JP3485273B2 - Metal-silicon composite alkoxide and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel metal-silicon composite alkoxide compound, and more particularly to a metal-silicon composite alkoxide compound useful as a surface treating agent, particularly as a primer.

[0002]

2. Description of the Related Art Conventionally, the surface of glass or the like has a refraction index for the purpose of cutting off ultraviolet rays and infrared rays (heat rays) in order to prevent the interior furniture from changing due to natural light, the discoloration of the furniture, and the excessive rise in the room temperature. Treatment with a thin film of high titanium oxide or the like is performed.

As such a method, there is known a method of using a metal alkoxide to form a coating film on the glass surface by a so-called sol-gel process, and a method of treating the glass surface by ion sputtering, CVD, PVD or the like. There is.

[0004]

However, such a glass is usually a substance mainly composed of a silica skeleton,
Therefore, it has a low affinity for titanium oxide, zirconium oxide, etc., which are effective against ultraviolet rays and infrared rays. Therefore, it is difficult to form a uniform film of titanium oxide and zirconium oxide on the glass surface by the sol-gel process, and the formed film also has problems in strength such as weather resistance and abrasion resistance. Ion sputtering,
Although it is possible to form a uniform and strong film by a physical or physicochemical method such as CVD or PVD,
It takes time to obtain a film having a sufficient thickness, and the cost is considerably high. Further, since the size of the article to be processed is limited by the size of the apparatus, it is difficult to process a large area article.

[0005]

In order to solve the above-mentioned problems, the present inventor has conducted extensive studies and as a result, a metal-silicon composite having an alkoxy group part bonded to silicon and an alkoxy group part bonded to titanium or zirconium. The inventors have found that a uniform and strong coating can be obtained by forming a coating of titanium oxide or zirconium oxide after subjecting the surface of glass to a primer with an alkoxide compound, and completed the present invention. That is, the present invention relates to a novel metal-silicon composite alkoxide compound represented by the general composition formula (1), which is useful as a primer for surface treatment of glass. Further, the present invention is a novel metal represented by the above general composition formula (1), which is produced by reacting an organosilicon compound of the general composition formula (2) with a metal alkoxide of the general composition formula (3). -A method for producing a silicon composite alkoxide compound.

[0006]

[Chemical 4] (However, in the formula, M represents Ti or Zr, R represents an alkyl group, may be different from each other or may contain the same ones, and R ^* represents an alkyl group having 4 or less carbon atoms, They may be different or the same as each other, Q represents a divalent hydrocarbon group or a divalent organic group containing a sulfur atom, and different from each other include the same one. Also, X represents a monovalent hydrocarbon group, which may be different from each other or may include the same ones, a represents an integer of 0 to 2, and n represents 1 to 2.)

[0007]

[Chemical 5] (However, in the formula, R represents an alkyl group, which may be different from each other or may include the same ones, and Q is a divalent group.
Hydrocarbon group or divalent organic group containing sulfur atom
Where R'has a carbon number less than Q and a carbon number of 3 or more.
Represents a monovalent hydrocarbon group below, and X represents a monovalent hydrocarbon group.
May represent the same or different from each other, and a represents an integer of 0 to 2. )

[0008]

[Chemical 6] (However, in the formula, M represents Ti or Zr, and R ^* represents an alkyl group having 4 or less carbon atoms, which may be different from each other or may be the same as each other.)

Specific examples of R'in the formula (2) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group or a group in which a hydrogen atom of these groups is partially substituted with a halogen atom. You can When the carbon number is 4 or more, the boiling point of the ester, which is a by-product of the reaction between the compound of the general composition formula (2) and the compound of the general composition formula (3), becomes high, and it becomes difficult to remove it from the reaction system. It is not preferable.

The compound of the general composition formula (2) can be synthesized, for example, by the following methods 1 and 2. 1. A method of reacting an acid anhydride represented by the following general formula (4) with a) a monohydrogensilane represented by the following general formula (5) in the presence of a platinum-based catalyst or b) the following general formula (6) ) A method of reacting with an alkoxylane having a mercapto group represented by the formula (1) under ultraviolet irradiation or in the presence of an organic peroxide.

[0011]

[Chemical 7] (However, Z represents a monovalent organic group having an unsaturated bond,
R'represents a monovalent hydrocarbon group having 3 or less carbon atoms)

[0012]

[Chemical 8] (However, R represents an alkyl group, which may be different from each other or may include the same ones, X represents a monovalent hydrocarbon group, and different from each other may include the same ones. Also, a represents an integer of 0 to 2.)

[0013]

[Chemical 9] (However, P represents a divalent hydrocarbon group, R represents an alkyl group, may be different from each other or may include the same ones, and X represents a monovalent hydrocarbon group and different from each other. Or may contain the same ones as each other, a
Represents an integer of 0 to 2. )

2. A method in which an acid derivative represented by the following general formula (7) is converted into an anhydride by a known organic reaction such as reacting with a compound represented by the following general formula (8).

