JPH0618930B2 - Titanium coupling agent - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to paints, plastics, adhesives, magnetic tapes,
In various composite material systems such as toner, in order to modify the surface of the filler such as inorganic powder or fiber to improve the function, stability, dispersibility, workability, etc. of the composite material using the filler. The present invention relates to a coupling agent of the present invention, and more particularly to improvement of a titanium-based coupling agent obtained by reacting an orthotitanate ester with a carboxylic acid.

2. Description of the Related Art Conventionally, silane-based coupling agents have been most widely used as coupling agents. However, the silane-based coupling agent has a drawback in that the object to be modified is limited to those containing silicon, such as glass and silica, and the applicable range is narrow.

In addition to silane coupling agents, titanium coupling agents are also known. Generally, the titanium-based coupling agent is more effective than the silane-based coupling agent for more kinds of fillers, and has been particularly attracting attention in recent years.

Titanium coupling agents have the general structure _{(R 1 O-) a Ti (} -R 2) be one represented by _b, in the formula, R ₁ is an alkyl group, R ₂ is an acyl group, a phenoxy group , An alkoxy group or a phosphite group. Also, a indicates a number of 1 to 3, and b indicates a number of 1 to 5. The titanium-based coupling agent is obtained by reacting a orthotitanate ester and a carboxylic acid, as its specific example, the structural formula (CH ₃₎ represented by _{2 CHO-Ti (-OCOC 17 H} 35) 9 Isopropyl triisostearoyl titanate.

The titanium-based coupling agent can be used, for example, as a modifier for a filler for plastics and paints, a toner, a magnetic tape, a conductive coating agent, a modifier for a magnetic material or a conductive material in a plastic magnet, etc. It has applications, and further has the effect of improving the processability and impact resistance of the compound containing a large amount of filler, improving the affinity between the filler and the vehicle, preventing powder blocking, and improving dispersibility.

Problems to be Solved by the Invention However, these titanium-based coupling agents have a modifying effect on more substances than silane-based coupling agents, but carbon black, carbon fiber, etc.
It has almost no effect of modifying the carbon-based filler, which is highly versatile. Also, the effect of modifying the magnetic powder and the metal powder was not sufficient.

The present invention has been made in view of such circumstances, and is a titanium-based coupling agent, which is particularly excellent in the effect of modifying a carbon-based filler, and is sufficiently modified even in a magnetic powder or a metal powder. It is intended to provide a titanium-based coupling agent having an effect.

Means for Solving the Problems The present invention provides a titanium-based coupling agent obtained by reacting a carboxylic acid with an orthotitanate, wherein the carboxylic acid is 10% by weight or more of the total amount of the carboxylic acid. It is characterized by including.

The coupling agent of the present invention is obtained by reacting an orthotitanate ester with a carboxylic acid, and is synthesized according to the following reaction formula.

Ti (OR ₁ ) ₄ + nR ₂ COOH → Ti (OR ₁ ) ₄ -n (OCOR ₂ ) _n + nR ₁ OH As the orthotitanate ester used in the present invention, tetrapropoxy titanium, tetra n-butoxy titanium, tetra Octoxytitanium, tetrastearoxytitanium, isopropoxy (2-ethylhexanediolato)
Titanium, isopropoxy (ethanediolate) titanium,
These mixtures are mentioned.

Therefore, in the present invention, in the above reaction formula, R ₂ C
As the carboxylic acid represented by OOH, rosin is used in part or in whole.

Examples of the rosin used in the present invention include gum rosin, tall oil rosin, wood rosin, disproportionated rosin of these rosins, hydrogenated rosin, and the like.
It is possible to use abietic acid, dehydroabietic acid, and the like isolated from these rosins, and further to use them in combination.

These rosins may be used alone as the carboxylic acid, but may be used in combination with other carboxylic acids.

The carboxylic acid used in combination with the rosin, with respect to the orthotitanate, it is necessary to have a reactivity, as an example, isostearic acid, oleic acid, lauric acid, octylic acid, acrylic acid, Examples thereof include carboxylic acids such as methacrylic acid, oxyacetic acid, benzoic acid, soybean oil fatty acid, tall oil fatty acid, castor oil fatty acid, and mixtures thereof.

