JPS63268785A - Inorganic surface modifying agent - Google Patents

Abstract

PURPOSE:To obtain the titled modifying agent, containing a reaction product of a specific tetraalkyl titanate with an aspartic acid derivative, having excellent dispersibility in organic media and water resistance, high safety, rich in stability and widely applicable to coatings, adhesives, medicines, etc. CONSTITUTION:The aimed modifying agent, containing a reaction product obtained by reacting (A) 1mol. tetraalkyl titanate expressed by the formula (R1O)4Ti (R1 is 1-8C alkyl or 5-7C cyclic alkyl) (e.g. tetramethyl titanate) with (B) an aspartic acid derivative expressed by the formula (R2 and R3 are 6-22C alkyl or alkenyl) (e.g. beta-2-ethylhexyl N-2-ethylhexyl aspartate) in a molar amount of 0.5-3.5 times based on the component (A) and capable of improving deterioration in processability, etc., even by blending in a large amount with plastics, since wettability and dispersibility in organic media are good. Furthermore, films having excellent strength and gloss are imparted to coatings without increasing viscosity thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a tetraalkyl titanate represented by the general formula (1) and a tetraalkyl titanate represented by the general formula (1), and a tetraalkyl titanate represented by the general formula (2)
) Regarding an inorganic modifier characterized by using at least one of the reaction products obtained by reacting aspartic acid with a conductor, the inorganic modifier was repurchased from Kinei 1 JliK, and the inorganic modifier is a paint, It can be applied to a wide range of fields such as plastics, adhesives, etc.

(R1O)4Ti...(1) R2NHC
HOOH...(2)C)12COOR5 (However, R1 is an alkyl group having 1 to 8 carbon atoms or 5 carbon atoms
~7 cyclic alkyl group, R2 and rL5 each have 6 carbon atoms
~22 alkyl or alkenyl groups, conventionally used in various fields such as multi-plastics, adhesives, paints, adhesives, adhesives, etc. to impart strength and rigidity, improve heat resistance and weather resistance, improve color tone and cure Calcium carbonate, Merck, kaolin, silica, alumina, titanium dioxide, zinc oxide, aqueous aluminum, magnesium hydroxide, and bethonite are used for the purpose of improving properties, reducing costs by increasing volume, or adding new functions such as conductivity. It is difficult to uniformly disperse inorganic fillers such as t-glass, red iron, gunji, chromium hydroxide, ferrite, metal powder, metal fibers, glass fibers, and asbestos in organic media such as paint, rubber, etc. However, it is not possible to obtain the desired composite material.

Therefore, in practice, volatile 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 salt, alkylbenzene sulfone #l salt, fatty acid salt, dialkyl sulfonate salt, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, alkyl quaternary ammonium salt, lecithin, alkyl betaine, etc. surfactant, or polystyrene, polypropylene,
Polyester, styrene-methacrylic acid corimer,
One polymer such as styrene-acrylic acid copolymer, silane type, or titanium type copolymer! Ring agents and the like are known.

Such inorganic surface modifiers have minerals (υ) that exhibit a high dispersion effect with the addition of a small amount (2) that reduce viscosity during processing or improve physical properties such as rigidity (3) that adsorb onto the filler surface. It is required to have properties such as being strong, causing desorption, and (4) being highly adaptable to various fillers.

However, in conventional inorganic surface modifiers, for example, surfactants such as stearates cause pluming when added in large amounts to improve dispersibility7?1. ! However, it is often observed that undesirable phenomena such as a decrease in water repellency and weather resistance of the final product occur, and that if the amount added is too small, the desired sufficient modifying 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 serves as the dispersion medium, causing detachment from the surface, making it difficult to use in paints, etc. In this case, there are inconveniences such as restrictions on the organic solvent. Also, silane-based power, 7'
In IJing agents, although they react with the surface functional groups of silicon-containing fillers such as glass and silica to achieve an excellent surface modification effect, they also react with other fillers, such as fillers such as calcium carbonate and magnesium oxide, or It has been pointed out that the target fillers lack versatility, such as not exhibiting the expected modification effect on inorganic pigments such as red iron and titanium white. In addition, titanium-based strength and f-ring agents are surface modifiers that are widely applicable to resins and inorganic fillers, but one type of titanium, tetraalkyl titanate, rapidly hydrolyzes and is removed when it encounters water or moist air. It is inconvenient to handle. Therefore, compounds in which a part of the alkyl group has been replaced with higher fatty acids, sinite esters, pyrosinba esters, etc. are generally used, but as their uses have diversified, they have become more safe and have a higher surface resistance. There is a growing demand for compounds with excellent reforming effects.

