JPH11140090A - Method for producing nitrogen silicon-containing compound - Google Patents

Abstract

(57) [Problem] To obtain a nitrogen silicon-containing compound excellent in various uses. SOLUTION: A monomer and / or oligomer of a tetraalkoxysilane and an amino group-containing compound represented by the following general formula (I) are prepared by converting the number of moles of amino group / (number of moles of amino group + mole of alkoxy group) Number) = 0.015 to 0.
A method for producing a nitrogen-silicon-containing compound, wherein the compound is blended at a ratio of 09. ^{R 2 R 3 N - [{} (CR 'R'') a -O-} b - (CR''' R '''') c] -OH ··· (I) (R 2, R 3 is At least one of hydrogen, an alkyl group, an alkenyl group and an aryl group, R ^′ , R ^″ , R ^{′ ″} and R
^'''' Is one or more of hydrogen, an alkyl group and a halogen. a and c are integers of 1 or more, and b is an integer of 0 or more. )

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition containing fillers such as paints, coating liquids, adhesives and various kinds of powders. The present invention relates to a novel silicon-containing compound having excellent functions such as improvement in stainability, scratch resistance, heat resistance, and adhesion.

[0002]

2. Description of the Related Art In recent years, many silane coupling agents having two different reactive groups in a molecule have been widely used in industry.

[0003]

An amino group-containing silane coupling agent, for example, γ-aminopropyltrimethoxysilane, can be used for resin or coating by surface treatment of existing resins and fillers and addition to coating agents and paints. The purpose is to improve the mechanical strength of the film, the adhesion between the coating film and the substrate, and the adhesive strength.

However, since the amino group-containing silane coupling agent reacts as a monomer, when it is used as a coating additive, it is difficult to exhibit its effect unless used in a large amount. It has disadvantages in that it often impairs its own properties and that it is difficult to form a siloxane bond, which greatly contributes to the improvement in hardness, because the reaction site is a monomer unit. Furthermore, the degree of contribution to improvement in heat resistance and scratch resistance was low.

The present invention has been made in view of the above-mentioned limitations of the state of the art, and an object of the present invention is to provide a material capable of achieving hardness development, adhesion improvement, and the like with a small amount of addition.

[0006]

Means for Solving the Problems The present inventors have made intensive studies in view of the above problems. Then, by reacting a specific silicon-containing compound and a specific nitrogen-containing compound, the obtained nitrogen-silicon-containing compound is added to a resin containing a filler such as an existing paint, coating liquid or various powders. It has been found that it is suitable as a coating material or a composite agent.

That is, the present invention relates to a method for converting a monomer and / or oligomer of a tetraalkoxysilane and an amino group-containing compound represented by the following general formula (I) into the number of moles of amino group / (number of moles of amino group) + Mole number of alkoxy group)
= 0.015 to 0.09 in a method for producing a nitrogen silicon-containing compound. ^{R 2 R 3 N - [{} (CR 'R'') a -O-} b - (CR''' R '''') c] -OH ··· (I) (R 2, R 3 is At least one of hydrogen, an alkyl group, an alkenyl group and an aryl group, R ^′ , R ^″ , R ^{′ ″} and R
^'''' Is one or more of hydrogen, an alkyl group and a halogen. a and c are integers of 1 or more, and b is an integer of 0 or more. )

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. (Silicon Compound) In the present invention, a specific silicon compound and a nitrogen compound are blended and reacted to obtain a nitrogen-silicon compound containing nitrogen and silicon.

First, as the silicon compound as one of the raw materials, there are a tetraalkoxysilane monomer represented by Si (OR) ₄ and an oligomer which is a low condensate obtained by hydrolyzing and condensing this monomer. Use one or more of Here, R is an alkyl group, preferably C
It is a 1-4 alkyl group, most preferably a methyl group.
By using such a tetraalkoxysilane monomer or oligomer, the resulting nitrogen silicon compound can have excellent physical properties such as hardness and stain resistance when formed into a coating film. Since a tetramethoxysilane monomer having a methyl group as R has toxicity, it is preferable to use a tetramethoxysilane oligomer which is a low condensate obtained by hydrolyzing and condensing the monomer.

