JPS60217270A - Inorganic surface modifier - Google Patents

Abstract

PURPOSE:The titled modifier, containing a reaction product obtained by reacting an aluminum trialkoxide with an N-acyl amino acid in a specific proportion, having a wide range of application, high safety and stability, and usable for fillers in composite materials. CONSTITUTION:A modifier obtained by reacting (A) an aluminum trialkoxide, preferably a compound of the formula (RO)3Al (R is 1-8C alkyl or 5-7C cyclic alkyl) with (B) an N-acyl amino acid, e.g. N-acetylglycine, in a molar amount of 0.5-2.5 times that of the compound (A) if necessary in a solvent, e.g. toluene, at ordinary temperature -100 deg.C for several hours. Preferably, 0.2-10wt% resultant modifier is added to an inorganic filler, e.g. calcium carbonate or TiO2, to modify the surface thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an inorganic surface modifier containing a reaction product of aluminum trialkoxide and N-acylamino acid.

'In recent years, in the production of composite plastics, paints, adhesives, rubbers, etc., it has been used to provide strength, rigidity, and adhesion, improve heat resistance and weather resistance, and improve color tone and viscosity characteristics.'Increase; In order to reduce costs due to quantity, and to add new functions such as conductivity, competition is increasing the use of inorganic fillers such as calcium carbonate, titanium dioxide, Merck, silica, ferrite 1 metal powder, metal fibers, and glass fibers. Composite materials made by mixing and dispersing in organic media such as resins and rubbers are used. Since it is covered, it has poor lipophilicity, and it is difficult to uniformly disperse it in an organic medium such as resin or rubber as it is, making it slow to obtain the desired composite material.

Therefore, in practice, various surface modifiers are used for the purpose of improving the wettability of the filler surface and improving the dispersibility.

Typical examples include dodecyl sulfate ester, argylbenzene sulfonate.

Surfactants such as fatty acid salts, dialkyl sulfosuccinic acid ester salts, polysecondary xyethylene sorbitan fatty acid esters, glycerin fatty acid esters, alkyl quaternary ammonium salts, lecithin, alkyl betaines, or polystyrene, polyglobylene, /lyester, styrene.
Coupling agents such as methacrylic acid-based cosf l)mers, styrene-acrylic acid-based colimers, silane-based, titanium-based, or aluminum-based coupling agents are known.

Such inorganic surface modifiers have the following properties: (1) exhibits a high dispersion effect even when added in a small amount; (2) reduces viscosity during processing or improves physical properties such as rigidity; and (3) adsorbs onto filler surfaces. It has properties such as strong compatibility with a variety of fillers, and (4) high adaptability to various fillers.

However, in conventional inorganic surface modifiers, if a large amount of surfactants such as stearate is added to improve dispersibility, it may cause pluming or reduce the water repellency and weather resistance of the final product. It is often seen that undesirable phenomena such as these occur, and that if the amount added is too small, the desired sufficient modification effect cannot be obtained. In addition, when surface modification is performed with a polymer such as polystyrene, the polymer coating the surface swells and dissolves in the organic solvent that acts as a dispersion agent, causing desorption from the surface, making it unsuitable for use in paints, etc. This causes inconveniences such as restrictions on organic solvents. In addition, silane coupling agents react with the surface functional groups of silicon-containing fillers such as glass and silica, and exhibit excellent surface modification effects, but other fillers, such as calcium carbonate and magnesium oxide, It has been pointed out that the target fillers lack versatility, as they do not exhibit the expected modification effect on fillers or inorganic pigments such as red iron oxide and titanium white. In addition, titanium-based coupling agents are surface modifiers that are widely applicable to resins and inorganic fillers, but one type of titanium coupling agent, tetraalkyl titanate, rapidly hydrolyzes and is removed when it encounters water or moist air. It is inconvenient to handle. Therefore, compounds in which part of the alkyl group is substituted with higher fatty acids, sinosinates, birosinate diesters, etc. are generally used. Aluminum-based cutting agents also contain some of the alkyl groups of aluminum trialkoxide. fatty acids,
Compounds substituted with phosphate esters, phosphoric acid esters, phosphoric acid esters, sulfonic acid esters, etc. are generally used, but as their uses have diversified, they have become safer and have better surface-modifying effects. Increasingly, people are becoming more aware of the quality of their products and hardware.

