SURFACE-TREATING AGENT, SURFACE-TREATED PLATELETLIKE PIGMENT AND PROCESS FOR PRODUCING THE SAME

Abstract: A surface-treating agent for use in an inorganic powder in which a metallic oxide layer and/or a hydrated metallic oxide layer is formed on the surface, characterized in that said surface-treating agent contains one or more kinds of a polyglycidyl ether compound represented by formula (A), a polyglycidyl ester compound represented by formula (B), and a diglycidyl polysiloxane compound represented by formula (C), wherein R1, R2, R3, R4, R5, n, p and q have the meanings as given in claim 1.

Description: Surf ace-Treating Agent, Surface-Treated Plateletlike Pigment and Process for Producing the Same Detailed Descrip -tion of the Ir.ven ___ .t .i .o.n Field of the Invention The present invention relates to a surface-treating agent for use in ar. inorganic powder, and a sur ace- treated plateletlike piciaent which is surface-treated wit the surface- treating agent. More specifically, the present: invention relates to a surf ce-treated piateletlike pigment, which can suppress formation of a hard cake in a paint or an ink owing to settling during storage, transportation, coating or printing, and which can provide a coated product or a printed product havinc an imorcved * ~ater resistance. Background Pigments in a paint or an ink and insoluble substances making up the paint are, after the production, separated by settling with time during storage, or are gradually retained in a dead space and separated during transportation of a pipe line in coating. As a result, the color is deviated from the initial color, or segregation occurs, making it impossible to conduct desired coating or printing. Further, when the kind of the paint or the ink is changed, the paint which has been retainer' in the dead space of the coating/printing line is mixed to give an adverse effect. In order to prevent the separation by settling, generally, a dispersant has been added or a paint has been blended with an anti-settling agent in advance. For example, anti-settling agents described in "Kanual of Paint Starting Materials", p. 188, "3.2.1.9. Prevention of Thickening and Settling, Prevention of Sagging", such as organic bentonite, amide wax, hydrogenated castor oil wax, -metallic soap, polyethylene oxide and sulfate ester anionic agent [for example, Oisparon Series (trade name for a product of Kusumo o Kasei K.K.) and 371 F (trade name for a product of Hoechst AG)} have been generally used. However, these anti-settling agents are not effective for any pigments and solids. The function and effect of the anti-settling agents vary depending on a combination of properties of the ingredients making up the paint or the ink. such as resins, solvents, pigments and dyes. Accordingly, the use of these anti-setting agents is limited. Besides, the anti-settling agent added acts not only on the effective site which is the surface of the solid, but is distributed throughout the system. Therefore, the anti-settling agent is consumed excessively, and the amount of the anti-settling agent tends to increase inadvantageously. Accordingly, development of a more effective anti-settling agent has been in demand. Meanwhile, a pigment which has itself an anti-settling property, that is, a pigment having a surface that undergoes an c -settling treatment has been developed. Examples of the surf ace- treated pigment which is proposed on the basis of this idea include a pearl pigment which is coated with a polyester- polyurethane block copolymer having a tertiary amino group by a plasticizer, a solvent and a surface active agent (see Japanese La id -Open Patent Application (Kokai) No.63-46,266), a plateletlike pigment coated with polyacrylate or polymethacryla e { see Japanese La id -Open Patent Application (Kokai) No. 5-171,058) and a flaky substrate to which fibrous particles having a particle diameter of from 0.1 to 20 μare adhered by a binder (see Japanese La id-Open Patent Application (Kokai) No. 5-186,707). On the other hand, a pearl pigment obtained by coating a metallic oxide or a hydrated metallic oxide on a plateletlike substrate and a plateletlike pigment based on a plateletlike metallic oxide have been generally used widely as pigments tor a paint, an ink and plastics. However, using