JPH0158229B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention modifies the hydrophilic surface by treating the surface of particulate materials such as fillers for polymer compounds and pigments with an aluminum compound to improve their dispersibility in organic media. This invention relates to surface modifiers. In general, the surface of substances such as fillers for polymer compounds and pigments (hereinafter simply referred to as fillers, etc.) is in a hydrophilic state due to the presence of hydrophilic functional groups such as hydroxyl groups and adsorbed water, so they are lipophilic. If the raw material is used as it is, it has poor dispersibility and miscibility in organic media such as paints, printing inks, and polymeric compounds, and if the raw material is used in large quantities, it may reduce the gloss, hiding power, or plastic properties of the paint or printing ink. Defects may occur in strength, etc. In order to eliminate such defects, it is generally known to add a surfactant or metal soap to an organic medium when using a filler or the like, or to treat the filler or the like with an organic silane coupling agent. In addition, a method for improving the dispersibility of fillers by adding aluminum triacylate or its derivatives to an organic medium (Japanese Patent Publication No. 44-17025
(No.), a method of treatment with a titanium compound having a partially hydrolyzable group (JP-A-50-145448), treatment with an aluminum alcoholate of a lower alcohol and a higher alcohol, or a compound in which some groups of the aluminum alcoholate are acylated. Methods such as (US Pat. No. 3,905,936) are known. However, many of these compounds have the disadvantage that they tend to undergo reaction crosslinking and gelation in a medium containing a large amount of functional groups such as hydroxyl groups and carboxyl groups such as alkyd resins. In order to prevent this, there is a method of using a relatively low-reactive oxyaluminum compound substituted with carboxylic acid, phosphates, or sulfonates (Japanese Patent Publication No. 17025/1982, Japanese Patent Application Laid-open No. 8393/1983). In addition, in Japanese Patent Publication No. 55-4132, a substituted alkoxyaluminum compound is added in an amount equal to or more than the equivalent molar amount to the functional group in the resin in order to substitute carboxylic acids, phosphates, and sulfonates with large steric hindrance to aluminum alkoxide, and to prevent gelation. I am using it. However, the purpose of this method is to dry the resin etc.
The aim is to improve durability and stability, and a large amount of aluminum compounds must be used. The present inventors solved the above-mentioned difficulties and researched a compound that does not cause gelation in the resin, is effective for surface treatment of fillers etc. with the addition of a small amount, and is easy to manufacture and handle. As a result, alkoxide and cidroxy compounds in which the aluminum atom was simultaneously substituted with carboxylic acids and sulfonic acids, as shown in the general formula (), satisfied the target conditions,
Furthermore, the present inventors have discovered that adding a small amount of pigments to printing inks and the like can provide a remarkable effect of improving sharpness that has never been seen before, leading to the completion of the present invention. That is, the present invention is based on the general formula () [However, in the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ³ is R ⁴ or R ⁵ O-, and R ² , R ⁴ and R ⁵ are each an alkyl group having 1 to 22 carbon atoms. , cycloalkyl group, carbon number 3 to
22 alkenyl group, aryl group, aralkyl group, or alkylaryl group, in which R ² and R ³ may be the same or different, but one of R ² and R ³ has 8 or more carbon atoms. must be a substituent, m and n are the average values per molecule, m = 0.5
~2, n=0.3~2, m+n=0.8~2.7. ]
The present invention relates to a surface modifier for particulate materials having a hydrophilic surface, which is characterized by containing at least one of the aluminum compounds shown in the following. The aluminum compound of the present invention will be described in more detail. In the general formula (), R ¹ O- is a hydrophilic functional group (for example, a hydroxyl group) or a group that is reactive with a hydrophilic surface such as a filler where adsorbed water is present, so strong reactivity is required ^. Those with long chains have weak reactivity and are unsuitable. Therefore, R ¹ is selected from a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and in practical terms, a hydrogen atom, an isopropyl group, a sec-butyl group,
Isobutyl group etc. are preferred. On the other hand, the carbon substituents in R ² and R ³ are groups that impart lipophilicity to the surface of fillers, etc., and are therefore selected from groups with long chains or a ^large number ^of carbon atoms as defined above. At least one of the carbon substituents must have 8 or more carbon atoms. Preferred examples include ethyl group, butyl group, octyl group, lauryl group, myristyl group, cetyl group, palmityl group, oleyl group, stearyl group, nonylphenyl group, dodecylphenyl group, and the like. In the general formula (), m, n, and 3-(m+n), which indicate the abundance ratio per molecule of R ¹ O-, carboxylate, sulfonate, etc., indicate that the aluminum compound of the present invention has a hydrophilic surface such as a filler. It is determined by considering the balance between the strength of the reaction and the lipophilicity to be imparted. In other words, as an average value per molecule, m is 0.5
n is 0.3 to 2, preferably 0.5 to 1.5, and m+n is
It is between 0.8 and 2.7. If the average value of m is less than 0.5, there will be fewer R ¹ O groups, resulting in poor reactivity with the hydrophilic surface. This is not desirable because it reduces Examples of the aluminum compounds of the present invention include those shown in Table 1 below.

