JPS6157663A - Titanium coupling agent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is applicable to paints, plus decks, adhesives, magnetic tapes,
In various composite material systems such as toner, the surface of fillers such as inorganic powders and fibers is modified to improve the UN(m), stability, dispersibility, workability, etc. of composite materials using the filler. The present invention relates to a coupling agent for 13Q'?1', and particularly relates to the improvement of a titanium-based coupling agent obtained by reacting an orthotitanate and a carboxylic acid.

BACKGROUND OF THE INVENTION Silane-based coupling agents are the most commonly used coupling agents. However, silane coupling agents have the disadvantage that the objects to be modified are limited to silicon-containing substances such as glass and silica, and the range of application is narrow.

In addition to silane coupling agents, titanium coupling agents are also known. Generally, titanium-based coupling agents are effective against more types of fillers than silane-based coupling agents, and have attracted particular attention in recent years.

Titanium-based coupling agents are generally represented by the following formula (%), where R+ represents an alkyl group, and 2 represents an acyl group, a phenoxy group, an alkoxy group, or a phosphorous ester group. . , a represents a number from 1 to 3, and b represents a number from 1 to 5.

This titanium-based coupling agent is obtained by reacting an orthotitanate ester with a carboxylic acid, and a specific example thereof is isopropyl triisostearoyl titanate represented by the structural formula %:).

Applications of titanium-based coupling agents include, for example, modifiers for fillers for plastics and paints, modifiers for magnetic and conductive materials in 1-ners, magnetic tapes, conductive coating agents, plastic magnets, etc. It can be used to improve the processability and impact resistance of compounds containing five fillers, improve the affinity between fillers and vehicles, prevent blocking of powders, and improve dispersibility. It has an effect.

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 they have a modification effect on more substances such as carbon black and carbon fiber.
It has almost no modification effect on highly versatile carbon-based fillers. Furthermore, the modification effect on magnetic powder and metal powder was not sufficient.

The present invention is a titanium-based coupling agent that is particularly effective in modifying carbon-based fillers, and is capable of sufficiently modifying magnetic powders and metal powders. The object of the present invention is to provide an effective titanium-based coupling agent.

As a means for solving the problems, the present invention is characterized in that in a titanium-based coupling agent obtained by reacting a carboxylic acid and an orthotitanate, the carboxylic acid contains rosin. .

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

■+ (OR+)4 + nR2cOOH→T+
(OR1)4-n (OCOR2)n + n R+
OH The orthotitanate esters used in the present invention include tetrapropoxy titanium, tetra n-butoxy titanium, tetraoctoxy titanium, tetrastearoxy titanium, isopropoxy (2-edylhexane diolato) titanium, isopropoxy ( (ethanediorad) titanium, and mixtures thereof.

Therefore, in the present invention, in the above reaction formula, R2C
Rosin is used as part or all of the carboxylic acid represented by OOH.

Examples of the rosin used in the present invention include gum rosin, tall oil rosin, wood rosin, disproportionated rosin of these rosins, hydrogenated rosin, etc. , abilic acid, dehydroabietic acid, etc., and it is also possible to use a mixture of these.

As the carboxylic acid, these rosins may be used alone, but they can also be used in combination with other carboxylic acids.

The carboxylic acid used in combination with 0-gin must be reactive with the orthotitanate ester, examples of which include isostearic acid, oleic acid, lauric acid, octylic acid, and acrylic acid. , methacrylic acid, oxyacetic acid, benzoic acid, soybean oil fatty acid, tall oil UjM, castor oil fatty acid, and mixtures thereof.

When rosin and other carboxylic acids are used together as carboxylic acids, there are no particular limitations on the proportions of these acids, but in order to achieve the effect of using rosin, the proportion of rosin in the total carboxylic acids must be The ratio is 10 melonffi
% or more.

The properties of the titanium-based coupling agent of the present invention vary depending on the type of carboxylic acid other than rosin used together and the fi of the orthotitanate ester, but those in which the proportion of rosin in the total carboxylic acid is small are liquid. , when the proportion exceeds approximately 50=lft)%, it becomes semi-solid or solid at room temperature. Therefore, when modifying a filler using the titanium-based camping agent of the present invention, if a treatment method is used in which the coupling agent and filler are brought into direct contact without using a diluent such as a solvent, In consideration of workability, the proportion of rosin in the carboxylic acid as a raw material for the titanium-based coupling agent is preferably 50 fn lit % or less.

In the present invention, the molar ratio of a3 (C1 carboxylic acid to or) titanate ((f of n in the above reaction formula)
l) is suitably about 0.2 to 3.7.

If this ratio is too small, the affinity with 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,
1) As described in r1, the orthotitanate ester is reacted with rosin or a mixture of [1 gin and another carboxylic acid. Since the reaction is exothermic, ol-1-titanic acid 1
It is preferable to drop a carboxylic acid containing rosin or a diluted solution of the carboxylic acid into the stell, mix and react.