As the carboxylic acid, the ratio of these in the case of using a rosin and another carboxylic acid in combination is not particularly limited, but in order to exert the effect of using the rosin, the rosin content The proportion is preferably 10% by weight or more.

The properties of the titanium-based coupling agent of the present invention are different depending on the type of carboxylic acid other than rosin used in combination and the type of orthotitanate ester, but the proportion of rosin in the total carboxylic acid is small, and is liquid. If the proportion exceeds about 50% by weight, the mixture becomes semisolid or solid at room temperature. Therefore, when modifying the filler using the titanium-based coupling agent of the present invention, if a treatment method of directly contacting the coupling agent and the filler without using a diluent such as a solvent is performed, Considering workability, the proportion of rosin in the carboxylic acid as the raw material of the titanium-based coupling agent is preferably 50% by weight or less.

In the present invention, the molar ratio of carboxylic acid to orthotitanate (value of n in the above reaction formula) is
About 0.2 to 3.7 is suitable. If this ratio is too small, the affinity for the matrix component in the composite material will be insufficient, and if this ratio is too large, the reactivity with the filler will be poor.

When producing the titanium-based coupling agent of the present invention,
As previously mentioned, the orthotitanate ester is reacted with rosin or a mixture of rosin and other carboxylic acids. Since the reaction is an exothermic reaction, a carboxylic acid containing rosin or a dilute solution of the carboxylic acid is dropped into orthotitanate and mixed to react. Further, if necessary, the reaction is carried out while removing the by-product alcohol.

The reaction temperature is preferably about 60 to 170 ° C. If this is excessively low temperature, the reaction rate becomes slow, and if it is too high, on the contrary, decomposition or polymerization reaction of titanic acid ester or generated coupling agent occurs, and ester of alcohol and carboxylic acid by-produced. It is not preferable because it involves a side reaction such as a chemical reaction.

Action Generally, a titanium-based coupling agent has an alkoxy group (—OR) as a highly reactive functional group and an acyl group (—OCOR) as a less reactive functional group. When a filler is treated with this coupling agent, a highly reactive alkoxy group reacts with a functional group on the filler surface and adheres to the filler surface, while an acyl group with low reactivity is
It remains to surround the outside of the filler.

Since the acyl group has lipophilicity, forming a composite material using the filler treated with this coupling agent improves the affinity between the acyl group and the matrix component surrounding the filler. Is done.

Therefore, in the present invention, rosin is contained as the acyl group, and the affinity with the matrix component of the composite material such as paint or toner is particularly excellent.

The method of modifying the filler using the coupling agent of the present invention may be appropriately selected from conventionally known methods.
For example, a method of directly mixing a titanium-based coupling agent and a filler, a method of mixing a titanium-based coupling agent and a filler diluted in a solvent, and a method of distilling off the solvent later if necessary, a titanium-based coupling There are a method of mixing the agent and the filler with the matrix component of the composite material, a method of previously mixing the filler and the matrix component, and then adding a titanium coupling agent and mixing them.

The amount of the titanium-based coupling agent used when modifying the filler varies depending on the type of the filler and the matrix component of the composite material and the type of the function to be improved, but is usually 0 for the filler. 1 to 10% by weight is suitable.

EFFECTS OF THE INVENTION The titanic acid coupling agent according to the present invention has stability and stability of composite materials such as paints and toners as compared with conventionally known titanium coupling agents synthesized from rosin-free carboxylic acid and orthotitanate ester. It is excellent in the function of improving dispersibility and the like, and is suitable as a coupling agent for improving various functions of a composite material system.

Examples Example 1 Tetraisopropoxy titanium 1 mol part and gum rosin 3
Titanium-based coupling agent by reaction with mol parts To a four-necked flask equipped with a stirrer, thermometer, dropping funnel and desolventizer, 100 parts by weight of tetraisopropoxytitanium was charged, and gently heated under stirring. Meanwhile, 710 parts by weight of a 50% by weight isopropanol solution of gum rosin (X grade, acid value 167) was added dropwise over 1 hour and 30 minutes. Since isopropanol began to distill when the temperature in the flask reached about 85 ° C., it was successively distilled off.