Problems to be Solved by the Present Invention As mentioned above, inorganic surface modifiers for plants have been developed, but they are lacking in dispersibility in organic media, water resistance, and versatility of the target inorganic materials. The reality is that no suitable inorganic surface modifier has been found.

Means for Solving the Problems In view of the above circumstances, the present inventors conducted intensive research and found that a tetraalkyl titanate represented by the general formula (1) as an inorganic surface modifier, and 0.5-3 for
．． The reaction product obtained by reacting 5 times the molar amount of Asuno's ginate brocade conductor represented by the general formula (2) has better dispersibility in organic media and water resistance than conventional titanate-based surface modifiers. The present inventors have discovered that the present invention is a compound that is applicable to a wide range of properties and target inorganic substances, is highly safe and stable, and has a surface-modifying effect.

(R,0)4Tl...(1) R2NHCHCO
OH...(2) cu2cooR5 (However, R1 is an alkyl group having 1 to 8 carbon atoms, or 5 carbon atoms
~7 cyclic alkyl group, Machi and R, each have 6 to 2 carbon atoms
Examples of the tetraalkyl nathanates represented by the above general formula (1) include tetramethyl titanate, tetraethyl titanate, tetrainglopyrtetanate, tetrabutyl titanate, tetraoctyl titanate, and Examples include tetracyclo(butyl titanate) and tetrahexyl titanate, with tetrainglovir titanate and tetrabutyl titanate being preferred from the viewpoints of reactivity and economy.

Further, the aspartic acid derivative represented by the above general formula (2) can be easily obtained by a known reaction using maleic anhydride as a starting material.

An example of the method is the method described in JP-A-59-176377;
) The method for synthesizing the aspartic acid derivative represented by () is not particularly specified, and it may be synthesized by other methods without any problem.

A typical example of the aspartic acid derivative represented by the above general formula (2) obtained by these methods is N-2-ethylhexyl aspartic acid-β-2-
Ethylhexyl ester, N-2-ethylhexyl aspartic acid-β-lauryl ester, N-lauryl asharachic acid-β-lauryl ester, N-lauryl asparagic acid-β-myristyl ester, N-lauryl asunolachic acid-β- Noglymicyl ester, N-palmityl acetate, inic acid β-palmityl ester,
N-stearylasunoragic acid-β-palmityl ester, N-stearylasufu 5! Examples include tR-β-stearyl ester.

The reaction product of the tetraalkyl titanate represented by the general formula (1) and the aspartic acid derivative represented by the general formula (2) used in the present invention is generally produced by the following method. That is, asAragine [vj derivative 0,5 to a5 mole is used per mole of tetraalkyl titanate,
A viscous liquid, wax or powder is obtained by reacting without a solvent or in a suitable solvent such as isopropyl alcohol at room temperature or at a temperature below 100°C for several hours, and then distilling off the alcohol produced and the solvent used. Obtained as a substance. When used as a surface modifier for inorganic fillers, the substance obtained by the above method may be used as it is, but it may also be used in the reaction solution before distilling off the alcohol or solvent.

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 inorganic filler's planting, specific surface area, and amount of water bound therein, but it ranges from 0.05 to 0.05 to the amount of water bound to the inorganic filler to be filled. 20% by weight, preferably 0.2-10% by weight. In addition, surface treatment methods include (1) a method of adding the present modifier to the filler as it is and co-pulverizing it using a crusher such as a Schichenschel mixer, Elji-Rumill, or Atomide colloid mill; and (2) a method of adding an appropriate M machine solvent. Methods include adding the modifier together with the filler, stirring, and removing the solvent after mixing.(3) Adding the present modifier directly into the mixture of the organic medium and filler with vinegar and mixing with a heated roll etc. .