Further, if necessary, the reaction is performed while removing alcohol by-produced by the reaction.

The reaction temperature is suitably about 60 to 170°C. If the temperature is too low, the reaction rate will be slow, and if the humidity is too high, the titanate ester and the coupling agent formed will decompose or polymerize, and the alcohol and carboxylic acid produced as by-products will This is not preferred because it involves side reactions such as esterification reactions.

Function Generally, a titanium-based coupling agent has an alkoxy group (-OR) as a highly reactive functional group and an acyl λ$ (-0COR) as a less reactive functional group.

When the filler is treated with this coupling agent, the highly reactive alkoxy groups react with the functional groups on the filler surface and stick to the filler surface, while the less reactive acyl groups attach to the outside of the filler. It remains in a surrounding form.

Since the acyl group has lipophilicity, when a composite material is formed using a filler treated with this coupling agent, the affinity between the acyl group and the matrix component surrounding the filler increases. is improved.

In the present invention, the acyl group contains rosin, and has particularly excellent affinity with matrix components of composite materials such as paints and toners.

The method for 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 diluted in a solvent and a filler, and adding a solvent to the titanium-based coupling agent if necessary, and a method of mixing a titanium-based coupling agent and a filler diluted in a solvent. and a filler into a matrix component of a composite material, filler and 7
There is a method in which the titanium-based coupling agent is mixed in advance with the 1-lix component, and then a titanium-based coupling agent is added and mixed.

The ml of titanium-based coupling agent used when modifying fillers varies depending on the type of matrix component of the filler or composite material, and the type of coupling agent to be improved, but it is usually A suitable amount is 0.1 to 10% by weight.

Effects of the Invention The titanic acid coupling agent according to the present invention is more effective in paints than in conventional titanium-based coupling agents synthesized from rosin-free carbibone and orthotitanate.
It is excellent in its ability to improve the stability and dispersibility of composite materials such as 1-su, and is suitable as a coupling agent for improving various functions of composite material systems.

Examples Example 1 Tomole parts of tetraisobrobodic titanium and gum rosin 3
Titanium-based coupling agent stirrer, thermometer, dropping funnel and Il+! by reaction with molar parts! In a four-bottle flask equipped with a solvent system, add 10% tetraisopropoxytitanium
Add 0mm portion and heat gently while stirring.
1 part of 7IC of a 50% by weight isopropanol solution of gum rosin (X class, acid value 167) was added dropwise over 1 hour and 30 minutes. As soon as the temperature in the flask reached approximately 85° C., isopropanol began to come out, and this was successively distilled off.

The temperature inside the flask after dropping the rosin solution is
The temperature was 110°C. After dropping, keep at this temperature for approximately 30 minutes.
After continuing the reaction for a minute, the reaction system was depressurized and the isopropanol in the flask was removed.

The final degree of decompression when you finish working as an improvised tool merchant is:
6011181-1ll, final temperature is 150℃
Met. The commercially available isopropanol has a value of 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 we examined the infrared absorption spectrum of the product, we found that the absorption of 1696C11' carboxylic acid observed in the raw material gum rosin was greatly reduced, and instead, the absorption of 1538C11+' due to the bond between the carboxylic acid of the rosin and titanium. Absorption appears, confirming the production of the titanium-based coupling agent of the present invention.

Example 2 Titanium-based coupling agent by reaction of 1 mole part of tetraisopropoxytitanium with 1 mole part of rosin and 2 mole parts of tall oil fatty acid Into the same reaction apparatus as in Example 1, 100 mfft part of tetraisopropoxytitanium was charged. , While heating gently, add 118 parts by weight of gum rosin (used in Example 1), tall oil fatty acid acid value 194, and O gin content 1.1%.
) 203, was added dropwise over 1 hour and 30 minutes. Thereafter, the reaction was carried out in the same manner as in Example 1, and by-produced isopropanol was removed to obtain a liquid reaction product. The amount of isopropanol distilled out was 60 fflffi parts, which agreed well with the theoretical value of 63 fflffi parts.

When the infrared absorption spectrum of the product was examined, it was found that 1712
The absorption of carboxylic acid of CII' was significantly reduced, and instead absorption of 1540- appeared based on the bond between carboxylic acid and titanium, and the production of a titanium-based coupling agent using rosin and tall oil fatty acid in combination. is recognized. However, 17
Absorption of carboxylic acid ester was observed at 36c+n',
It was observed that a small amount of ester of tall oil fatty acid and isopropanol was produced as a by-product.

Comparative Example 1 Titanium-based coupling agent by reaction of 1 mole part of De1-Litebu I coboxiditan and 3 mole parts of tall oil fatty acid Into the same reaction apparatus as in Example 1, 100 parts by weight of tetraisopropoxytitanium was charged and gently reacted. Tall oil fat while heating! (Used in Example 2) 305 parts by weight was added dropwise over 1 hour and 30 minutes and reacted in the same manner as in Example 1. I got it. The mother of the distilled isopropanol is a 57-year-old husband and 1! I! 63ff of logical value!
The value was close to 1 part ff.

