum diameter, 0.2-20 microns in width and 0.05-20 microns in thickness, more preferably about 2-10 microns in the maximum diameter, 2-10 microns in width and 0.1-1 microns in thickness, wherein the maximum diameter means herein the longest diameter on the platelet, and the width means the length of a diameter at right angles to the longest diameter. The improvements may be due to the layer orientation of barium sulfate platelets in the resin compositions. However, particles larger than 20 microns in the maximum diameter are not ideal for use as an extender pigment since such large particles are perceivable as clear particles in the composition, and lower the gloss, whereas particles smaller than 0.2 microns in the maximum diameter cause little improvement in physical strength of resin products. It is preferred that the resin composition of the invention contains the platelet barium sulfate in amounts not more than 50% by weight of the resin in the composition. The incorporation of the barium sulfate in too large an amount may cause deterioration of the resulting composition on the contrary.

Various resins may be used in the resin composition of the invention. When resin moldings are intended, suitable resins for use are, for example, thermoplastic resins such as polyvinyl chloride, polyethylene, polypropylene, polystyrene, polycarbonate, ABS resins, acrylic resins and polyurethane, and thermosetting resins such as epoxy resins, polyester resins, urea resins, melamine resins, alkyd resins and dial lyl phthalate resins. When coating compositions inclusive of an ink composition are intended, for example, thermosetting acrylic resins, alkyd resins, polyester resins and epoxy resins are preferably used. The resin composition may, depending on the resin, contain additives which have been heretofore conventionally incorporated into coating compositions. The additive may be, for example, plasticizers, fillers, reinforcing agents, curing agents, catalysts, colorants, antioxidants, lubricants and solvents.

As previously described, the aqueous feed slurry of barium sulfate to be surface-treated may be prepared by any known method. Therefore, the following is illustrative only. The primary particle size of spherical barium sulfate produced in the aqueous solution reaction is usually controllable by the amount of barium ions or sulfate ions contained in excess in the reaction solution as well as reaction temperatures, concentrations of reactants, stirring, etc. For example, barium sulfate 0. 1 micron or less in average particle size may be prepared by the aqueous solution reaction under a vigorous stirring wherein the solution 45 contains barium ions in excess, as is disclosed in Japanese Patent Application No. 54-145951.

On the contrary, barium sulfate in the form of platelets may be prepared, for example, by the stoichiometric reaction of barium sulfide and sulfuric acid at a pH of about 3-6 in an aqueous solution. The primary particle size may also be controllable by reaction conditions such as temperatures, concentrations of reactants and manners and efficiency of stirring during the reaction.

The invention will be more clearly understood by reference to the following examples, which however are intended only to illustrate methods of producing resins according to the invention and are not to be construed as limiting the scope of the invention.

Example 1 (a) Preparation of surface-treated barium sulfate An aqueous solution of sulfuric acid (110 g/l, 200C) and an aqueous solution of barium sulfide (120 g/l, 500C) werefed to an 850 ml-capacity reaction vessel provided with a stirrerwith a rate of 700 I/hour of sulfuric acid solution so thatthe resulting slurry, under a vigorous stirring, stayed therein forO.17 seconds in average, and contained barium sulfide in excess in amounts of about 6 g/l, therebyto provide a slurry of 60 spherical barium sulfate of 0.02-0.1 microns in primary particle size and about 0.05 microns in average particle size.

The slurry was divided into two, and one of them was filter-pressed and washed, and the resulting wet cake was again suspended in water to provide a slurry containing 500 g/I of barium sulfate. The slurry was then spray-dried and hammer-milled to provide barium sulfate particles as a comparative sample (A). 65 4 GB 2 174 999 A 4 The other slurry of the two was heated to 70'C, a 10% aqueous solution of sodium silicate was added thereto in amounts of 20% by weight in terms of silica (Si02) based on the barium sulfate in the slurry to deposit barium silica on the barium sulfate. Hydrochloric acid solution was then added to the slurry to adjust it at a pH of 2 to decompose the barium silicate to hydrous silica and the slurry was left standing for 30 minutes foraging followed by the addition thereto a 20% aqueous solution of sodium hydroxide to adjust 5 the slurry at a pH of 7, and the slurry was aged for 30 minutes. The slurry was then filter-pressed and washed with water, dried with an electric heater, and hammer-mil led to provide particles (1) about 10 microns in average particle size, which are according to the invention.