The temperature in the flask after the dropping of the rosin solution is
It was 110 ° C. After the dropping is completed, the temperature is further 30
After continuing the reaction for a minute, the reaction system was depressurized to distill off the isopropanol in the flask.

When the distillation of isopropanol is completed, the final degree of vacuum is
It was 60 mmHg and the final temperature was 150 ° C. The amount of isopropanol distilled off was 410 parts, which is in good agreement with the theoretical value of 418 parts.

The product was a solid with a softening point of 89 ° C. When the infrared absorption spectrum of the product was examined, the absorption of the carboxylic acid at 1696 cm ⁻¹ found in the raw gum rosin was significantly reduced,
In place of this, absorption at 1538 cm ⁻¹ due to the bond between carboxylic acid of rosin and titanium appears, and production of the titanium-based coupling agent of the present invention is recognized.

Example 2 Titanium Coupling Agent by Reaction of 1 mol Part of Tetraisopropoxy Titanium with 1 Part by Mole of Rosin and 2 Part by Mole of Tall Oil Fatty Acid 100 parts by weight of tetraisopropoxy titanium was added to the same reaction apparatus as in Example 1. 118 parts by weight of gum rosin (used in Example 1) and tall oil fatty acid (acid value 194, rosin content 1.1%) 2 while being charged and gently heated
A mixture with 03 parts by weight was added dropwise over 1 hour and 30 minutes. Then, the reaction was carried out in the same procedure as in Example 1 to remove the by-produced isopropanol and obtain a liquid reaction product. The amount of isopropanol distilled out was 60 parts by weight, which was in good agreement with the theoretical value of 63 parts by weight.

When the infrared absorption spectrum of the product was examined, it was found to be 1712
The absorption of carboxylic acid at cm ^-1 is significantly reduced, and instead, the absorption at 1540 cm ^-1 based on the bond between carboxylic acid and titanium appears, indicating that a titanium-based coupling agent using rosin and tall oil fatty acid in combination is used. Generation is observed. However, 173
Absorption of carboxylic acid ester was observed at 6 cm ^-1 , and it was confirmed that ester of tall oil fatty acid and isopropanol was slightly produced as a by-product.

Comparative Example 1 Titanium Coupling Agent by Reaction of 1 mol Part of Tetraisopropoxy Titanium and 3 Molar Parts of Tall Oil Fatty Acid 100 parts by weight of tetraisopropoxy titanium was charged into the same reactor as in Example 1 and gently heated. Meanwhile, 305 parts by weight of tall oil fatty acid (used in Example 2) was added dropwise over 1 hour and 30 minutes. After that, the reaction was carried out by the same procedure as in Example 1, the by-produced isopropanol was distilled off, and a liquid reaction product was obtained. The amount of isopropanol distilled out was 57 parts by weight, which was close to the theoretical value of 63 parts by weight.

When the infrared absorption spectra of the raw material tall oil fatty acid and the product were examined, the absorption of carboxylic acid (1710 cm ⁻¹ ) found in the tall oil fatty acid was significantly reduced in the product,
Instead, absorption of the bond between carboxylic acid and titanium (1556
cm ⁻¹ ) appeared, and formation of a titanium-based coupling agent was confirmed. Similarly to the case of Example 2, absorption of carboxylic acid ester was observed at 1736 cm ^−1, and it was confirmed that ester of tall oil fatty acid and isopropanol was by-produced.

Comparative Example 2 Titanium-based coupling agent obtained by the reaction of 1 mol part of tetraisopropoxytitanium and 3 mol parts of isostearic acid 100 parts by weight of tetraisopropoxytitanium was charged into the same reaction apparatus as in Example 1 and gently heated. Meanwhile, 312 parts by weight of isostearic acid (acid value 190) was added dropwise over 1 hour and 30 minutes. Then, the reaction is carried out by the same procedure as shown in Example 1 to distill off the by-produced isopropanol,
A liquid reaction product was obtained. The amount of isopropanol distilled out was 58 parts by weight, which was close to the theoretical value of 63 parts by weight.