these plateletlike pigments as such in a paint, an ink or the like for outdoor use, for example, for automobiles poses a problem with respect to a weatherability. A technology in which the weatherability has been improved is disclosed in, for example, Japanese Patent Publication Nos. 55-4,147 and 6-43,565 and Japanese Laid-Open Patent Application (Kokai) No. 1-292,067. Nevertheless, the pigment having the improved weatherabili y is not said to have a satisfactory anti-settling effect which is a serious problem when the pigment is actually used in the paint or the ink. A pigment that exhibits both the anti-settling property and the weatherability when producing a coated product or a printed product has not been provided so far. Disclosure of the Invention The present inventors have assiduously conducted investigations and development to solve the above-mentioned problems, and have consequently provided successfully a novel surface-treated plateletlike pigment which can suppress separation by settling of a plateletlike pigment in storage, transportation and use of a paint, an ink and the like and formation of a hard cake owing to the separation by settling, and which is useful for a paint, an ink and the like having a water resistance . That is , the present invention is to provide a surface- treating agent for use in an inorganic powder in which a metallic oxide layer and/or a hydrated meta llic oxide layer is formed on the surface , characterized in that sa id surface- treating agent contains one or more kinds of a polyglycidyl ether compound represented by formula (A) wherein R, denotes a dihydric or higher alcohol residue , and p is a figure of 2 or more, a polyglycidyl ester compound represented by formula ( B) wherein R Σ CO- denotes a divalent or higher aromatic or aliphatic carboxylic acid residue, and q is a figure of 2 or more , and a diglycidyl polysiloxane compound represented by formula ( C ) CH 2 CHCH 2 OR 2 (SiO)nSiR 3 OCH 2 CHCH 2 Ra a wherein R 3 denotes a polymethylene chain of the formula - {CH-.) n - in which m is a figure of from 1 to 12, n is a figure of from 1 to 12, and R t and R $ are the same or different and each denotes hydrogen or an alkyl group containing from 1 to 6 carbon atoms , a surface-treated plateletlike pigment which is surface- treated with the surface-treating agent, and a process for producing the same. The present invention will be described in more detail below. The polyglycidyl ether compound of formula (A) which is the surface-treating agent of the present invention is, for example, a polyglycidyl ether compound in which R, is a polyhydric alcohol residue such as alkylene glycol, glycerol, trimethylolprσpane, diglycerol, polyglycerol, neopentyl glycol, pentaerythritol or sorbitol. Specific examples of the polyglycidyl ether compound include (poly) propylene glycol diglycidyl ether, (poly)ethylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6- hexanediol diglycidyl ether, glycerol (poly )glycidyl ether, trimethylolpropane (polyjglycidyl ether, diglycerol (poly )glycidyl ether, polyglycerol (poly )glycidyl ether, sorbitol (poly )glycidyl ether, triglycidyl tris(2- hydroxyethyl ) isocyanurate, pentaerythritol ( polyjglycidyl ether, and sorbitol (polyjglycidyl ether. Examples of the polyglycidyl ester compound of formula (B) include diglycidyl phthalate and diglycidyl adipate. Examples of the compound of formula (C) include a diglycidyl polysiloxane compound in which in of R, is 3, n is 1, and R t and R 5 are methyl groups and having epoxy equivalent (weight per epoxy equivalent) of 180 (for example, l,3-bis(3- glycidoxypropyl)-l, 1 , 3, 3-tetramethyldisiloxane) , a diglycidyl polysiloxane compound in which n is 3 and having epoxy equivalent of 260, and a diglycidyl polysiloxane compound in which n of j is 3, R t and R 5 are methyl groups, and n is 8 and having epoxy equivalent of 450. The amount of the surface-treating agent used is from 0.3 to 10 % by weight, preferably from 0.5 to 5 % by weight based on the plateletlike pigment, though it slightly varies depending on the type of the surface-treating agent. When the amount is less than 0.3 % by weight, the desirous effect is not enough. When the amount is more than 10 % by weight, the effect is not increased so much. The