) In view of the above circumstances, the present inventor conducted research on the lead content of a new surface modifier that has the characteristics required of an inorganic surface modifier as described above, and found the following results: 1. A new reaction product of aluminum 4 minium tria-rukoxide and N-acyl amino acid is more applicable and has a wider range of use than the conventional aluminum and miniram-based surface modifiers, and has been shown to be safer and more stable. Moreover, it has now been found that an excellent inorganic filler can be obtained by using at least two of these compounds as a surface modifier for inorganic textiles, and this book, O who completed the invention 2. That is, the present invention uses aluminum trialkoxide (5
) and 0.5 to 2.5 times the molar amount of N-acylamino acid to the reaction product, which is used to surface-modify the inorganic substance.

The amino acid components of the N-acyl amino acids used in the raw materials of the present invention include glycine, alanine, β-alanine, phenylalanine, leucine, isoleucine, α-aminobutyric acid, β-aminobutyric acid, γ-aminobutyric acid, ε-aminobutyric acid, Tyrosine.

Tryptophan, histidine, methionine, cysteine, cystine, proline, oxyproline.

Serine, threonine, Asno-matric acid, Asno-9-ragin, glutamic acid, glutamine, ornithine.

Examples of the acyl group include lysine, N-dimethyllysine, and arginine. Examples of the acyl group include aliphatic acyl having 2 to 22 carbon atoms, group acyl, cycloaliphatic acyl, aromatic acyl, and the like.

Specific examples of these N-acylamino acids include N-
Acetylglycine, N-caproylglycine, N-myri-stoylglycine.

N-lauroylalanine, N-hardened beef fatty acid reed (6
) Lualanine, N-lauroyl-β-alanine, N-acetylvaline, N-benzoylvaline, N-oleoyl-noline, N-caproylleucine, N-oleoyl-β
-aminobutyric acid, N-noglumitoyl-r-aminobutyric acid,
N-coyl-8-aminocaproic acid, N-lauroylserine, N-cagroylthreonine, N-acetylmethionine, N-lauroylmethionine, N-acetylcysteine, N-benzoylphenylalanine, N-acetyltyrosine.

N-lauroylzololine, N-lauroyltryptophan *N-2 uroylhistidine, N-oleoyl aspartic acid, N-cyclohexanecarbic acid acylasuno-yalaic acid, N-lauroylglutamic acid, N-cocoylglutamic acid, N-instearoylglutamine [,
N-hardened beef tallow fatty acid acylglutamic acid I N"-cagroyl ornithine, Na-oleoyl lysine y6-myristoyl lysine, N"N'-cicapryloyl lysine, N6-2 uroyl Na, N"-tumethyl lysine N
11-myristoylNaNaN") rimetherlysine, and mixtures thereof.

Note that these N-acyl amino acids may be optically active or racemic. In addition, the other raw material, aluminum trialkoxide, has the general formula % (% formula %) (wherein R is a straight chain or branched alkyl group having 1 to 8 carbon atoms or a cyclic alkyl group having 5 to 7 carbon atoms. For example, methyl, ethyl, n and isozolobyl, -class and secondary butyl, pentyl and cyclopentyl, hexyl and cyclohexyl, octyl groups, etc.), and aluminum triisopropoxide is preferred from the viewpoint of reactivity and economy. is preferred.

