Method for modifying surface of powdered material having hydrophilic surface

[Detailed Description of the Invention]

After processing the surface of a powder-like substance which has a hydrophilic surface like a bulking agent for high molecular compounds, and paints in the present invention by Rhenium chelate compound A surface treatment is again carried out by beta-Diketone., Therefore, a hydrophilic surface is denatured and it is related with a dispersibility all improved surface modification method to inside of an organic medium. Generally it is the surface of substances (it is only called a bulking agent etc. for short below), such as a bulking agent for high molecular compounds, and paints, Since it is in the existence for absorptive water [ a hydrophilic functional group like a hydroxyl group ] etc. at the state of V hydrophilicity, it is lacking in oleophilicity, in Grant 1 of A month ago, the dispersibility and miscibility to the inside of organic media, such as a paint, printer's ink, and a high molecular compound, are bad -- base -- when a side uses for the Deadlock large quantity, a defect may be produced about the intensity of the gloss of a paint or printer's ink, concealment power, adhesive strength, or tic A flask, etc. In order to remove such a defect, generally the method of adding a surface-active agent and metal soap into organic Hika, when using a bulking agent etc., or processing by coupling agents of a Aircraft Silang system, such as a bulking agent, is known. fc -- obtaining -- the method (Patent Publication 11H44-17025 No.) of adding in an aluminum Triath rate, or its organic derivative all the media, and raising the dispersibility of a bulking agent, How to process with the titanium system compound which has a partial hydrolysis machine (% Opening No. 145448 [ 50 to ]), How to process with the compound which acylated a part of bases of the aluminum Arco lard of lower alcohol and Crystal class alcohol, or aluminum Arco lard (U.S. Pat. No. 3905936), The method (JP,56-125475,A) of aluminum chelate compound all adding etc. which replaced a part of bases of aluminum Arco lard by Alkyl acetoacetic ester are known. However, many of these compounds have a rash fault which carries out reaction bridge construction and is easy to gel functionality machines, such as hydroxyl machines, such as alkyd resin, and a carboxyl group, in the medium contained mostly. In order to prevent this, it is carboxylic acid to a Okizi aluminium compound with comparatively low reactivity, How to carry out phosphate sulfonate Substitution and use (JP,44-17025,B) This [ Appear's ] is [ JP,56-8393,A ] also insufficient in many cases, and it is at Up 1 To and JP,55-4132,B, making the big carboxylic acid of steric exclusion, phosphate, and sulfonate replace by aluminum Alkoxide, and receiving the functionality machine in resin at all the gelling prevent sake -- etc. -- the substitution alkoxy aluminium compound more than Mol is used. The object is placed on improvement in the drying characteristics of resin etc., endurance, and stability, and ', however this method are a lot of aluminium compounds? It must use. These artificers A vote the above difficulties and do not cause gelling in resin, An effect inquires about Lari and a compound with manufacture handling easy moreover to surface treatments, such as a bulking agent, by a little addition. - Result carried out, The target conditions are fulfilled by carrying out the surface treatment of the bulking agent etc. with a specific aluminium compound, and carrying out a surface treatment again by beta-Diketone continuously, and -- finding out that the good dispersibility which is not seen by coming out one now by a little addition to paints, such as printer's ink, according to an easy surface treatment process and the prominent color definition improvement effect are acquired -- misfire 8J1'f! It came to do :completion of. That is, the present invention is a powder-like substance which has a hydrophilic surface General formula (I) (However, inside R of a formula R3 or R 400% R1 the Alkyl machine of carbon numbers 1 thru/or 6) R2, R3, and R4 are the Alkyl machines of carbon numbers 1 thru/or 22, respectively, Although the alkenyl group of carbon numbers 3 thru/or 22 and The of carbon numbers 6 thru/or 14 are also good, Although any must contain one a with a carbon numbers of eight or more Alkyl machine, a with a carbon numbers of three or more alkenyl group, or an aromatic nucleus and R2, R3, or R4 is in m and n by either of 0.1.2.3 at least, m and n are the average value per molecule, and are +n =0.5~2.7.n=0.3~2.5.m+n=0.8~3. To about the reforming method of the powder-like substance which has a hydrophilic surface by which it is carrying-out-by beta-Diketone-how many animal surface treatment all characterized after carrying out a surface treatment with the aluminium compound which comes out and contains at least one sort of the aluminum chelate compound shown which comes out. The