plateletlike pigment used in the present invention may be a plateletlike pigment of which the surface may be coated with the metallic oxide or the hydrated metallic oxide. Examples of the plateletlike pigment include a plateletlike pigment in which one or more metals selected from titanium, tin, iron, zirconium, cerium, zinc, chromium, cobalt, aluminum, silicon, manganese and copper are coated as an oxide or a hydrated o:-:ide on a plateletlike substrate selected f rom plateletlike clay minerals such as mica , synthetic mica , sericite, kaolin and ta lc , and the plateletlike pigment which is further treated with a εi lane coupling agent to impart a weatherability. The plateletlike pigment is preferably a pearl pigment obtained by coating on mica a metallic oxide such as titanium oxide , iron oxide, zirconium oxide, tin oxide , cerium oxide, zinc oxide , chromium oxide , cobalt oxide, aluminum oxide , silicon oxide, manganese oxide or copper oxide, or the metallic oxide which is hydrated, or a complex composition (mixture or layer) thereof . The typical example thereof is Iriodin ( trade name for a product of Merck Japan ) . A pearl pigment in which titanium oxide coated on mica is lower titanium oxide that is partially reduced is naturally used . Anyhow, the plateletlike pigments which are produced by the known method are used . Further, Iriodin WII (trade name ) which is produced by a method described in Japanese La id -Open Patent Application (Kokai ) No . 1 -292 , 067 is also used as the plateletlike pigment in the present invention . Examples of other plateletlike pigments which are used in the present invention include plateletlike metal lie oxides such as plateletlike iron oxide , plateletlike aluminum dissolved iron oxide in which aluminum is dissolved in iron oxide , plateletlike titanium oxide , plateletlike silicon oxide and plateletlike zirconium oxide; plateletlike pigments obtained by coating these plateletlike metallic oxides with metallic oxides different from those plateletlike metallic oxides , which are selected from titanium oxide, iron oxide, zirconium oxide, tin oxide, cerium oxide, zinc oxide, chromium oxide, cobalt oxide, aluminum oxide, silicon oxide, manganese oxide and copper oxide or those metallic oxides that are hydrated; those plateletlike pigments which are treated to impart a weatherability by a method described in Japanese La id-Open Patent Application (Kokai) No. 1-292,067. These pigments will be called "plateletlike pigments" hereinafter unless otherwise indicated. As a process for producing the surface-treated plateletlike pigment in the present invention, the following a) or b) is employed. a) A process which comprises charging a plateletlike pigment into a stirring mixer, adding gradually to the stirring mixer one or more kinds of the compounds represented by formulas (A), (B) and (C) as such or a solution obtained by diluting once the compound (s) with a solvent while stirring at a stirring blade head speed of from 3 m/sec to 80 m/sec, further mixing the mixture while stirring at the stirring blade head speed of from 3 m/sec to 80 m/sec, and then heat- tre.. ting the reaction mixture at from 60 to 160 t. b) A process which comprises charging a plateletlike pigment into a stirring mixer, heating the plateletI i ke pigment at from 60 to 160 β C while stirring at a stirring blade head speed of from 3 m/sec to 80 m/sec, adding gradually to the stirring mixer one or more kinds of the compounds represented by formulas (A), (B) and (C) as such or a solution obtained by diluting once the compound(s) with a solvent, and further mixing the mixture while stirring at the stirring blade head speed of from 3 m/sec to 80 m/sec. Examples of the stirring mixer which is used in the process of the present invention include a Waring blender, a Henschel mixer, a flow mixer, and a microspeed mixer. The stirring blade head speed is preferably from 3 m/sec to 80 m/sec. When the head speed is as low as less than 3 m/sec, part of the substances are agglomerated or granulated, or the treating agent is adhered non-uniformly, making it impossible to obtain a surface-treated plateletlike pigment having desirous properties. When it is higher than 80 m/sec, the plateletlike pigment is destroyed undesirably. The heat treatment