Effects of the Invention The surface modifier of the present invention, the reaction product of the tetraalkyl titanate represented by the general formula (1) and the aspartic acid derivative represented by the general formula (2), is characterized by various inorganic It has a wide range of applications for fillers.

For example, it can be applied to an extremely wide range of inorganic fillers such as calcium carbonate, titanium dioxide, kaolin, Merck, silica, alumina, magnesium hydroxide, ferrite, chromium disilonide metal powder, metal fiber, glass fiber, and asbestos. .

Further, the inorganic filler surface-modified with the surface-modifying agent of the present invention may be natural rubber or styrene-tutadienedimu,
Synthetic rubbers such as urethane rubber, polyolefin resins such as I-lyethylene and polypropylene, tetraacrylonitrile, polygetadiene, copolymers of butadiene and acrylonitrile, ethylene and monomers copolymerizable with it, such as propylene, l-butene, vinyl acetate, Copolymers with maleic anhydride, polycarbonate-fats, phenoxy resins, polyvinyl chloride, co-arrangements of vinyl chloride and vinyl acetate or other vinyl esters, polyvinyl acetate, polyvinyl acetal, polyvinylidene chloride, It can be mixed with various organic media such as copolymers of vinylidene chloride, vinyl chloride, and 7/IJ acid, epoxy fat-resistant resins, phenol 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 a large amount of inorganic pigment is added to the glass material, the decrease in workability and the brittleness of Product A are significantly improved compared to when filled with an inorganic substance treated with stearic acid. However, the increase in viscosity is negligible, making it easy to apply and providing a coating film with extremely good strength and gloss.

(11) When an inorganic filler treated according to the present invention is used as a ceramic raw material, it is wetted even in a green tape, for example, and the fractional property is very good. - can be reduced;
As a result, a surface product with small shrinkage changes due to firing can be obtained.

As described above, the inorganic filler whose surface has been modified by the surface modifying agent of the present invention can be applied to a wide range of fields such as gelaste, paint, rubber, etc., as well as medical drainage, cosmetics, etc. I can do it.

Next, the content of the present invention will be explained in detail by giving examples. Similarly, the following examples do not limit the scope of the present invention,
It is provided to more clearly illustrate the nature of the invention.

Synthesis Example 1 In a 100d round bottom flask equipped with a stirrer and condenser, N-2
- Add 35.79 (0.1 mol) of ethylhexyl aspartate β-2-ethylhexyl ester and 3011 L/l of inoprobil alcohol, and stir 14.2 y (0.05 mol) of tetraisoglobil titanate. The mixture was gradually added at room temperature while reacting for 6 hours under reflux.

Isoprozyl alcohol was distilled off from this reaction solution under reduced pressure to obtain a pale yellow viscous liquid, which was designated as Sample 1 and shown in Table 1.

Synthesis Example 2~lO Same as Synthesis Example 1, N-2-ethylhexyl aspartic acid-β-myristyl ester 66.2,! i'(α1
5 mol) and 50 g of xylene in a T-7 flask, and add 14.2 g (α05M) of tetraisoglobil titanate).
The mixture was gradually added while stirring without stirring, and the mixture was reacted at 100° C. for 6 hours. From this reaction solution, xylene and by-produced tutyl alcohol t-m were removed under reduced pressure to obtain a pale yellow waxy substance. This one was named Su/Guru 2.

Furthermore, reaction products of each aspartic acid enzyme derivative and isoprobyl titanate were obtained by similar operations and are shown in Table 1 as Temple Tomb 3-1O.

Synthesis Example 11 Tetraptyl titanate (substituent for 9-tetrainoglovir titanate used in Synthesis Example 1) 17.0 g (0.05 mol) In,N-octyl aspartic acid β-octyl ester for t-35.71 :0.15 mol) in a toluene solvent at 100°C for 8 hours.