For a further comparative example, an aqueous solution of barium sulfide was reacted with an excess amount of sulfuric acid in the same manner as above to provide an aqueous slurry of barium sulfate having a 10 pH of 1 which contained no barium ion. An aqueous sodium hydroxide solution was added to the slurry to adjust it at a pH of 7, and then was added a 10% aqueous solution of sodium silicate in amounts of 20% by weight in terms of silica based on barium sulfate in the slurry. The resulting slurry was worked up in the same manner as above to provide comparative paticles of barium sulfate (B).

(b) Preparation of resin sheet and properties thereof A compound was prepared which was composed of 100 parts of polyvi nylch lo ride resin, 45 parts of dioctylphthalate, 5 parts of epoxidated soybean oil, 0.7 parts of cadmium stearate and 0.3 parts of barium stearate, all the parts by weight. Each sample of barium sulfate particles was added in amounts shown in Table 1 in relation to 100 parts by weight of the resin to the compound and kneaded by rolls at a temperature of 1250C for 7 minutes, and then formed into a sheet. The sheet was then pressed at a temperature of 160'C 20 for 10 minutes to provide a test sheet 1 mm thick.

The transparency of the test sheet was determined in terms of Hunter L value by a color meter, and the dispersability of particles therein was determined by counting the number of aggregates perceived by the naked eye. The results are shown in Table 1.

TABLE 1

Barium Sulfate Added 0 5 10 20 5 30 Hunter L values (%) Dispersability ComparativeA 94 73 61 43 some Comparative B 94 70 56 35 many 35 Invention 1 94 88 86 80 none Parts byweight in relation to 100 parts byweightof resin.

Example 2 (a) Preparation of surface-treated barium sulfate The aqueous slurry of barium sulfate containing 6 g/I of barium sulfide which was prepared in Example 1 was heated to a temperature of 70'C, and was added thereto a 10% aqueous solution of sodium silicate in amounts of 5% by weight in terms of silica based on the weight of barium sulfate in the slurry. To the slurry was added hydrochloric acid to adjustthe slurry at a pH of about 4, and the slurry was aged for 30 minutes. Thereafter a 20% aqueous solution of sodium aluminate was added to the slurry in amounts of 10% by weight in terms of alumina (A1203) based on the weight of barium sulfate in the slurry while maintaining the slurry at a pH of about 6 by the addition thereto hydrochloric acid. To the resultant slurry was added a 20% aqueous solution of sodium hydroxide to adjust the slurry at a pH of about 7 followed by a 30-minute aging, to deposit hydrous alumina on the surface of barium sulfate. The slurry was then filtered, washed with water, 50 dried by an electric heater and jet-milled to provide spheric particles of barium sulfate 4 microns in average particle size of the invention (11).

For comparison, the same aqueous slurry as above which contained barium sulfide in excess was made acidiG and then the same solution of sodium aluminate used in the above was added to the slurry in amounts of 10% by weight in terms of alumina based on the weight of barium sulfate in the slurry while maintaining it 55 at a pH of about 5 by the addition thereto hydrochloric acid. Thereafter a 20% aqueous solution of sodium hydroxide was added to the slurry to adjust it at a pH of about 7, and then the resultant slurry was left standing for 30 minutes for aging. The slurry was then worked up in the same manner as above to provide a comparative particles of barium sulfate (C) 13 microns in average particle size.

(b) Preparation of coating composition and properties thereof.

A resin solution was prepared which was composed of 17.5 parts of baking alkyd resin, 8.9 parts of melamine resin and 4.9 parts of xylene, all the parts by weight. To the resin solution was added 15 parts by weight of a sample of barium sulfate particles and dispersed therein by a paint conditioner, and the size of particles in the resultant dispersion was determined every five minutes by a fineness gage. The results are shown in Table 2. As apparent, the barium sulfate of the invention has an improved dispersability in the GB 2 174 999 A 5 vehicle.