aluminum chelate compound of the present invention is described still in detail. R10- is a reactant machine for hydrophilic tables, such as a bulking agent in which hydrophilic functional groups (for example, hydroxyl group etc.) and absorptive water exist in the aluminum chelate compound of Be supposed to and the present invention, and is l! On the other hand, R2 and/or R are 119 and a basis which gives oleophilicity to the surfaces, such as this bulking agent. Therefore, as for the short thing of chain length called the Alkyl machine of carbon numbers 1 thru/or 6 in R1 being chosen in the above-mentioned general formula (1), the strong reactivity with the hydrophilic surface of a bulking agent etc. of this alkoxy group R10- is for To be, and a long-chain thing has weakly unsuitable reactivity. R1 has an isopropyl group, a 5ee-butyl group, a preferred isobutyl machine, etc. from practical use. It is a Alkyl machine of the alcohol which constitutes the acetoacetic ester which forms the chelate group of R2H general formula (1). these R2 is a fatty series machine with unsaturated saturation Tortoise of carbon numbers 1 thru/or 22 -- as good Oxide Example -- an octadecyl group, a Maille machine, a benzyl group, etc. -- raising -- 1L To. R of a general formula (1) -- R3 -- or R4CO all front [ all the ] is carried out, and these R3 and R4 are the same as the definition of 11J account R2. The Remaining machine of carboxylic acid, such as stearic acid, oleic acid, benzoic acid, abietic acid, and acrylic acid, is raised to a thing desirable as R4Co, for example. As mentioned above, in the aluminum-ized V-compound of the present invention, since it is a thing where R2, R3, and R4 raise the compatibility of a bulking agent etc. and which carries out work content, there must be these R2Rs and at least 1 of R4 at a with a carbon numbers of eight or more substitution machine. Each of R2, R3, and R4 may be replaced by functional groups, such as a Completion Minot machine and a hydroxy group. In R, R3 set and R4C and zero set may live together. in a general formula (1) -- Rt, and R2 and R -- m, n, and 3- (m+n) which show a per each molecule existence rate are determined in consideration of the balance of the strength to which chelate compound of the present invention reacts to the hydrophilic surface of a bulking agent etc., and the oleophilicity which it is going to give. namely, -- it is the average value per molecule of the aluminum chelate compound of the present invention, and 1., and m is 0.5 thru/or 2.7, and Is 1 thru/or 2 spread good 1 -- n -- 0.3 thru/or 2.5 -- a squirrel and m10n are 0.8 thru/or 3 in 1 thru/or 2 spreading good 1. since the average value of an R10-basis of m decreases in a whirlpool in the end of 05 -- j with scarce reactivity with a hydrophilic surface, and 2.7' (when it z exceeds, reactivity spreads strong-j In person good 1 -- there is nothing.) If n becomes insufficient [ less than 03 / what oleophilic mosquito to the surfaces, such as a bulking agent, ] and exceeds 2 or 5 stitches, R+0- which is a reactant machine for hydrophilic tables decreases, and it is not desirable. If the present invention carries out aluminum chelate compound When, it is Diynoxypropyl aluminum mono oleyl aceto acetate, Mono-4 Sopro Boxy aluminum and Sule oil aceto acetate, Mono-isopropoxy monometer Cryl mono oleyl aceto acetate, Mono-Impopogisi aluminum monooleate monoethyl acetoacetate, Mono-isopropoxy aluminum monoethyl acetoacetate mono-Leoylacetate acetate, Diisopropoxy aluminum Monolauryl aceto acetate, diisopropoxy aluminum Monostearyl aceto acetate, Diyne Proxy aluminum mono-isostearyl Acetoacetate, Mono-propoxy aluminum bis Oleyl acetoacetate, mono-Sorzoroboxy aluminum monometer Creatorate monooleaire 7 Triacetate, Mono-isopropoxy aluminum Ethyl acetoacetate, Monoin bloboxifumuminium mono rosinate Monolauryl acetophosphate, Diinpropin aluminum Monoabietyl aceto acetate and Monoino propoxy aluminum mono- N-lauroyl beta-Alany, Tomono lauryl aceto Acetate is raised. It is considered as beta-Diketone used as a re-finishing agent in the present invention, and then, Acetyl acetone, Dibesosoyl methane, Alkyl acetoacetic ester, Alkyl acetoacetic acid amide, etc. can be blown, and it is kicked. Respectful use of the aluminium compound in the present invention are 0.1 thru/or 30-fold Attitude preferably 0.5 thru/or 20 weight charge to a bulking agent etc. use of beta-Diketone in the present invention -- a shield is 005 thru/or 20-fold Raiding, Is 0.2 spread good 1, or 10fN A shrine to a bulking agent etc. as for the surface treatment method in the present invention, 1 Normal temperature f It was is warming -- the bottom (theta°C~200degreeC) -- an aluminium compound -- a bulking agent etc. -- as it is -- or it dilutes with a suitable diluent, and a surface treatment is mixed and carried out with a mixer, or it adds together with a bulking agent etc. into the organic solvent, and carries out a surface treatment. Then, re-IL