The reaction product of N-acylamino acid and aluminum trialkoxide used in the present invention is generally produced by the following method. That is, aluminum trialkoxy P1
Using 0.5 to 2.5 moles of N-acyl amino acid 'e per mole, without solvent or in a suitable solvent such as toluene,
By reacting for several hours at room temperature or below 100°C, and then distilling off the alcohol produced and the solvent used, a viscous liquid, wax, or powder material is obtained. When used as a surface modifier for an inorganic filler, the substance obtained by the above method may be used as it is, but it may also be used in a reaction solution in which the alcohol or solvent is distilled off. Moreover, there is no problem in using it in combination with conventionally known surface modifiers. The amount of the surface modifier used in the present invention varies depending on the type of inorganic filler, specific surface area, and amount of water bound therein, but it is 0.05 to 20% relative to the inorganic filler to be filled. % by weight, preferably from 0.2 to 10% by weight. In addition, surface treatment methods include (1) Adding the present modifier to the filler as it is, using Henschel mixer, Solmill, and Atomide.

Method of co-pulverization using a crusher such as a colloid mill (2)
Method of adding the filler together with the filler into a suitable organic solvent, stirring, and then removing the solvent (3) Adding the present modifier directly into the mixture of the promoter medium and the filler and mixing with a heated roll, etc. Examples include methods.

” The surface modifier of the present invention, the reaction product (9) of aluminum trialkoxide and other N-acyl amino acids, has a wide range of applications.

For example, calcium carbonate, titanium dioxide, and kaolin.

It can be applied to extremely wide range of inorganic fillers such as talc, silica, ferrite, chromium dioxide, metal fibers, glass fibers, and asbestos. The inorganic filler surface-modified by the surface-modifying agent of the present invention is natural rubber, synthetic rubber such as styrene-butadiene rubber, urethane rubber, or polyethylene.

Dilyolefin resins such as polypropylene: I-lyacrylonitrile, polybutadiene, copolymers of butadiene and acrylonitrile, copolymers of ethylene and monomers copolymerizable therewith, such as zolopylene, 1-butene, vinyl acetate, maleic anhydride, polycarbons nate resins, phenoxy resins, polyvinyl chloride, copolymers of vinyl chloride and vinyl acetate or other vinyl esters, polyvinyl acetate.

I libinyl acetal, f! vinylidene chloride, a copolymer of vinylidene chloride, vinyl chloride and acrylic acid,
It can be mixed with various organic media (10) such as epoxy resins, phenolic resins, silicone resins, and polyester resins.

Inorganic substances surface-treated with the modifier of the present invention have extremely good wettability and dispersibility in organic media.

Therefore, even if large amounts of inorganic pigments are added to plastics, the decrease in processability and the brittleness of the product are significantly improved compared to when filled with inorganic substances treated with stearic acid, etc. It is easy to apply because there is almost no increase in viscosity, and a coating film with extremely good strength and gloss can be obtained.

In addition, the reaction product of aluminum trialkoxide and N-acylamino acid of the present invention has almost no irritation to the skin, and even if it is decomposed by heat, light, water, etc., it can be used as a cosmetic material with aluminum hydroxide. It is an extremely safe compound because it is an N-acyl amino acid.

Hereinafter, -Synthesis #I,) Lσ + color A series of its I tea 9 pieces:i
Synthesis Example 1 Put aluminum triisopropoxide 10.2.9 (0.05 mol) and toluene 50I into a 2001 round bottom flask with a stirrer and cooling pipe material, and add N-lauroylmethionine 16.6F ( 0.05 mol) was gradually added at room temperature while stirring, and after stirring at room temperature for 6 hours, 1. The reaction was continued under heating (60° C.) for an additional 3 hours. Toluene and by-produced isoglopanol were distilled off from the reaction solution under reduced pressure to obtain colorless and transparent crystals. This product was designated as sample A1.

Synthesis Example 2 In the same manner as in Synthesis Example 1, 10.2.9 (0.05 mol) of aluminum triisopropoxide and 50.9 of toluene were placed in a flask, and 1
0.4# (0.05 mol) was gradually added at room temperature while stirring, and after stirring at room temperature for 6 hours, the mixture was heated (60
The reaction was continued at 10°C. A white powder was obtained by distilling off toluene and by-produced isoglono f-nol from the reaction solution under reduced pressure. This product was designated as sample A2.