[Table] To obtain these aluminum compounds, a general method is to react an aluminum alcoholate such as aluminum isopropoxide or aluminum butoxide with carboxylic acids and sulfonic acids, as shown in the following reaction formula. The amount of aluminum compound used in the present invention is 0.1 to 20 weight percent, preferably 0.5 to 3 weight percent, based on the filler and the like. Addition treatment methods include adding the filler as it is or a solution diluted with an appropriate diluent and treating it in a mixer, or adding it together with the filler in an organic solvent and removing the solvent after treatment. , organic medium
Either of the methods of directly adding the filler etc. to the system can be adopted. Examples of fillers whose surfaces are modified by the aluminum compound of the present invention include calcium carbonate, carrion, mica, aluminum hydroxide, titanium dioxide, silica, zinc yellow, red lead, red iron oxide, zinc white, talc, and carbon. These include, but are not limited to, inorganic or organic fillers and pigments such as black, barium sulfate, magnesium carbonate, asbestos, glass fiber, phthalocyanine blue, quinacridone yellow, and Lake Red C. Substances with hydrophilic properties are widely applied. The substance having a hydrophilic surface is one having a hydrophilic functional group such as a hydroxyl group or water of crystallization on the surface, or one having adsorbed water on the surface. Fillers whose surfaces have been modified with the aluminum compound of the present invention can be applied to a wide range of organic media. Examples of the organic medium include drying oils such as linseed oil, tung oil, soybean oil, synthetic drying oils such as dehydrated castor oil, maleated oil, styrenated oil, vinyltoluenated oil, rosin, hydrogenated rosin,
Natural and processed resins such as polymerized rosin, rosin ester, maleic resin, shellac, zein, synthetic resins such as phenolic resin, xylene resin, modified alkyd resin, coumaron-indene resin, rubber derivatives such as chlorinated rubber, cyclized rubber, Paints such as cellulose derivatives such as nitrocellulose and ethyl cellulose, vehicles such as printing inks, solvents and diluents such as hexane, toluene, xylene, and cellosolve, polyethylene resins, polypropylene resins, polystyrene resins, polyvinyl chloride resins,
Polymer compounds for molding processing include polyester resin, polycarbonate resin, silicone resin, acrylic resin, fluorine resin, epoxy resin, ABS resin, and BS resin. In combination with the above-mentioned organic medium, fillers etc. whose surface has been treated with the aluminum chelate compound of the present invention can be used for printing inks, paints, PVC plastic tiles, flame-retardant plastics containing a large amount of aluminum hydroxide or calcium carbonate, It can be applied to a wide variety of products such as non-polluting plastics made of polyolefin resin and calcium carbonate. The filler modified by the present invention has various practical effects, including (1) improved clarity in paints and printing inks; (2) Increased gloss and hiding power can be obtained, (3) Mixing time during manufacturing can be shortened, and in the case of plastics, (1) the filling ratio of fillers, etc. can be increased, (2) fluidity (3) the physical properties of the product are improved, and (4) the mixing time is shortened. especially,
In the case of plastics, it is necessary to combine fillers and resins in order to improve their physical strength, and the present invention is expected to be effective in this respect. These effects are due to the fact that the aluminum compound in the present invention has a group that easily reacts with hydroxyl groups on the surface of the filler, etc., and a lipophilic group bonded to stable sulfonic acid groups and carboxylic acid groups. This is thought to be due to improved miscibility between the organic medium or resin, etc. The present invention will be explained in more detail with reference to Examples below. The compound numbers in the examples are shown in Table 1. Production Example 1 A four-necked flask from Step 2 was equipped with a stirrer, a thermometer, a dropping funnel, and a condenser, and 204 g (1 mol) of aluminum isopropoxide and 400 ml of toluene were added to the flask, and the mixture was added dropwise at room temperature while stirring. A solution of 327 g (1 mole) of dodecylbenzenesulfonic acid and 100 ml of toluene was added dropwise through the funnel over 30 minutes. Then, 282 g (1 mol) of oleic acid was added dropwise in the same manner.
The mixture was heated under reflux for 30 minutes, and toluene and produced isopropyl alcohol were distilled off under reduced pressure to obtain 693 g of Compound (2) as a viscous oil. Production Example 2 After dodecylbenzenesulfonic acid and oleic acid were added to aluminum isopropoxide in accordance with Production Example 1, a solution of 18 g (1 mole) of water and 100 ml of isopropyl alcohol was added over 5 minutes. Then, the mixture was heated to reflux and the same operation was performed to obtain 651 g of Compound (4) as a viscous oil. Example 1 In order to examine the stability of the aluminum compound of the present invention in an organic medium, 3% of the aluminum compound was added to No. 3 varnish, which has many functional groups, and the viscosity change of the solution was measured under a constant temperature of 50°C. The subjects were followed for one month. The results are shown in Table 2. In addition, solid materials that were difficult to dissolve were liquefied with a small amount of toluene and added. Γ Control product; diisopropoxyaluminum oleate