In particular, the oligomer has a hydrolysis rate of 30
The use of a compound having a content of from 60% to 60%, particularly preferably from 40% to 55%, facilitates handling of the oligomer itself, and also has excellent compatibility with resin components and solvents when blended in various paints, which is preferable. Here, the hydrolysis rate indicates the amount of water when water is added to a monomer of tetraalkoxysilane for hydrolytic condensation, and the alkoxy group of tetraalkoxysilane can be theoretically hydrolyzed and condensed to 100%. The amount is expressed as a percentage, that is, 100% of water, which is 1/2 mole times the alkoxy group of the tetraalkoxysilane.

As such oligomers, tetramethoxysilane oligomers such as “MKC silicate MS51” and “MKC silicate MS56” manufactured by Mitsubishi Chemical Corporation are manufactured and sold, and these oligomers have toxicity. It has a very low monomer content of tetramethoxysilane, has excellent storage stability, and has very good physical properties. When a monomer of a silicon compound and a nitrogen compound are mixed in advance and oligomerization is performed, a desired oligomer may be difficult to obtain because an amino group of the nitrogen compound acts very strongly as a catalyst.
Therefore, it is desirable to obtain an oligomer of a silicon compound in advance and add a nitrogen compound to the oligomer.

In general, a single type of alkoxy group of tetraalkoxysilane is sufficient, but a monomer or oligomer having a plurality of types of alkoxy groups may of course be used. (Amino Group-Containing Compound) The amino group-containing compound as one of the raw materials of the present invention is represented by the following general formula (I).

[0013] ^{R 2 R 3 N - [{} (CR 'R'') a -O-} b - (CR''' R '''') c] -OH ··· (I) (R 2, R ³ is one or more of hydrogen, an alkyl group, an alkenyl group, and an aryl group, R ^′ , R ^″ , R ^{′ ″} and R
^'''' Is one or more of hydrogen, an alkyl group and a halogen. a and c are integers of 1 or more, and b is an integer of 0 or more. )) As described above, the amino group-containing compound used in the present invention has one OH group at one terminal. This OH
However, by reacting with the alkoxy group of the silicon compound described above, a nitrogen-containing functional group can be introduced into the silicon compound by a transesterification reaction.
In the case of a nitrogen compound having two or more OHs, crosslinking between molecules proceeds, and the composition gels, and it is difficult to use the composition for applications such as a coating liquid.

Further, the other end has one amino group, whereby the characteristics of the amino group can be exhibited. (Transesterification reaction) The silicon compound described above and the amino group-containing compound are blended at a specific blending ratio and reacted. That is, an alkoxy group of the silicon compound,
The number of moles of amino group / (number of moles of amino group + number of moles of alkoxy group)
= 0.015 to 0.09.
Preferably, the number of moles of the amino group / (the number of moles of the amino group +
(The number of moles of alkoxy group) = 0.03 to 0.07.
If the amount of the nitrogen compound does not reach 0.015 in the above molar ratio, amino group characteristics are not sufficiently exhibited. On the other hand, if the molar ratio exceeds 0.09, the amount of the amino group introduced into the silicon compound is too large, and in this system in which the amino group acts as a catalyst, the catalytic activity is so strong that Hydrolysis makes handling difficult.

In the transesterification reaction, the silicon compound and the amino group-containing compound are mixed, and an alkoxy group and an O group are mixed.
The reaction proceeds if the alcohol generated by the dealcoholation reaction with the H group is distilled off. The method of distillation is not particularly limited, but inert gas blowing, vacuum distillation and other general methods are sufficient. In the reaction, a solvent or a catalyst may be used.However, when the silicon compound and the amino group-containing compound are almost uniformly mixed, a solvent is not necessary, and a catalyst is not necessarily required. The reaction proceeds by the catalytic action of the amino group.