After a 60-minute dispersion, the resultant coating composition was applied on a glass plate by an applicator to form a coating 6 mil thick, dried at room temperature and was then baked at 14WC for 20 minutes. The 2C2O'gloss and the Hunter L value transparency of the baked film were determined by a gloss 5 meter and a color meter. respectively. The results are shown in Table 3.

TABLE 2

Dispersing Time Fineness of Barium Sulfate (microns) (min.) 11 C A 10 25 35 45 15 25 28 9 18 15 20 5 15 10 is below 5 13 8 12 6 10 below 5 8 60 7 20 TABLE 3

Barium Sulfate 25 11 C A Hunter L values (%) 96 92 95 200/200 Gross 160 98 155 30 Example 3 (a) Preparation of surface-treated barium sulfate An aqueous solution of sulfuric acid (1.28 moles/[, 25'Q and an aqueous solution of barium sulfide (0.74 moles/[, 480C) were continuously fed to a 250 I-capacity reaction vessel provided with a stirrer at the rates of 35 900 I/hour and 1600-1800 1/hour, respectively, so that the reaction mixture stayed in the vessel for 6 minutes in average at temperatures of about 52'C and had barium ion in excess in amounts of 0.03 moles/I by controlling the feed rate of barium sulfide solution, to provide an aqueous slurry containing spherical particles 0.2 microns in average particle size.

The slurrywas divided into four. The first slurry wasfiltered, washed with water, dried and jet-milled to 40 provide a comparative sample of barium sulfate particles (D).

The second slurry was heated to a temperature of 70'C, and was added thereto a 30% aqueous sodium hydroxide solution to adjust it at a pH of about 10. Thereafter an aqueous solution of sodium silicate of the concentration of 100 g/I in terms of silica was added to the slurry in amounts of 1.0% by weight in terms of silica based on the weight of barium sulfate in the slurry and the slurry was stirred for 10 minutes. Then a 45 10% aqueous hydrochloric acid was added to the slurry to adjust it at a pH of about 6 followed by the aging for 30 minutes to deposit hydrous silica on the surface of barium sulfate. The slurrywas worked up in the same manner as above to provide particles of barium sulfate of the invention (111).

The third slurry was worked up in the same manner as in the preparation of particles (111) inclusive of the step of aging. Thereafter a 30%-aqueous sodium hydroxide solution was added to the slurry to adjust it at a 50 pH of about 7, and -y-methacryloxypropyltrimethoxysilane was added in amounts of 0.5% by weight based on the weight of barium sulfate followed by a 30 minute aging. The resultant slurry was worked up in the same manner as above to filter, dry and pulverize, thereby to provide particles of barium sulfate of the invention (IV).

Thefourth slurrywas treated in the same manneras in the preparation of particles (111) to provide a slurry 55 of barium sulfate having a coating of hydrous silica thereon at a pH of about 6. Then an aqueous solution of sodium aluminate was added to the slurry in amounts of 2.0% by weight in terms of alumina based on the weight of barium sulfate in the slurry, and then a 1 0%-hydrochloric acid was added to adjust the slurry at a pH of about 7 to deposit hydrous alumina on the surface of barium sulfate. The slurry was worked up in the same manner as above to provide particles of barium sulfate of the invention (V).

(b) Preparation of coating compositions and properties thereof A mixed solvent composed of Solvesso 150, n-butanol and butyl cellosolve (70/20/10 in the weight ratio) was added to a solution of mixed resin of polyester resin and melamine resin (85/15 in the weight ratio) to prepare a resin solution containing the resins in 50% by weight.

Each of the barium sulfate obtained above or marketed titanium dioxide having a silica-alumina coating 65 6 GB 2174999 A 6 thereon and average particle size of 0.3 microns was added to the resin solution in amounts shown in Table 4 together with carbon black to provide a coating composition. Each coating composition was adjusted to have a proper viscosity and applied on a zinc phosphate-treated steel plate by a spray to form a coating 30 microns thick. The coating was then baked at a temperature of 1600C for 30 minutes to form a film.