during that time is conducted to fix the surface-treating agent on the surface of the plateletlike pigment. Unless the heat treatment is conducted, the effect is decreased. Accordingly, it is presumed that the compounds undergo some reaction on the surface. The temperature of the heat treatment is preferably from 60 to 160 β C An appropriate temperature is set depending on the boiling point and the reactivity of the surface-treating agent. It is advisable that the temperature of the heat treatment be f om 100 to 150 β C in trimethylolpropane (poly)glycidyl ether (compound of formula (A)), from 80 to 150 β C in diglycidyl phthalate (compound of formula (B)), and from 90 to 150 β C in l,3-bis(3- glycidoxypropyl)-1,1 ,3,3-tetramethyldisiloxane (epoxy equivalent 180) . When the temperature of the heat treatment is lower than 60 β C, the surface-treating agent is not fixed enough. When it is higher than 160 β C, the surface-treating agent is evaporated or thermally decomposed, with the result that the effect is reduced and the heat loss in the production is great. Thus, it is undesirable. This heat treatment is conducted while mixing the plateletlike pigment with the surface-treating agent through stirring (b) or the heat treatment is conducted separately after mixing the plateletlike pigmentwith thesurface-treating agent through stirring (a). Especially, the method (b) is preferable fromthe standpointof production efficiencybecause the agglomerationof particles is prevented sinultaneouslywith the heat treatment. In the method (a) in which the heat treatment is conducted after the mixing through stirring, a milling step also is introduced thereafter. The milling may be conducted by means of the mixing stirrer or another new mill such as a beater mill or the like. when the surface-treating agent of the present invention has a high viscosity, a solvent which does not affect a paint or an ink may be selected appropriately in advance and used as a diluent. Examples of the solvent include alcohols such as methanol and ethanol, ketones such as acetone, MEK and MIBK, and aromatics such as B, T and X. In this case, the solvent is evaporated simultaneously with the heat treatment. For example, the pressure is reduced or an inert gas is passed. Effects It has been confirmed that the surface-treated plateletlike pigment of the present invention has quite excellent characteristics that formation of a hard cake in a paint or an ink during storage, transportation and use can be suppressed and the water resistance of the coated f lm and the printed product can be improved. Further, the surface-treated plateletlike pigment of the present invention can be utilized, similarly to general pigments, in the field that does not require the water resistance so much, for example, in the kneading into plastics. The present invention will be illustrated more specif ically by referring to Examples, various evaluation tests and Application Examples . However, the present invention is not limited by these descriptions. Examples - Production of a surface-treated plateletlike pigment - Example 1 One hundred grams of Iriodin 103 as a plateletlike pigment and 2 g of trimethylolpropane polyglycidyl ether were charged into a Waring blender and stirred at a blade head speed of 72 m/sec for 30 seconds. The obtained powder was heat-treated in a constant-temperature bath at 130 T_ for 15 hours. The heat- treated powder was further stirred by means of the Waring blender at the blade head speed of 72 m/sec for 15 seconds to give a surface-treated plateletlike pigment. Examples 2 to 10 Surface-treated plateletlike pigments shown in Table 1 were obtained in the same manner as in Example 1 except that the plateletlike pigment and the surface-treating agent were changed as shown in Table 1. Table 1: Production of surface-treated plateletlike pigments *1) Iriodin 103: mica coated with rutile titanium oxide *2) Iriodin 103WII: Iriodin 103 which is subjected to treatment with a hydrous zirconium oxide-type inorganic substance and an organic substance (hereinafter called "Wll-treated-product) *3) Iriodin 300: mica coated with titanium oxide and iron oxide *4) Iriodin 300WII: Wll-treated-product of Iriodin 300 x ample 11 One hundred grams of Iriodin 504 (mica coated with iron