Thus, according to the present invention, a silicon compound and an amino group-containing compound can be reacted to obtain an amino group-introduced silicon-containing compound. The nitrogen-silicon-containing compound thus obtained can be suitably used for various applications, but is particularly preferably represented by the following chemical formula. SiO _x (OR ¹ ) _y (O-[(CR ^''' R ^'''' ) _c- ｛O- (CR ^{'
_{R '') a} b]}} -NR 2 R 3) z ( wherein, R ^2, R ³ is hydrogen, is an alkyl group, one or more of alkenyl group and aryl group .R ^{', R'',} R ^'''
And R ^{″ ″} is one or more of hydrogen, an alkyl group, and halogen. a and c are integers of 1 or more, and b is an integer of 0 or more.

0 ≦ x ≦ 1.8, 0.02 ≦ z / (y +
z) ≦ 0.2, R ¹ is one or more of an alkyl group, an alkenyl group, and an aryl group having 1 or more carbon atoms. R ² and R ³ are one or more of hydrogen, an alkyl group, an alkenyl group and an aryl group. Here, 0 ≦ x ≦ 1.8 is satisfied when 1.8 <x.
This is because the nitrogen-silicon-containing compound has a high viscosity, is inconvenient to handle, has low compatibility with a resin component or a solvent or the like when blended in a paint or the like, and it is difficult to perform one-packing. Particularly preferably, x ≦ 1.4. When 1.4 <x, the stability of the compound itself is low, and problems such as gelation and change in characteristics may occur.

R ¹ is at ^{least one} of an alkyl group, an alkenyl group and an aryl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Examples of the alkenyl group include a vinyl group, an allyl group, an acroyloxypropyl group, and a methacryloyloxypropyl group. Examples of the aryl group include a phenyl group.

The selection of R ¹ can be appropriately made according to the purpose of use of the nitrogen-containing compound of the present invention.
Incidentally, the monomers and / or oligomers of tetraalkoxysilanes as described above to obtain a compound having an alkyl group as R ¹ as a raw material, it is be reacted with an amino group-containing compounds described above, the alkyl group as R ¹ When it is desired to have a group other than the above, for example, a means of introducing a desired functional group into the silicon-containing compound obtained by the above-described production method by a transesterification reaction may be employed.

In the nitrogen-silicon-containing compound of the present invention, when R ¹ is an alkyl group, the compatibility with various resins and solvents is excellent as the number of carbon atoms increases. The function expression (especially abrasion resistance and mechanical strength) of the composite material is low. As R ¹ having a particularly excellent balance of these properties, R ¹ is an alkyl group having 1 to 4 carbon atoms. Most preferably, R ¹ has a methyl group.

X, y, and z in the chemical formula of the silicon-nitrogen-containing compound of the present invention can be determined by the following methods. (1) The amount of R ¹ OH produced by completely hydrolyzing the silicon-nitrogen-containing compound of the present invention using an acid or an alkali is measured by gas chromatography to determine y. (2) The peak area ratio of Q0 to Q4 is determined by ²⁹ Si-NMR measurement, and x is calculated. (3) z is calculated by 2x + y + z = 4.0.

Since the nitrogen silicon-containing compound of the present invention has an amino group, it can react with organic materials such as acid anhydrides and acylated compounds. In addition, it has many siloxane bonding parts that exhibit heat resistance, mechanical strength, scratch resistance, and the like. Accordingly, physical properties such as scratch resistance and mechanical strength of a coating film or a resin composite material containing the silicon-containing compound of the present invention are improved. Preferably, either R ² or R ³ is hydrogen. More preferably, both R ² and R ³ are hydrogen.

0.02 ≦ z / (y + z) ≦ 0.2. This is because when 0.1 <y / (y + z), problems such as a decrease in storage stability due to gelation of the compound alone, a rapid increase in viscosity of the compound, and a hardening are unsuitable for use. Probably, it can be said that it is an index of the ratio of the amino group and the organic group such as the alkoxy group which the nitrogen silicon-containing compound of the present invention has. This is considered to be due to the fact that a reaction easily occurs with the silicon atom to which R ¹ is bonded. Particularly preferably, 0.05 ≦
z / (y + z) ≦ 0.15. (Use) The nitrogen-silicon-containing compound of the present invention is suitable for improving the adhesion, abrasion resistance, weather resistance, heat resistance, chemical resistance and adhesive strength of paints, coating liquids, primers and adhesives.