The mechanical strength of the film in terms of Erichsen value (JIS Z 2247 A-method) and shock resistance 5 (JIS K 5400-6.13), pencil hardness (JIS K 5400-6.14) and 20/20 specular gloss were determined, and the results are shown in Table 4. As apparent, the film from the coating composition which contains barium sulfate of the invention is comparable with or superior to the film from the composition containing titanium dioxide in the gloss, strength and hardness whereas the film from the compositions which contain the comparative particles of barium sulfate is inferior to the above films in such properties.

TABLE 4 is a b Coating Compositions c d e Compositions Resin solution 100100 100 100 100 Barium sulfate 111 20 20 Barium sulfate IV 20 Ba ri u m su Ifate V 20 Barium sulfate D 20 Titanium dioxide 20 20 20 20 40 Carbon black 0.35 0.35 0.35 0.35 0.7 25 Properties 20Y2O'Gross 77 80 81 70 78 Pencil hardness 3H 3H 3H 2H 3H Erichsen values 5.1 5.3 5.4 4.8 5.2 30 Shock resistance (cm) 40 40 40 35 40 Parts by weight Example 4 (a) Preparation of surface-treated barium sulfate An aqueous solution of sulfuric acid (125 g/l, 200C) was fed to a 250 kcapacity reaction vessel provided with a stirrer at a rate of 200 I/hrtogether with an aqueous solution of barium sulfide (125 g/l, 50'C) so that the reaction mixture in the vessel had a pH of about 4 by controlling the feed rate of barium sulfide solution to provide an aqueous slurry of barium sulfate in the form of plate 5 microns long, 5 microns wide and 0.5 40 microns thick in average.

The thus prepared slurry was divided into five. The first slurry was filter-pressed to provide a wet cake, and the cake after drying was hammer-milled to provide a comparative sample of barium sulfate particles (E).

In the second slurry was dissolved barium sulfide in amounts of 0.5 mole % based on the barium sulfate in the slurry, and the resultant slurry was heated to a temperature of 70C. Thereafter a 10% aqueous solution of sodium silicate was added to the slurry in a mounts of 1.0% by weight in terms of silica based on the weight of barium sulfate in the slurry to deposit barium silicate on the barium sulfate. Then to the slurry was added hydrochloric acid to adjust the slurry at a pH of about 2 to decompose barium silicate on the barium sulfate to hydrous silica. After a 30 minute aging, a 30% aqueous sodium hydroxide solution was added to the slurry to adjust it at a pH of about 7. Then the slurry was filtered, washed, dried and pulverized to provide 50 particles of barium sulfate of the invention (VI).

The third slurry was treated in the same manner as in the preparation of particles (VI) to form a coating of hydrous silica on barium sulfate. To the resultant slurry at a pH of about 7 was added -methacryloxypropy Itrimethoxysilane in amounts of 0.3% by weight based on the weight of barium sulfate in the slurry. After a 30 minute aging, the slurry was worked up in the same manner as above to provide particles of barium sulfate of the invention (VII).

The fourth slurry was treated in the same manner as above to form a slurry of barium sulfate having a coating of hydrous silica. Then a 30% aqueous solution of sodium hydroxide was added to the slurry to adjust the slurry at a pH of about 6, and was added thereto an aqueous solution of sodium aluminate in amounts of 1.0% by weight in terms of alumina based on the weight of barium sulfate in the slurry followed 60 by the addition of hydrochloric acid to adjust the slurry at a pH of about 7 to deposit alumina on the surface of barium sulfate. The slurry was then worked up in the same manner as above to provide particles of barium sulfate of the invention (Vill).

For the preparation of another comparative sample of barium sulfate particles, an aqueous sodium hydroxide solution was added to the fifth slurry to adjustthe slurry at a pH of about 7, and was added thereto 65 7 GB 2 174 999 A 7 the same silane coupling agent as used above in the same amount followed by a 30 minute aging. Then the slurry was worked up in the same manner as above to provide a comparative sample of particles (F).

(b) Preparation of resin moldings and properties thereof 20 parts by weight of each barium sulfate obtained above and 80 parts by weight of isotactic polypropylene were mixed in a Henschel mixer, granulated and injection- molded to a test molding. The mechanical strength of the molding (JIS K 6758) are shown in Table 5. As apparent, the moldings which contain barium sulfate of the invention have larger bending moduli and Izod impact values than the moldings which contain the comparative barium sulfate particles.

(c) Preparation of coating compositions and properties thereof To 100 parts of the same resin solution as used in Example 3 (b) was added 10 parts of each barium sulfate,10 0.7 parts of carbon black and 40 parts of titanium dioxide, all the parts by weight, and dispersed thereinto provide a coating composition. The composition, after being adjusted in the viscosity, was applied on a zinc phosphate-treated steel plate, and baked to form a film in the same manner as Example 3(b) above. The Erichsen value and shock resistance (JIS K 5400-6.13) were determined and the resluts are shown in Table 5.

As apparent, the film from the coating composition which contains barium sulfate of the invention has an 15 improved mechanical strength.

TABLE 5

Barium Sulfate 20 Vi Vil Vill E F Resin moldings Bending modulus (kg/cm) 22000 24630 23500 16500 16700 25 Izod impact values 130 140 135 91 90 Coating films Shock resistance (cm) 35 40 35 30 30 Erichsen values () 5.5 6.2 5.8 4.5 4.7

Claims

1. A resin composition which includes surface-treated barium sulfate particles therein, the barium sulfate particles being produced by a method which comprises:

(a) adding an aqueous solution of an alkali silicate to an aqueous feed slurry of barium sulfate which 35 contains barium ions in excess, the alkali silicate being added in amounts of 0.1-30% by weight in terms of silicate based on the weight of barium sulfate in the slurry, to deposit barium sulfate on the surface of barium sulfate in the slurry; and then, (b) adding a mineral acid to the resultant slurry and adjusting it to a pH of not greater than about 7 to decompose the barium silicate to hydrous silica.

2. A resin composition according to claim 1 in which barium sulfate particles in the feed slurry are spherical and not more than about 0.5 microns in average primary particle size.

3. A resin composition according to claim 1 in which barium sulfate particles in the feed slurry are platelets and are 0.2-20 microns in the maximum diameter, 0.2-20 microns in width and 0.05-20 microns in thickness.

4. A resin composition according to any preceding claim in which the feed slurry contains barium ions in amounts of about 0.1-20 mole% based on barium sulfate in the slur.

5. A resin composition according to any preceding claim in which the alkali silicate is sodium silicate, potassium silicate or a mixture of these.

6. A resin composition according to any preceding cl.aim in which the method further includes the steps 50 of (c) adding an aqueous solution of a water-soluble metal compound to the aqueous slurry of barium sulfate having hydrous silica thereon, the metal compound being added in amounts of 0.1-30% by weight in terms of the weight of anhydrous oxide of the metal based on the weight of barium sulfate in the slurry; and then, (d) adjusting the slurry to a pH of not greater than about 7 so as to decompose the metal compound to water-insoluble hydrous oxide of the metal and to deposit the hydrous oxide of the metal on the surface of barium sulfate.

7. A resin composition according to claim 6 in which the water-soluble metal compound is at least one of water-soluble sulfates, basic sulfates, complex salts, halides or nitrates of magnesium, aluminium, zinc, 60 zirconium or titanium.

8 GB 2 174 999 A 8 8. A resin composition according to claim 6 in which the water-soluble metal compound is sodium aluminate.

9. A resin composition according to any of claims 1 to 5 in which the method further includes the step of treating barium sulfate having hydrous silica thereon with a silane coupling agent.

10. A resin composition according to any preceding claim in the form of a molding.

11. A resin composition according to any preceding claim for use as a coating composition.

12. A resin composition substantially as described.

13. A resin composition substantially as described with reference to the examples.

Printed in the UK for HMSO, D8818935, 9186, 7102. Published by The Patent Office, 25 Southampton Buildings, London, WC2A lAY, from which copies may be obtained.