By shrinking the reaction solution by 1 m, a pale yellow wax-like substance was obtained. This was designated as Sample 11 and shown in Table IK.

Synthesis Example 12 Tetraisoglovir titanate (tetraisoglovir titanate) was added to the same apparatus as Synthesis Example 1.
14.277 (0.05M) with N-2-ethylhexyl asno and lyic acid β-octyl ester 17,9
g (0,05M > t-Heating with stirring (80℃
) A pale yellow viscous liquid was obtained by distilling off the by-produced pyral alcohol from the 0 reaction solution which was added gradually in the absence of a solvent and reacted for 8 hours.This was designated as sample 12 and is shown in Table 1. Ta.

Example 1 The surface modifier L0,5+ shown in Table 1 was mixed with toluene 120-
Calcium carbonate (Nitto Powdered Chemical (JLL)) is dissolved in
l) N5-100) 200 and Ft- were added and stirred. After distilling off the toluene, it was sufficiently dried in a straight dryer at 50° C. to prepare a sample. Next, a cylindrical glass tube (45■φ×
100g of diocterphthalate) was added to the above-obtained surface-saturated calcium carbonate under low-speed stirring (stirrer: Shinshu Kagaku (not yet) 600G), and then
The mixture was stirred at high speed for 10 minutes. Next, the viscosity was measured using an Ill viscosity needle to evaluate the surface modification effect. In addition, as a comparative example, untreated, polyoxyethylene oleoyl ether, stearyl trimethyl ammonium chloride and titanate-based strength, 7# ring agent bis (dioctyl pyrophosphate) oxyacetate titanate (KR-1
Table 1 shows the results when treated with 388).

As is clear from Table 1, the surface modifier of the present invention had a significant viscosity reducing effect compared to the comparative example.

Example 2 The same treatment as in Example 1 was performed except that calcium carbonate in Example 1 was replaced with titanium dioxide, and the contact angle of the treated titanium dioxide was measured. The results are shown in Table 2. To measure the contact angle, a test piece was prepared by pressing powder of approximately 150 Da for 3 minutes at a pressure of 100 kl/cyt.A certain amount of water droplet was dropped onto this test piece, and the test piece immediately after dropping was compared with the water droplet. The contact angle was calculated.

Table 2-1 Kao Atlas Pere, Ri, '1.0T-P Medium 2 Tetrisof O lobilpis (dioctyl phosphite) nathanate As is clear from Table 2, titanium dioxide modified with the surface modifier of the present invention It can be seen that the contact angle of is high, indicating that it is hydrophobic.

Example 3 Magnetic paint components having the following composition were mixed and dispersed in a paint shaker for 20 hours to obtain 14 g of magnetic paint t-a, which was coated on an aluminum plate to a dry coating thickness of 6 μm and dried. Running the dispersive line of F.20s 311: Gidenken a
Observe with a mirror and the results are shown in Table 3. Also shown in the same table are the results of treatments with untreated stearic acid, lecithin, and nonylphenyl phosphorus esters as comparative examples.

r-Fe2O2 1.00M polyurethane 15 parts hardening agent
0.75 parts Surface modifier 1 part! ! ! 3 As is clear from Table 3, the submagnetic powder modified with the surface modifier of the present invention had better dispersibility than the comparative example.

Claims (1)

[Claims] A tetraalkyl titanate represented by general formula (1),
Inorganic surface modifier (R_1O) containing at least one reaction product obtained by reacting 0.5 to 3.5 times the molar amount of an aspartic acid derivative represented by general formula (2) with respect to this. ＿4Ti...(1)▲There are mathematical formulas, chemical formulas, tables, etc.▼...(2) (However, R_1 has 1 carbon number
~8 alkyl group or a cyclic alkyl group having 5 to 7 carbon atoms,
R_2 and R_3 each represent an alkyl group or an alkenyl group having 6 to 22 carbon atoms).