[Table] Example 2 In order to examine the sharpness improvement effect of the aluminum compound of the present invention in printing ink, 5% of the aluminum compound was added to a commercially available ink, and a color development test was conducted after kneading. Visual comparison with a blank to which no aluminum compound was added revealed a clear improvement in sharpness. This effect was also manifested as a clear difference in the light reflectance on the surface of the colored test piece. When the color tristimulus values X, Y, and Z were measured using a color difference meter, it was found that the values of the portions corresponding to the complementary colors of each ink decreased. That is, the values of Z decreased for red ink, X for blue ink, and X, Y, and Z values for black ink. Table 3 shows the reduction rates of X, Y, and Z values relative to the blank when an aluminum compound was added in black ink. In addition, solid materials that were difficult to dissolve were liquefied with a small amount of xylene and added.

[Table] Example 3 In order to examine the dispersion effect of the aluminum compound of the present invention, 0.03 g of the aluminum compound, 0.3 g of titanium dioxide, and 30 ml of xylene were added to a test tube and shaken thoroughly to disperse the titanium dioxide. The degree of sedimentation was determined as the sedimentation degree, and the relationship between the standing time and the sedimentation degree was compared with a blank and a control product. The results are shown in Table 4. Samples used for Γ test Control (1): Commercial product (diamine oleate) Control (2): Blank Γ Sedimentation degree = (height of settling surface / height of solution immediately after standing) x 100

[Table] Example 4 To examine the viscosity-lowering effect of the aluminum compound of the present invention, 0.2 g of the aluminum compound, 10 g of calcium carbonate, and 5 g of xylene were thoroughly mixed in a mortar, and the viscosity at 25°C was measured. Table 5 shows the results compared with the blank.

[Table] Example 5 100 parts by weight of calcium carbonate having an average particle size of 2 μm and 3 parts by weight of an aluminum compound were treated using a Henschel mixer. This was added to 100 parts by weight of granular polypropylene resin, and 100%
The mixture was kneaded and ground for a minute. Next, the pulverized material was heated to 200°C.
5.1Kg/cm ² , injection molded with mold sealing time of 30 seconds,
Izot impact value of the obtained molding liquid (with notch)
was measured. The results are shown in Table 6.

【table】

Claims (1)

[Claims] 1 General formula () [However, in the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ³ is R ⁴ or R ⁵ O-, and R ² , R ⁴ and R ⁵ are each an alkyl group having 1 to 22 carbon atoms. , cycloalkyl group, carbon number 3 to
22 alkenyl group, aryl group, aralkyl group, or alkylaryl group, in which R ² and R ³ may be the same or different, but one of R ² and R ³ has 8 or more carbon atoms. must be a substituent, m and n are the average values per molecule, m = 0.5
~2, n=0.3~2, m+n=0.8~2.7. ]
A surface modifier for a particulate material having a hydrophilic surface, characterized by containing at least one kind of aluminum compound represented by: