JPS6324516B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel aluminum compound and a surface modifier for particulate materials having a hydrophilic surface made of the compound. 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
method of treatment with a titanium-based compound having a partially hydrolyzable group (JP-A-50-145448), treatment of aluminum alcoholate of lower alcohol and higher alcohol or a part of aluminum alcoholate with a compound in which the group is acylated. (U.S. Pat. No. 3,905,936), a method of adding carboxylic acid to aluminum oxyoligomer,
A method of treating aluminum alcoholate with a compound substituted with phosphates or sulfonates (Japanese Patent Publication No. 44-17025), a method of treating aluminum alcoholate with a compound substituted with carboxylic acid, phosphates, sulfonates, etc. (Japanese Patent Publication No. 49-5924) ) etc. are known. All of these methods are effective in improving the dispersibility of fillers, etc., but these methods have relatively low effectiveness, are not easy to manufacture, tend to become solid, have low solubility, and require a large amount of solvent for processing. There were drawbacks such as the need for As a result of research to solve these drawbacks, the present inventors found that a new aluminum compound represented by the following formula shows high effectiveness in surface modification of fillers, etc.
Furthermore, they found that it is easy to make an oily substance, and that it is easy to manufacture and handle, and completed the present invention. The novel aluminum compound of the present invention has the general formula () [However, in the formula, R ¹ is a hydrogen atom or a carbon number of 1
to 6 alkyl group, R ² is an alkylaryl group having an alkyl chain of 10 to 14 carbon atoms, 10 carbon atoms
~14 alkoxy groups and alkyl groups having 1 to 4 carbon atoms, R ³ is a methyl group or phenyl group, R ⁴ is an alkenyloxy group or alkoxy group having 16 to 20 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. R ² and R ⁴ may be the same or different from each other, unless either R ² or R ⁴ has 8 or more carbon atoms. It won't happen. ] It is an aluminum compound shown by. The aluminum compound of the present invention will be described in more detail. First, in the aluminum compound of the present invention, R ¹ O- is a hydrophilic functional group (such as a hydroxyl group) or a group reactive with a hydrophilic surface such as a filler containing adsorbed water, while R ² and/or
R ⁴ is a group that imparts lipophilicity to the surface of this filler. Therefore, in the general formula ()
R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which has a short chain length, is selected because R ¹ O
- is required to have strong reactivity with hydrophilic surfaces such as fillers, and long-chain ones are unsuitable because they have a weak reaction pattern. From a practical standpoint, R ¹ is preferably a hydrogen atom, an isopropyl group, a sec-butyl group, an isobutyl group, or the like. Preferred functional groups for R ² in the general formula () include dodecylphenyl group, dodecyloxy group, methyl group, etc., and preferred functional groups for R ⁴ include 9-
Examples include octadecenyloxy group, octadecyloxy group, methyl group, and octylamino group. Since these are groups that impart lipophilicity to the surface of fillers and the like, at least one of R ² and R ⁴ must be a substituent having 8 or more carbon atoms. Examples of the novel aluminum compounds of the present invention include the following. (1) (4-Dodecylphenylsulfonate-
O) (9-octadecenyl 3-oxobutanoate-O ¹ , O ³ ) (2-propanolate)-aluminum(2) (4-dodecylphenylsulfonate-
O) Hydroxy-(9-octadecenyl 3-oxobutanoate-O ¹ , O ³ )-aluminum(3) (dodecyl sulfate-O) (9-octadecenyl 3-oxobutanoate-O ¹ , O ³ )
(2-Propanolate) - Aluminum (4) (4-Dodecyl phenyl sulfonate -
O) (9-octadecenyl 3-oxo-3-phenylpropionate-O ¹ , O ³ ) (2-propanolate)-aluminum(5) (methylsulfonate-O) (9-octadecenyl 3-oxobuta Noate - O ¹ , O ³ )
(2-Propanolate) - Aluminum (6) (4-Dodecyl phenyl sulfonate -
O) (2,4-pentanedionate-O,O ¹ )
(2-Propanolate) - Aluminum (7) (4-Dodecyl phenyl sulfonate -
O) (octyl 3-oxobutanamide-O ¹ ,
O ³ )(2-propanolate)-aluminum These aluminum compounds can be obtained, for example, by the following method. Aluminum alcoholates such as aluminum isopropoxide and aluminum butoxide are reacted with sulfonic acids and beta-keto esters. The amount of parent 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. Either of the following methods can be adopted: 1. Adding the organic medium directly to the filler, etc. system. Examples of fillers whose surfaces are modified by the aluminum compound of the present invention include calcium carbonate, kaolin, mica, aluminum hydroxide, titanium dioxide, silica, zinc yellow, red lead, iron oxide, zinc white, talc, and carbon. Inorganic or organic fillers and pigments such as, but not limited to, black, barium sulfate, magnesium carbonate, asbestos, glass fiber, phthalocyanine blue, quinacridone yellow, and Lake Red C can be mentioned; Substances with sexual 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, and soybean oil, synthetic drying oils such as dehydrated castor oil, maleated oil, styrenated oil, and vinyltoluenated oil, rosin, hydrogenated rosin, polymerized rosin, Natural and processed resins such as rosin esters, maleic resins, shellac, zein, synthetic resins such as phenolic resins, xylene resins, modified alkyd resins, polyamide resins, coumaron-indene resins, rubber derivatives such as chlorinated rubber, cyclized rubber, etc. Paints such as cellulose derivatives such as nitrocellulose and ethylcellulose, vehicles such as printing inks, solvents and diluents such as hexane, toluene, xylene, and cellosolve, polyethylene resins,