clothes side processing is carried out in a similar way using beta-Diketone. The bulking agent etc. and]7 The to which property modification of the surface is carried out by the present invention method, Calcium carbonate, kaolin, mica, aluminium hydroxide, a titanium dioxide, Silica, zinc yellow, red lead oxide, red ocher, a flower of zinc, talc, carbon black, Although a bulking agent, the paints and metal fine powder of inorganic matter or organicity, such as barium sulfate, magnesium carbonate, asbestos, glass fiber, carbon textiles, copper phthalocyanine blue, cinchona bark Kriton yellow, Prussian blue, and lake red C, and metal oxide fine powder can be raised, Not the thing that runs to these but the substance in which the surface carries out a hydrophilic Ke owner is applied widely. In thing ih which has this hydrophilic surface, the Sufficient agent to which absorptive water exists in what has hydrophilic functional groups and crystal water, such as a hydroxyl group, on the surface, or the surface, and property modification of the surface was carried out by the aluminium compound of To and the present invention, beta-, and Diketone is applicable to a wide range organic medium. As this organic medium, it is drying oil, such as flaxseed oil, tung oil, and soybean oil, for example, Synthetic drying oil, such as drying castor oil, mullein-ized oil, styrene-ized oil, and vinyltoluene-ized oil, Rosin, hardened rosin, polymerization rosin, rosin Esral, maleic acid resin, Nature, such as seven racks and Semen, processing resin, phenol resin, xylene resin, denaturation alkyd resin, polyamide resin, and coumarone-indene resin -- urethane resin -- a synthetic resin, chlorinated rubber -- cyclized rubber -- rubber ?dj >9 body and nitroglycerine cellulose, Vehicle, such as paints, such as faFry matter 9 union of ethyl cellulose etc., and printer's ink, Solvents >, such as hexane, toluene, xylene, and cello Sorbuyo U diluent, Polyethylene resin, polypropylene II++h, polyethylene a1 fat, Polyvinyl chloride jHJi&, polyester resin, non-Gloomy l polyester 4'J l1tj, ; the high molecular compound for forming processing of 1; liquor Bonate resin, silicon resin, acrylics tree j111, fluorine resin, an epoxy resin, A B S resin, BS resin, etc. -- raising -- t carrying out -- combination with To and the account organicity medium of 1'+Q, A surface treatment is carried out by the aluminum chelate compound of negligent Qli, and beta-Diketone, and they are fc bulking agents, It is applicable to a variety of products, such as pollution-free plastic cement consisting of the flame retardant plastic and polyolefin resin which are included in printing 4 Niki, a paint, vinyl chloride Vlasta Lubricant, aluminium hydroxide, or all the calcium carbonate large quantities, and calcium carbonate. Practical effects, such as a bulking agent in which property modification was carried out by the present invention, are Rolling, for example, a paint and printer's ink e Roughly, very much, (1) In 'i:f'c plastic by which the mixed time at the time of (4) manufactures whose (3) adhesive strength from which increase of (2) glosses whose color definition improves, or concealment power is obtained improves is shortened, (1) The effect of that the physical property of (3) M article in which (2) mobility becomes good which can increase rates of a fill factor, such as a bulking agent, is improved, (4) mixture time being shortened is acquired. Although the detailed reason of these effects of the present invention is unknown, Since [ which, on the other hand, has stable oleophilicity with the basis to which the aluminium compound in un-inventing reacts with the hydroxyl group of the surfaces, such as a bulking agent, easily ] it goes berserk and has '-A machine and a carboxylic acid group, a bulking agent etc. and organic medium A crown are considered for miscibility with resin etc. to improve. The active large residual alkoxy group and absorptive water of an aluminium compound which originate in -C1 aluminium compound by the re-document surface treatment by beta-Diketone performed by continuing at the surface treatment by 1fc aluminium compound, the hydroxyl group which arose by a reaction with crystal water etc. changes to stable chelate compound, when chelated by 7y-Tecton -- the original characteristic -- the dispersing agent effects, such as a To bulking agent, -- To lose -- it is thought that there are nothings and the gelling agent characteristic is prevented. It is the present invention by a following example? It explains still in detail. It is based on the combination rate in an example at the amount of vehicles. Example 1 It scales to the beaker of Tait (aluminium compound) k 100 d. After carrying out churning mixture for 30 minutes at normal temperature, it is on a hot bath and was air-dry. Subsequently, to these paints, Agitation 71 during 30 minutes was together put at the Acetyl acetone (beta-Diketone) shown in the 1st table, n-hexane 30fi, in addition normal temperature, and subsequently it is on a hot bath, it was air-dry, and obtained surface treatment finishing paints to them. 1st Table Note (1): made in [ colon Vya Ann carbon company ] brand name [Rahaeng 101,255J Note (2): brand name r Cyanine blue LBG J, the product made from Sumitomo Chemical ■ Note (3): brand name r Lionol Red DWG J, the product made from TOYO INK MFG. ■ (Exhibition color examination) coloring oil gamma In order to see the color definition improvement effect in Printing, Inc. of the processed paints for tables which showed in NTJ1 table, the processed paints for tables were added to No. 4 festival, and it got entangled in Hoover Mahler (100X3 times), and obtained. subsequently, the view wheat gluten (1 ability inspection) Exhibition color this coloring oil to Colored paper and according to meat [and a spectrum -- light IIL -- Geodesy: of the reflectance depended comparatively -- it carried out. Those results are as follows. (1) Carbon Hook 1 combination, No. 4 7.:: (Note) A 7 (charge of one copy +ajj 3 o f41+2) It was obtained from unsettled paints, it was made fC71'- and Crude oil gold leather quasi, and the degree of thickening was made sensuous Rebuke 1. 3) Color tone:blackness; gloss etc. were sensuously evaluated on the basis of the coloring oil obtained from unsettled paints with the naked eye. 4) reflectance in the wavelength of 600 nm is made into Because and the coloring The oil conference standard which was able to be acquired from unsettled paints, and this is received -- decreasing rate kn took out. The degree of black is so large that a numerical value is large. (2) Copper phthalocyanine blue 1 1 combination: (Note) A color tone, gloss, bronze, transparency, etc. were sensuously evaluated on the basis of profitable coloring oil ! with the naked eye from 70 copies of No. 4 varnish ten 30 copies of paints 2 unsettled paints. 3) The decreasing rate to this was computed on the basis of the coloring oil which was able to obtain the reflectance in the wavelength of 720 nm from Because and unsettled paints. a numerical value is thick -- it is and there is no degree redness -- coming -- n -- Not -- it is blue. (3) The 4th table of red azo rake 1ゝ (Note) It is made coloring Oil Eating Nose and \ Tea room which were obtained from 1 combination No. 4 festival 65K (S+ paints: % 5 in part 2) unsettled paints, and is evaluation E7 sensuously in ? naked eyes, such as a color tone, gloss, bronze, and transparency. 3) this is received on the basis of eye reflectance Custody in the wavelength of 570 nm, and the coloring oil obtained from unsettled paints -- carrying out fall Heavy metal calculation -- 1 This. It is such beautiful red and is To that a numerical value is large. In the application to Printing, Inc., the color definition of a color carries out the same as the above of the paints processed by the present invention method, and also they have the feature that no thickening by guru-izing used as the paints which carried out single processing with the aluminum chelate compound Mira 7 is so that clearly from the above result. Example 2 It distributed to * To 7150 A go to carbon black 5 Q 9 f 11-, Diisozoropogin aluminum mono oleyl aceto acetate 59 was added, and 2:00 B churning mixture was carried out at room temperature. Subsequently, after adding 2.5 g of dibenzo Il methane and carrying out churning mixture at room temperature for 1.5 hours, Xan was distilled off to n- and surface treatment finishing paints were obtained. It was obtained in this way and the Exhibition color examination was done like 'fc paints all example 1. The result is shown in the 5th table. 5th Table Example 3 Titanium dioxide 30 f/, n-hexane 902, and Diisogloboxy aluminum mono oleyl aceto acetate 3? f It scaled to the 200 ml beaker. At normal temperature, churning mixture was carried out for 30 minutes, and it is after 7 It was and on a hot bath, and was air-dry. Subsequently, churning mixture was carried out for 30 minutes at normal temperature [ n-hexane 10 f carats ] with oleyl aceto aceto amide 22, n-Hexaneke distilling off was carried out and the surface treatment finishing titanium dioxide was obtained. It added into the above-mentioned surface treatment finishing titanium dioxide 0.39 and xylene 3O-all test tube, and it shook enough, and it was made to distribute and the relation between Because, the settled time, and the degree of sedimentation was compared with contrast (1) and contrast (2) by making into the degree of sedimentation the degree to which a titanium dioxide sediments. a result -- Ke -- it is shown in the 6th table. - The sample used for the examination Contrast (1); commercial-item (Gia Min's oleic acid salt) contrast (2): Unsettled - The degree of sedimentation - (height / U +Q'4.' of a sedimentation side (height of the solution after four) (the X100 6th table)) (Note) 1 contrast article company commercial item-0,039, titanium dioxides 0 and 3v, and xylene 30- were mixed and measured.