Further, the nitrogen silicon-containing compound of the present invention comprises
It is also suitable for improving the mechanical strength, weather resistance, chemical resistance and abrasion resistance of reinforced plastics by treating glass fibers, modifying the surface of inorganic fillers, and directly mixing with synthetic resins. Further, it is also suitable for being added to a resin composition containing a filler such as other various powders to form a coating material or a composite material.

[0025]

EXAMPLE 1 688.7 g of an oligomer of tetramethoxysilane (hydrolysis rate: 40%) and 44.9 g of monoaminoethyl alcohol were put in a reactor and heated at 80 ° C. for 1 hour in a nitrogen atmosphere. The temperature was further raised to 100 ° C. to remove ethyl alcohol generated by the reaction. Subsequently, the tetramethoxysilane generated by the depolymerization was distilled off under reduced pressure to obtain a nitrogen silicon-containing compound.

The chemical formula of the obtained nitrogen silicon-containing compound is shown below. SiO _0.954 (OCH ₃ ) _1.87 (OC ₂ H ₅ NH ₂ ) _0.218

[0027]

According to the present invention, a nitrogen-containing compound excellent in various uses can be obtained.

Continued on the front page (72) Inventor Takeshi Sawai 1-1 Kurosaki Castle Stone, Yawatanishi-ku, Kitakyushu City Inside Mitsubishi Chemical Corporation Kurosaki Office

Claims (10)

[Claims] 1. A tetraalkoxysilane monomer and / or
Alternatively, the oligomer and the amino group-containing compound represented by the following general formula (I) may be prepared by converting the number of moles of amino group / (number of moles of amino group + number of moles of alkoxy group) = 0.015 to 0.0
9. A method for producing a nitrogen-silicon-containing compound, which is blended at a ratio of 9. ^{R 2 R 3 N - [{} (CR 'R'') a -O-} b - (CR''' R '''') c] -OH ··· (I) (R 2, R 3 is At least one of hydrogen, an alkyl group, an alkenyl group and an aryl group, R ^′ , R ^″ , R ^{′ ″} and R
^'''' Is one or more of hydrogen, an alkyl group and a halogen. a and c are integers of 1 or more, and b is an integer of 0 or more. ) 2. The method according to claim 1, wherein R ² is hydrogen. 3. The method of claim 1, wherein R ² and R ³ are both hydrogen.
Or the method for producing a nitrogen-silicon-containing compound according to 2. 4. The method for producing a nitrogen silicon-containing compound according to claim 1, wherein the alkoxy group of the tetraalkoxysilane has 1 to 4 carbon atoms. 5. The method according to claim 1, wherein a is an integer of 1 to 5. 6. A coating liquid containing the nitrogen-silicon-containing compound obtained by the method according to claim 1. 7. A rational formula _{^{SiO x (OR 1) y (}} O - [(CR '''R'''') c - {O- (CR' R
^'' ) _a } _b ] -NR ² R ³ ) A nitrogen-containing compound represented by _z . (Wherein, R ² and R ³ are one or more of hydrogen, an alkyl group, an alkenyl group and an aryl group. R ^′ , R ^″ , R ^{′ ″} and R ^{″ ″} are hydrogen, an alkyl group And at least one of halogen.
a and c are integers of 1 or more, and b is an integer of 0 or more. 0 ≦
x ≦ 1.8, 0.02 ≦ z / (y + z) ≦ 0.2, R ¹
Is at least one of an alkyl group, an alkenyl group and an aryl group. R ² and R ³ are one or more of hydrogen, an alkyl group having 1 or more carbon atoms, an alkenyl group, and an aryl group. ) 8. The nitrogen silicon-containing compound according to claim 7, wherein 0.05 ≦ z / (y + z) ≦ 0.15. 9. The nitrogen-silicon-containing compound according to claim 7, wherein 0 ≦ x ≦ 1.4. 10. A coating liquid comprising the nitrogen-containing compound according to claim 7.