Examples include polymeric compounds for molding such as polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyester resin, polycarbonate resin, silicone resin, acrylic resin, fluororesin, 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 fillers modified by the present invention have various practical effects, such as (1) improved sharpness in paints and printing inks, (2) increased gloss and hiding power, ( 3) The mixing time during manufacturing is shortened, and for plastics, (1) the filling ratio of fillers, etc. can be increased, (2) fluidity is improved, and (3) the physical properties of the product are improved. (4) Effects such as shortening of mixing time can be obtained. These effects are due to the fact that the novel aluminum compound of the present invention has a group that easily reacts with hydroxyl groups on the surface of fillers, etc., while also having lipophilic groups bonded to stable sulfonic acid groups and chelate groups. This is thought to be due to improved miscibility with organic media or resins. The present invention will be explained in more detail with reference to Examples below. In addition, the compound number in the examples is the number mentioned in the above-mentioned example of the novel aluminum compound. 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 mole) of aluminum isopropoxide and 400 ml of toluene were added to the flask, and the mixture was stirred at room temperature and poured into the dropping funnel. 352 g (1 mol) of acetoacetic acid oleyl ester, then 327 g (1 mol) of dodecylbenzenesulfonic acid.
was dripped. After dropping, heat and reflux for 30 minutes.
The toluene and the produced isopropyl alcohol were distilled off under reduced pressure, and the structural formula 762 g of compound (1) was obtained as an oily liquid. Aluminum content; analytical value 3.64% theoretical value 3.54% Infrared characteristic absorption; (chelate C=O structure 1605cm ^- ) (SO ₂ structure 1125cm ^-1 , 1040cm ^-1 ) Example 2 Aluminum isopropoxide/toluene in Example 1 The procedure was exactly the same as in Example 1 until oleyl acetoacetate and dodecylbenzenesulfonic acid were added dropwise to the solution, and then 18 g of water was added.
(1 mol) was dissolved in 100 ml of isopropyl alcohol and added dropwise. After the dropwise addition was completed, it was heated to reflux for 30 minutes, and the toluene and produced isopropyl alcohol were distilled off under reduced pressure. 721 g of compound (2) as an oily liquid having the following properties were obtained. Aluminum content; analytical value 3.85% theoretical value 3.75% Infrared characteristic absorption; (OH structure 3400 cm ^-1 ) (Chelate C=O structure 1605 cm ^- ₊ ) (SO ₂ structure 1125 cm ^-1 , 1040 cm ^-1 ) Example 3 Aluminum iso A reaction was carried out according to Example 1 using 204 g (1 mol) of propoxide, 352 g (1 mol) of acetoacetic oleyl ester, and 266 g (1 mol) of dodecyl sulfate, and the structural formula 702 g of compound (3) as an oily liquid having the following properties were obtained. Aluminum content; analytical value 3.77% theoretical value 3.85% Infrared characteristic absorption; (chelate C=O structure 1605 cm ^-1 ) (O-SO ₂ -O structure 1060 cm ^-1 ) Example 4 Aluminum isopropoxide 204 g (1 mol) , 415 g of benzoyl acetic acid oleyl ester (1
The reaction was carried out according to Example 1 using 327 g (1 mol) of dodecylbenzenesulfonic acid, and the structural formula 826 g of compound (4) was obtained as an oily liquid. Aluminum content; analytical value 3.25% theoretical value 3.27% Infrared characteristic absorption; (chelate C=O structure 1605cm ^- ) (SO ₂ structure 1125cm ^-1 , 1040cm ^-1 ) Example 5 Aluminum isopropoxide 204g (1 mol), A reaction was carried out according to Example 1 using 352 g (1 mol) of acetoacetic acid oleyl ester and 96 g (1 mol) of methanesulfonic acid, and the structural formula 532 g of Compound (5) was obtained as a viscous liquid having the following properties. Aluminum content; analytical value 5.02% theoretical value 5.08% Infrared characteristic absorption; (chelate C=O structure 1605 cm ^- ) (SO ₂ structure 1140 cm ^-1 , 1050 cm ^-1 ) Example 6 Aluminum isopropoxide 204 g (1 mol), 2,4-pentanedione 100g (1 mol),
A reaction was carried out according to Example 1 using 327 g (1 mol) of dodecylbenzenesulfonic acid, and the structural formula 511 g of semi-solid compound (6) having the following formula was obtained. Aluminum content; analytical value 5.52% theoretical value 5.64% Infrared characteristic absorption; (chelate C=O structure 1590 cm ^- ) (SO ₂ structure 1125 cm ^-1 , 1030 cm ^-1 ) Example 7 Aluminum isopropoxide as in Example 1 204g (1 mol), acetoacetic caprylamide
213g (1 mol), dodecylbenzenesulfonic acid
Using 327 g (1 mol), the reaction was carried out according to Example 1, and the structural formula 624 g of semi-solid compound (7) having the following formula was obtained. Aluminum content; analytical value 4.25% theoretical value 4.33% Infrared characteristic absorption; (NH structure 3320 cm ^-1 ) (Chelate C=O structure 1600 cm ^-1 ) (SO ₂ structure 1125 cm ^-1 , 1040 cm ^-1 ) Example 8 Present invention In order to examine the sharpness improvement effect of the new aluminum compound in printing ink, 5% of the aluminum compound was added to a commercially available ink, kneaded, and then a color development test was conducted. Visual comparison with a blank to which no aluminum compound was added revealed a clear improvement in sharpness. This effect also appears 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 1 shows the reduction rates of X, Y, and Z values relative to the blank when an aluminum compound was added in black ink.