oxide) as a plateletlike pigment and 2 g of l,3-bis(3- glycidoκypropyl)-l,l,3, 3-tetramethyl isiloxane (epoxy equivalent 180) were charged into a Waring blender and stirred at a blade head speed of 50 m/sec for 1 minute- The obtained powder was heat-treated in a constant-temperature bath at 130 β C for 15 hours. The heat-treated powder was further stirred by means of the Waring blender at the head blade speed of 50 m/sec for 15 seconds to give a surface-treated plateletlike pigment. Example 12 A surface-treated plateletlike pigment was obtained in the same manner as in Example 11 except that the platelet like pigment was replaced with Iriodin 504KII (Wll-treated-product of iron oxide-coated mica). Example 13 One hundred grams of Iriodin 103 as a plateletlike pigment and 2 g of propylene glycol diglycidyl ether as a surface- treating agent were charged into a Waring blender end stirred at a blade head speed of 72 m/sec for 30 seconds. The obtained powder was heat-treated in a constant-temperature bath at 110 * C for 15 hours. The heat-treated powder was further stirred by means of the 'Waring blender at the blade head speed of 72 m/sec for 15 seconds to give a surface-treated plateletlike pigment. Example 14 One hundred grams of Iriodin 103 as a plateletlike pigment were charged into a Waring blender and heated to 130 : while stirring at a head speed of 30 m/sec. Two grams of l,3-bis(3- glycidoxypropyl )-l , 1 , 3, 3-tetramethyldisiloxane (epoxy equivalent 180) as a surface-treating agent were charged, and the mixture was treated at the blade head speed of 72 m/sec for 10 minutes. Further, the temperature was maintained at 130 C, and the heat treatment was conducted for 30 minutes while stirring at a blade head speed of 30 m/sec to obtain a surface- treated plateletlike pigment. Example 15 Three kilograms of Iriodin 103WII as a plateletlike pigment were charged into a 20- liter Henschel mixer. Sixty grams of 1 , 3 -bi s ( 3 -g 1 ycidoxypropy 1 ) - 1 , 1 , 3 , 3- tetramethyldisiloxane(3-glycidoxypropyl)-l, 1,3,3- tetramethyldisiloxane (epoxy equivalent 180) as a surface- treating agent were gradually added while stirring at a head speed of 10 m/sec. The mixture was heat-treated at the blade head speed of 50 m/sec for 10 minutes. Further, the temperature was elevated to 130 C while stirring at the blade head speed of 10 m/sec, and the heat treatment was conducted for 30 minutes to obtain a surface-treated plateletlike pigment. Example 16 One hundred grams of a plateletlike iron oxide pigment having a particle diameter distribution of rom 3 μm to 35 μ and an average particle diameter of 15 μn as a plateletlike pigment and 2 g of l,3-bis( 3-glycidoxypropyl )-l , 1 , 3 , 3- tetramethyldisiloxane (epoxy equivalent 180) were charged into a Waring blender, and stirred at a blade head speed of 50 m/sec for 1 minute. The obtained powder was heat-treated in a constant-temperature bath at 130 "C for 15 hours. Further, the heat-treated powder was stirred by means of the Waring blender at the blade head speed of 50 m/sec for 15 seconds to give a surface- treated pigment. Example 17 One hundred grams of the Wll-treated-product of the plateletlike iron oxide and 2 g of 1, 3-bis( 3-glycidoxypropyl )- 1 , 1 , 3, 3-tetramethyldisiloxane (epoxy equivalent 180) as a sur ace-treating agent were charged into a Waring blender, and stirred at a blade head speed of 50 m/sec for 1 minute. The obtained powder was heat-treated in a constant-temperature bath at 130 β C for 15 hours. Further, the heat-treated powder was stirred by means of the Waring blender at the blade head speed of 50 m/sec for 15 seconds to obtain a surface-treated pigment. - Test for a settling property - Examples 18 to 34 Preparation of solvent-type pigments for evaluation and evaluation of the pigments: Each ( 2.54 g) of the surface-treated plateletlike pigments obtained in Examples 1 to 17 and 105 g of a paint resin composition having the following formulation were mixed by means of a shaker to obtain a paint for evaluation. Formulation of a paint resin composition for evaluation: Acridic 47-712 (made by Dainippon Ink And Chemicals, Inc . ) : 70 parts by weight Super Beckermin G821-60 (made by Dainippon Ink and Chemicals, Inc.): 30 parts by weight Toluene: 30 parts by weight Ethyl acetate: 