When the infrared absorption spectra of the raw material isostearic acid and the product were examined, the absorption of the carboxylic acid (1712 cm ⁻¹ ) found in isostearic acid was significantly reduced in the product, and instead the bond between the carboxylic acid and titanium was found. Absorption of (15
58 cm ⁻¹ ) appeared, and formation of a titanium-based coupling agent was observed. Also, as in Example 2, 1736 cm
^{In -1} , absorption of carboxylic acid ester was observed, and it was confirmed that ester of isostearic acid and isopropanol was produced as a by-product.

Performance Test In order to confirm the effect of improving the function of the composite material when the titanium-based coupling agent according to the present invention is used, an example used in magnetic powder for toner is shown in Reference Example 1, and an example used in carbon black for paint. Is shown in Reference Example 2.

Reference Example 1 Preparation of Toner 100 parts by weight of iron tetraoxide are added to the above Examples 1-2 and Comparative Example 1
10% by weight of each titanium-based coupling agent obtained in
Add 20 parts each of toluene solution and toluene,
After thorough mixing, the solvent was removed by vacuum drying. After mixing with a ball mill for 10 hours, styrene-acrylic resin (Haimer SBM-73 manufactured by Sanyo Kasei Co., Ltd.) 100
Parts and 4 parts of carbon black were added and mixed for 10 hours. Next, after kneading with a heat roll and cooling and solidifying,
It was pulverized with a jet mill to obtain a magnetic toner having an average particle size of 18μ.

Performance Test Each magnetic toner prepared by the above operation was allowed to stand in a thermostat at 50 ° C. for 20 days, and the state of aggregation of toner particles was observed.

The results are shown in Example 1 and Example 2. In the magnetic toner using the titanium-based coupling agent of the present invention,
No agglomeration was observed and it had good fluidity. On the other hand, in the magnetic toners using the titanium-based coupling agent of Comparative Examples 1 and 2, some aggregation was observed. Further, in the magnetic toner prepared by using only toluene without using the titanium-based coupling agent, remarkable aggregation was observed.

Reference Example 2 Preparation of paint Soybean oil-modified alkyd resin (Harifu Tar SL-1055, Harima Chemical Co., Ltd., oil length 62%) was used with carbon black (MA-150, Mitsubishi Kasei Co., Ltd.).
The paint was adjusted with a ball mill.

PWC was 5% by weight, and when the resin and carbon black were kneaded, the titanium-based coupling agents obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were added to carbon black in an amount of 2.
5 wt% was added and mixed to form a paint. Also, as a blank, a paint containing no titanium-based coupling agent was made into a paint by the same operation.

After adding a drier to the obtained paint at a ratio of 0.05% of cobalt, 0.40% of lead and 0.10% of calcium to the solid content of the alkyd resin, the viscosity becomes 25 seconds in a Ford cup. Diluted with mineral spirits,
The performance test described below was performed.

Performance test The paint whose viscosity was adjusted was applied to a cold-rolled steel plate (bright plate) to a thickness of 20 to 25 μm with a NO.36 bar coater, and 20
After drying at 7 ° C for 7 days, the coating film was tested for physical properties. Further, the paint whose viscosity was adjusted was sealed in a glass pin and allowed to stand in a thermostat at 50 ° C. for 14 days, and then the stability of the paint was evaluated from the separated state of the pigment.

The test results are shown in the following table.

From the table, the paints treated with the titanium-based coupling agent of Examples 1 and 2 show excellent results in stability and gloss as compared with Comparative Examples 1 and 2 and the blank.

Front page continuation (72) Inventor Hiroaki Yoshimoto 5 No. 263, Niya, Noguchi-cho, Kakogawa-shi, Hyogo (56) References Japanese Patent Publication No. 57-10891 (JP, B2)

Claims (1)

[Claims] 1. A titanium-based coupling agent obtained by reacting a carboxylic acid and an orthotitanate,
The titanium-based coupling agent, wherein the carboxylic acid contains 10% by weight or more of rosin based on the total amount of carboxylic acid.