[Table] Example 9 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 2. Γ Samples used in the 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 10 In order to examine the viscosity reducing effect of the aluminum compound of the present invention, 0.2 g of the aluminum compound,
10 g of calcium carbonate and 10 g of liquid paraffin were thoroughly mixed in a mortar, and the viscosity at 25°C was measured. Table 3 shows the results compared with the blank.

【table】

[Table] Example 11 100 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 molded plate (with notch)
was measured. The results are shown in Table 4.

【table】

Claims (1)

[Claims] 1 General formula () [However, in the formula, R ¹ is a hydrogen atom or a carbon number of 1
to 6 alkyl group, R ² is an alkylaryl group having an alkyl chain of 10 to 14 carbon atoms, 10 carbon atoms
~14 alkoxy groups and alkyl groups having 1 to 4 carbon atoms, R ³ is a methyl group or phenyl group, R ⁴ is an alkenyloxy group or alkoxy group having 16 to 20 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. R ² and R ⁴ may be the same or different from each other, unless either R ² or R ⁴ has 8 or more carbon atoms. It won't happen. ] An aluminum compound represented by 2 General formula () [However, in the formula, R ¹ is a hydrogen atom or a carbon number of 1
to 6 alkyl group, R ² is an alkylaryl group having an alkyl chain of 10 to 14 carbon atoms, 10 carbon atoms
~14 alkoxy groups and alkyl groups having 1 to 4 carbon atoms, R ³ is a methyl group or phenyl group, R ⁴ is an alkenyloxy group or alkoxy group having 16 to 20 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. R ² and R ⁴ may be the same or different from each other, unless either R ² or R ⁴ has 8 or more carbon atoms. It won't happen. ] A surface modifier for a particulate material having a hydrophilic surface, characterized by comprising at least one of the aluminum compounds shown below.