50 parts by weight N-butanol: 10 parts by weight Solvesso #150 (made by Dai shin Kagaku K.K. ): 40 parts by weight Disparon 6900-20X (made by Kusumoto Kasei K.K. ): 0.3 part by weight One hundred cubic centimeters of the thus-obtained solvent-type pigment for evaluation were charged into a stopper-equipped 100 cc cylinder (settling tube), and allowed to stand at room temperature for 24 hours. The cylinder was mounted on a shaker, and the number of shakings required to disperse the pigment which was separatee by settling was measured. The small number of shakings means the less formation of a hard cake through separation by settling. Table 2 shows the number of shakings in the test for the settling property (Examples 18 to 3*.) when using the plateletlike pigments which were not surface-treated (Comparative Examples 1 to 8) and the surface-treated plateletlike pigments (Examples 1 to 17) which were surface- treated according to the present invention. As a result, it was observed that the surface-tre ted plateletlike pigments according to the present invention all show the small number of shakings, meaning that the formation of the hard cake in the layer separated by settling is suppressed. Table 2: Test for a settling property Number of Plateletlike pigment used shakings Iriodin 103 70 Comparative Example 1 Sample in Example 1 24 Example 18 Sample in Example 2 25 Example 19 Sample in Example 3 20 Example 20 Sample in Example 4 24 Example 21 Sample in Example 5 26 Example 22 Sample in Example 6 28 Example 23 Sample in Example 7 28 Example 24 Sample in Example 13 30 Example 25 Sample in Example 14 25 Example 26 Iriodin 103WII 60 Comparative Example 2 Sample in Example 8 40 Example 27 Sampio in Example 15 42 Example 28 Iriodin 300 72 Comparative Example 3 Sample in Example 9 30 Example 29 Iriodin 300WII 65 Comparative Example 4 Sample in Example 10 30 Example 30 Iriodin 504 42 Comparative Example 5 Sample in Example 11 21 Example 31 Iriodin 504WII 52 Comparative Example 6 Sample in Example 12 25 Example 32 Plateletlike iron oxide (particle diameter 3-35 μ average particle diameter 15 |) 50 Comparative Example 7 Sample in Example 16 30 Example 33 Wll-treated-product of plateletlike iron oxide 53 Comparative Example 8 Sample in Example 17 32 Example 34 - Test T r water resistance - Preparation of a paint: A (solvent-type): One hundred grams of a solvent-type resin composition having the following formulation were mixed with 4.35 g of the plateletlike pigment for evaluation to form a base paint. Formulation of a solvent-type resin composition Acridic 47-712 (made by Dainippon Ink And Chemicals, Inc. ) : 70 parts by weight Super Beckermin G821-60 (made by Dainippon Ink and Chemicals, Inc.): 30 parts by weight Toluene: 30 parts by weight Ethyl acetate: 50 parts by weight N-butanol: 10 parts by weight Solvesso #150 (made by Oaishin Kagaku K.K. ) : 40 parts by weight A solvent-type resin composition having the following formulation was used as a top clear resin composition Formulation of a top clear resin composition: Acridic 47-179 (made by Dainippon Ink And Chemicals, Inc.): 70 parts by weight Super Beckermin L-l 17-60 (made by Dainippon Ink and Chemicals, Inc.): 30 parts by weight Toluene: 20 parts by weight MIBK: 20 parts by weight Butyl cellosolve: 10 parts by veight B (aqueous): One hundred grams of an aqueous resin composition having the following formulation were mixed with 4.2 g of the plateletlike pigment for evaluation to form a base paint. Formulation of an aqueous resin composition: Water Sol S-751 (made by Dainippon Ink And Chemicals, Inc. ) : 70 parts by weight Water Sol S-695 (made by Dainippon Ink And Chemicals, Inc. ) : 30 parts by weight Isopropanol: 100 parts by weight Production of a black coated plate: An under coat baking paint having the following formulation was coated on a bonderized plate by means of a spray (spray pressure 4 kg/cm 2 ) such that a thickness of a dry coated film became from 30 to 35 μra. The thus-coated plate was air- dried for 10 minutes, and baked at 150 β C for 40 minutes. Further, the surface of the coated film was polished with water and dried clean. Formulation of an under coat baking paint: Superlack F47 black (made by Nippon Paint Co., Ltd. ): 100 parts by weight Nippe Thinner 741 (made by