Synthesis Examples 3 to 14 In the same manner as in Synthesis Example 1, 10.2II (0.05 mol) of 1-aluminum triisozolopoxide and 50 g of toluene were placed in a flask, and 19.9. 9 (0.10 mol) was gradually added with stirring, stirred at room temperature for 5 hours, and then heated for an additional 3 hours (60 mol).
The reaction was continued at 10°C. Colorless and transparent crystals were obtained by concentrating the reaction solution. This product was designated as sample shop 3.

Furthermore, reaction products of various N-y)v amino acids and aluminum triisopropoxy F were obtained by similar operations. These samples were designated as samples A4 to A14 and are also shown in Table 1.

Synthesis Example 15 12.3 g of aluminum tri-5ea-butoxide was used in place of the aluminum triisopropoxide used in Synthesis Example 1.
Using (0.05 mol), 20.7 #t of N-isostearoylglutamic acid was gradually added under stirring and heating (50° C.) in the absence of solvent and allowed to react for 6 hours. By concentrating the reaction solution, a pale yellow viscous liquid was obtained. This was designated as sample A15.

(13) Table 1 *2 Reaction product obtained by removing the solvent after the reaction Example 1 The modifier shown in Table 1 was dissolved in 100 ag of J iisozorono'Pnol, and calcium carbonate was added therein. (Nitto Funka Co., Ltd. MS-100) 100# was added and stirred. After distilling off the isopro/IP norwon, heat (50°C
) and was thoroughly dried in a vacuum dryer and used as a sample. Next, turbine oil (class 1, ISOV G32) 100.9 was placed in a cylindrical glass tube (45 mφ x 120 m), and the above-mentioned surface-treated calcium carbonate was added to it under low speed stirring using a stirrer (600G, Shinto Kagaku Co., Ltd.). After the addition, the mixture was further stirred at high speed for 10 minutes. Next, the viscosity was measured using an E-type viscometer to evaluate the surface modification effect. In addition, as a comparative example, the results of untreated cases and cases treated with polyoxyethylene oleoyl ether, stearyltrimethylammonium chloride, and aluminum-based coupling agent, acetalkoxyaluminum diisozolopyre) (AL-M) are also shown in Table 2. Indicated.

Example 2 Magnetic paint components having the following composition were mixed and dispersed in a paint shaker for 48 hours to prepare a magnetic paint, which was coated on an aluminum plate to a dry film thickness of 6 μm and dried. The dispersion state of r-Fe20s was observed using a scanning electron microscope. The results are shown in Table 3. In addition, as a comparative example, the results of untreated samples and those treated with stearic acid, lecithin, and nonylphenyl phosphate ester are also shown in the same table.

r-Fe20. 100 parts by weight Vinyl chloride-vinyl acetate copolymer 20 l Methyl ethyl ketone 100 I Toluene 100 # Surface modifier 2N (17) Example 3 Surface modifier of the present invention 1.5 II in chloroform 20011
After dissolving, r-Fe2es 100 Ji' was added and mixed with stirring for 30 minutes. Chloroform was distilled off under reduced pressure and heating (500Q).Furthermore, it was thoroughly dried in a vacuum dryer at 50°C, and the surface treatment was carried out. This treatment r-F
50cc of the following combination of e20s and nylon 6 was manufactured by Toyo Seiki Seisakusho. Inside the gelasto mill mixer (temperature 260
℃), and after cross-mixing, processing characteristics such as maximum torque were measured, and the results are shown in Table 4. In addition, as a comparative example, untreated cases and cases treated with lecithin were also conducted.

Nylon 6 12 parts by weight r-F’520388 # Surface modifier 1.31

Claims (3)

[Claims] (1) An inorganic surface modifier containing a reaction product obtained by reacting aluminum trialkoxide with 0.5 to 2.5 times the molar amount of N-acylamino acid. (2) Aluminum trialkoxide is represented by the general formula % (wherein R represents an alkyl group having 1 to 8 carbon atoms or a cyclic alkyl group having 5 to 7 carbon atoms). ) The inorganic surface modifier described in section 2. (3) The acyl group of the N-acylamino acid has 2 to 2 carbon atoms.
The inorganic surface modifier according to claim (1)]J, which is an aliphatic acyl, aromatic acyl or alicyclic acyl group of No. 22.