When we investigated the infrared absorption spectra of the raw material tall oil fatty acid and the product, we found that the absorption of carboxylic acid (1710 cw+') seen in the tall oil fatty acid was significantly reduced in the product, and instead it was due to the absorption of carboxylic acid and titanium. Absorption of bonds (15
56 cm') appeared, and the formation of a titanium-based coupling agent was observed. In addition, as in the case of Example 2, 173
Absorption of carboxylic acid ester was observed at 6 cm, and it was observed that ester of tall oil fatty acid and isopropanol was produced as a by-product.

Comparison/Example 2 A titanium-based coupling agent produced by reacting 1 mol part of tetraisopropoxy titanium with 3 mol parts of isostearin rlJ. Into the same reaction apparatus as in Example 1, 100 parts by weight of tetraisopropoxytitanium was charged, and while being heated gently,
312 parts of isostearic acid (acid value: 190) was added dropwise over 1 hour and 30 minutes. Thereafter, the reaction was carried out in the same manner as shown in Example 1, and the produced isopropanol was sold to obtain a liquid reaction product. The volume of distilled isopropanol was 58 parts by weight, which was the theoretical value of 63ff1.
The value was close to 1 part.

When we investigated the infrared absorption spectra of the raw material isostearic acid and the product, we found that the absorption of carboxylic acid (1712 cm') seen in isostearic acid was significantly reduced in the raw acid, and instead it was due to the bond between carboxylic acid and titanium. absorption (1
558cni') appeared, and the formation of a titanium-based coupling agent was observed. J: Similarly to "M" in Example 2, absorption of Nisder carboxylic acid was observed at 1736 cm', and ester of isostearic acid and isobutylpanol was observed to be by-produced.

Performance test In order to confirm the effect of improving the functionality of composite materials when using the titanium-based coupling agent according to the present invention, reference example 1 shows an example in which it was used in magnetic powder for l-ner, and an example in which it was used in carbon black for paint. An example of this is not shown in Reference Example 2.

Reference Example 1 Preparation of Toner To 100 parts of triiron tetroxide, 1 part weight % toluene solution of each titanium coupling agent obtained in Examples 1 to 2 and 'Comparative Examples 1 to 2 and toluene were added at 20 parts each. After thoroughly mixing, the solvent was removed by vacuum drying. After mixing in a ball mill for 10 hours, 100 parts of styrene/acrylic resin (Himer 55M-73 manufactured by Sanyo Chemical Co., Ltd.) and 4 parts of carbon black were added, and the mixture was further mixed for 10 hours.

The mixture was then kneaded with a heat roll, cooled and solidified, and then pulverized with a diene 1-mill to obtain a magnetic toner with an average particle size of 18 .mu.m.

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

As a result, in the magnetic toner using the titanium-based coupling agent of the present invention shown in Examples 1 and 2,
No agglomeration was observed and the magnetic toners had good fluidity.On the other hand, some aggregation was observed in the magnetic toners using the titanium-based coupling agents of Comparative Examples 1 and 2. In addition, significant aggregation was observed in the magnetic toner prepared only with toluene without using a titanium-based coupling agent.

Reference Example 2 Preparation of Paint Soybean oil-modified algide resin (Harifthal 8m-1055, manufactured by Yuma Kasei Co., Ltd., oil length 62%) was mixed with carbon black (Mitsubishi Kasei Co., Ltd. VMA-150).
The paint was prepared using a ball mill.

PWC was 5% by weight, and when kneading the resin and carbon black, 1g of the titanium-based coupling agent added in Examples 1 and 2 and Comparative Examples 1 and 2 was added to the carbon black in an amount of 2g.
．． 51 fft% was added and mixed to form a paint. In addition, a blank material to which no titanium-based coupling agent was added was also made into a paint using the same procedure.

The resulting paint contains 1 to 0.05% of Kobal, 0.40% of Lead, and 0.10% of Calcium based on the alkyd resin solid content.
After adding 7- to the dry mixture at a ratio of 7-1, it was diluted with mineral spirit so that the viscosity was 25 seconds per A-cup, and the performance test described below was conducted.

Performance test: Apply the paint with adjusted viscosity to a thickness of 20 to 25 μm on a cold rolled steel plate (Prite plate) using a NO.36 bar coater.
After drying at 20° C. for 7 days, the physical properties of the coating film were tested.

In addition, the viscosity-adjusted paint was sealed in a glass bottle and heated to 50°C.
After leaving it in a thermostatic chamber for 14 days, the state of separation of the pigment showed that
The stability of the paint was evaluated.

The results of the test were as shown in the table below.

From the table, the paint treated with the titanium-based coupling agent of Example 1.2 shows superior results in stability and gloss compared to Comparative Example 1.2 and the blank.

Claims (1)

[Claims] 1. A titanium-based coupling agent obtained by reacting a carboxylic acid and an orthotitanate, characterized in that the carboxylic acid contains rosin.