Nippon Paint Co., Ltd. ): 100 parts by weight Production of a coated plate: A (solvent-type): The above-mentioned solvent-type base paint was coated on the above-mentioned black coated plate to a thickness of from 96/32446 -23- 15 to 20 μm by means of a spray (spray pressure 5 kg/cur ) , a nd air-dried for 10 minutes . Then, a top clear paint was coated to a coated film thickness of from 25 to 30 μm, a ir-dried for 30 minutes , and baked at 130 " C for 20 minutes by means of an explosion-proof dryer to produce a coated plate for test . B (aqueous ) : An aqueous base paint was coated on the above-mentioned black coated plate to a thickness of from 15 to 20 μm by means of a spray (spray pressure 6 kg/cm 2 ) , air-dried for 10 minutes , and then predried at 80 *C for 20 minutes . Subsequently, a top clear paint was coated such that a thickness of a dried coated film became from 25 to 30 μ . The thus-coated plate was air- dried for 30 minutes , and baked by means of an explosion-proof dryer at 140 *C for 30 minutes to produce a coated plate for test . Test for water resistance and a method for evaluating the water resistance : A (solvent-type) : The coated . plate produced in the above-mentioned Production A was dipped in a bath containing hot water of 80 * C , and withdrawn f rom the bath . A change of a shrinkage in the dipped portion was visually observed and evaluated with three grades . B ( aqueous ) : The coated plate produced in the above-mentioned Production B was dipped in a bath containing hot water of 80 ' C, and withdrawn from the bath. A change of a shrinkage in the dipped portion was visually observed and evaluated with three grades. Table 3 shows the results of the evaluation in the test for water resistance when using the plateletlike pigments which were not surface-treated and the surface-treated plateletlike pigments obtained in the present invention. TabLe 3: Results of the test for water resistance Plateletlike pigment used Solvent- type paint Aqueous paint Iriodin 103 x x Sample in Example 1 o Δ Sample in Example 2 Δ Δ Sample in Example 3 o Δ Sample in Example 4 Δ Δ Sample in Example 5 Δ Δ Sa_mple in Example 6 Δ Δ Sample in Example 7 Δ Δ Sample in Example 13 Δ Δ Sample in Example 14 Δ Δ UTmrVriL Δ x Sample in Example C o Δ Sample in Example 15 o Δ iriodin 300 " Δ x Sample in Example 9 o Δ lrxoα n JUUWir i Δ Sample in Example 10 o o Iriodin 504 x x Sample in Example 11 Δ Δ Iriodin 504WII Δ x Sample in Example 12 o Δ Plateletlike iron oxide x x (particle diameter 3-35 μ average particle diameter 15 μ) Sample in Example 16 Δ Δ Wll-treated-product of plateletlike iron oxide & x Sample in Example 17 o Δ x: notable shrinkage ώ slight shrinkage o: negligible shrinkage From the above table, it has been found that the plateletlike pigments (Examples 1 to 17) treated in accordance with the present invention are greatly improved in the water resistance . Application Examples Application Example 1 This Application Example shows an example of an aqueous gravure ink in which a pigraent is used for printing ink. Formulation of an ink: Aqua PAC Medium (made by Toyo Ink Mfg. Co. , Ltd. ) 50 parts by weight Pigment obtained in Examples: 12.5 parts by weight Deionized water was added to the ink having the above- mentioned formulation, and the viscosity was adjusted to 20 sec by Zahncup No. 3. The printing was then conducted. Application Example 2 This Application Example shows an example of a gravure ink in which a pigment is used for printing ink. Formulation of an ink: CCST Medium (nitrocellulose resin: made by Toyo Ink Mfg. Co. , Ltd. ) : 40 parts by weight Pigment obtained in Examples: 8 parts by weight An NC102 solvent (made by Toyo Ink Mfg. Co., Ltd. ) was added to the ink having the above-mentioned formulation, and the viscosity was adjusted to 20 sec by Zahncup No. 3. The printing was then conducted. Application Example 3 This Application Example shows an example in which a pigment is used for coloration of plastics. Formulation: Polyethylene resin (pellets): 100 parts by weight Pigment obtained in Examples: 1 part by weight Zinc stearate: 0.2 part by weight Liquid paraffin: 0.1 part by weight The pellets having the above-mentioned formulation were dry-blended, and injection-molded by means of an injection- molding machine.

Claims: What We Claim Is 1. A surface-treating agent for use in an inorganic powder in which a metallic oxide layer and/or a hydrated metallic oxide layer is formed on the surface, characterized in that said surface-treating agent contains one or more kinds of a polyglycidyl ether compound represented by formula (A) wherein R, denotes a dihydric or higher alcohol residue, and p is a figure of 2 or more, a polyglycidyl ester compound represented by formula (B) wherein R,CO- denotes a divalent o ~ igher aromatic or aliphatic carboxylic aci residue, and c is a figure of 2 or more, and a diglycidyl polysiloxane compound represented by formula (C) O R 4 R 4 O / \ i I / \ CH 2 CHCH2θR2(SiO n 3θCH 2 CHCH2 wherein R } denotes a polymethylene chain of the formula - (CH 2 ) β - in which m is a figure of from 1 to 12, n is a figure of from 1 to 12, and R t and R } are the same or different and each denotes hydrogen or an alkyl croup containing from 1 to 6 ca bon atoms . 2. A. surface-treated plateiotlike pigment which is surface-treated with the surface-treating agent of claim 1 in an amount of from 0.3 to 10 % by weight based on the plateletlike pigment. 3. The surface-treated plateletlike pigment of claim 2 wherein the plateletlike pigment is formed by coating a metallic oxide layer and/or a hydrated metallic oxide layer on a plateletlike substrate selected from plateletlike clay minerals such as mica, synthetic mica, sericite, kaolin and talc. 4. The su face- ree ed plateletlike pigment of claim 2 or 3 wherein the metallic oxide and/or the hydrated metallic oxide is an oxide and/or a hydrated oxide of one or more metals selected from titanium, tin, iron, zirconium, cerium, zinc, chromium, cobalt, aluminum, silicon, manganese and copper. 5. The surface-treated plateletlike pigment of claim 2 wherein the plateletlike pigment is a plateletlike metallic oxide selected from plateletlike iron oxide, plateletlike aluminum dissolved iron oxide, plateletlike titanium oxide, plateletlike silicon oxide and plateletlike zirconium oxide, or the plateletlike metallic oxide further coated with other metallic oxide and/or hydrated metallic oxide. 6. The surface-treated plateletlike pigment of claims 2 to 5 wherein other metallic oxide and/or hydrated metallic oxide coated on the plateletlike metallic oxide is an oxide and/or a hydrated oxide of one or more different metals selected from titanium, tin, iron, zirconium, cerium, zinc, chromium, cobalt, aluminum, silicon, manganese and copper. 7. The surface-treated plateletlike pigment of any one of claims 2 to 6 wherein the plateletlike pigment is treated with a silane coupling agent. 8. A process for producing a surface-treated plateletlike pigment which comprises charging a plateletlike pigment into a stirringmixer, adding gradually to the stirring mixer one or more kinds of the compounds represented by formulas (A), (B) and (C) as such or a solution obtained by diluting once the compound(s) with a solvent while stirring at a stirring blade head speed of from 3 p./sec to 80 m/sec, further mixing the mixture while stirring at the stirring blade head speed of from 3 m/sec to 80 m/sec, and then heat-treating the reaction mixture at from 60 to 160 t. - SI¬ S' process for producing a surface-tceated plateletlike pigment which comprises charging a plateletlike pigment into a stirring mixer, heating the plateletlike pigment at from 60 to 160 *C while stirring at a stirring blade head speed of from 3 m/sec to 80 ro/sec, adding gradually to the stirring mixer one or more kinds of the compounds represented by formulas (A), (B) and (C) as such or a solution obtained by diluting once the corapound(s) with a solvent, and further mixing the mixture while stirring at the stirring blade head speed of from 3 m/sec to 80 m/sec. 10. A paint composition or an ink composition containing the surface-treated plateletlike pigment of any one of claims 2 to 7.

Inventors: HORIE YOSHIFUMI, KUNII KOSHIRO, HORIE, YOSHIFUMI, KUNII, KOSHIRO
Applicants: HORIE YOSHIFUMI, KUNII KOSHIRO, MERCK PATENT GMBH, HORIE, YOSHIFUMI, KUNII, KOSHIRO
Application year: 1996
Main classification: C09C1
IPC codes: C09C1, C09C3, C09D5, C09D7, C09D11, C09D183