[0015]

[Chemical 10] (However, in the formula, R represents an alkyl group, which may be different from each other or may include the same ones, and Q is a divalent group.
Hydrocarbon group or divalent organic group containing sulfur atom
In the formula, X represents a monovalent hydrocarbon group, which may be different from each other or may be the same as each other, and a is 0 to 2
Represents the integer. )

[0016]

[Chemical 11] (However, R'represents a monovalent hydrocarbon group having 3 or less carbon atoms)

The acid anhydride represented by the general formula (4) is
For example, the compound of the following general formula (9) and the following general formula (10)
Can be synthesized by a known organic reaction such as a reaction with a compound of formula (11) or a compound of the following general formula (11) with a compound of the following general formula (12), and the acid derivative represented by the general formula (7) is , A compound represented by the following general formula (9) and a) a monohydrogensilane represented by the general formula (5) are reacted in the presence of a platinum-based catalyst, or b) the general formula (6) It can be synthesized by reacting with an alkoxylane having a mercapto group represented by the formula (1) under UV irradiation or in the presence of an organic peroxide.

[0018]

[Chemical 12] (However, Z represents a monovalent organic group having an unsaturated bond)

[0019]

[Chemical 13] (However, R'represents a monovalent hydrocarbon group having 3 or less carbon atoms.)

[0020]

[Chemical 14] (However, Z represents a monovalent organic group having an unsaturated bond.)

[0021]

[Chemical 15] (However, R'represents a monovalent hydrocarbon group having 3 or less carbon atoms.)

The titanium or zirconium alkoxide represented by the above general composition formula (3) is specifically titanium tetramethoxide, titanium tetraethoxide,
Titanium tetraisopropoxide, titanium tetra-n-propoxide, titanium tetra-n-butoxide, titanium tetraisobutoxide, titanium tetra-sec-butoxide, titanium tetra-tert-butoxide, zirconium tetramethoxide, zirconium tetraethoxide, Zirconium tetraisopropoxide, zirconium tetra-n-propoxide, zirconium tetra-n-butoxide, zirconium tetraisobutoxide, zirconium tetra-sec-butoxide, zirconium tetra-te.
Examples include rt-butoxide.

Further, the method for producing the metal-silicon composite alkoxide of the present invention will be described in detail.

When the organosilicon compound of the present invention is produced, the organosilicon compound represented by the general composition formula (2) is reacted with the metal alkoxide represented by the general composition formula (3). In this reaction, it is preferable to use an organic solvent other than alcohol. When alcohol is used, as a side reaction, esterification with the alkoxysilane compound represented by the general composition formula (3) proceeds, and the main reaction does not proceed quantitatively. As the organic solvent other than alcohol, any solvent capable of dissolving both metal alkoxide and alkoxysilane compound may be used, and specific examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, diethyl ether, diisopropyl ether and the like. Examples thereof include ethers, esters such as methyl acetate and ethyl acetate, ketones such as methyl ethyl ketone and acetone, tetrahydrofuran, dimethyl sulfoxide and the like, and mixtures thereof. Among them, ethers and hydrocarbons are particularly preferable. . These solvents may be used as they are, but in order to suppress the hydrolysis reaction of the compounds represented by the above general composition formulas (2) and (3), metal sodium, metal magnesium, etc. are reacted and distilled. It is more preferable to use it after dehydration purification by the method.

The reaction temperature is not particularly limited, but it is usually preferable to carry out under reflux conditions at the boiling point of the solvent used from the viewpoint of reaction temperature control. Further, the reaction is preferably carried out under a dry condition, for example, under an inert gas stream such as argon or dry nitrogen in order to prevent decomposition of the alkoxide portion. After the reaction is completed, the organic solvent used and the ester which is a side reaction product can be removed by a means such as vacuum distillation, reduced pressure distillation, and freeze-drying to take out the desired organosilicon compound.

The present invention will be described in more detail below with reference to production examples of the organosilicon compound represented by the general composition formula (2).

[0027]

[Production Example 1] 36.9 g of 10-undecenoic acid was added to a three-necked flask equipped with a reflux condenser, a stirrer and a gas inlet tube.
39.3 g of mercaptopropyltrimethoxysilane and 300 ml of benzene were weighed out and mixed with stirring. further,
A solution prepared by dissolving 0.5 g of azobisisobutyronitrile in 100 ml of benzene was added to this solution and mixed with stirring. After bubbling with dry nitrogen gas at room temperature for 1 hour while continuing stirring, the mixture was heated and refluxed at the boiling point of benzene for 12 hours. After the reaction was completed, it was cooled in an ice bath.
Further, 100 ml of triethylamine was added and mixed with stirring. A solution prepared by dissolving 18.5 g of propanoyl chloride in 100 ml of benzene was gradually added dropwise to this solution while cooling with an ice bath and stirring. After the addition was complete, stirring was continued for another 30 minutes. After the white precipitate that had formed was filtered off, the solvent was removed by a rotary evaporator to obtain a viscous liquid. IR and NMR measurements showed that this liquid was an organosilicon compound represented by the formula (13).

[0028]

[Chemical Formula 16] (Where, Q is _{-CH 2 (CH 2) 8 CH} 2 SCH 2 CH 2 CH
Represents _2- . )

[0029]

[Production Example 2] 18.0 g of acetic acid, 400 ml of tetrahydrofuran and 100 ml of triethylamine were weighed out in a three-necked flask equipped with a reflux condenser, a stirrer and a gas inlet tube, and mixed with stirring. 31.4 g of methacryloyl chloride was added to this solution while cooling with an ice bath and continuing stirring.
Was dissolved in 100 ml of tetrahydrofuran and the solution was gradually added dropwise. After the addition was complete, stirring was continued for another 30 minutes. After the white precipitate that had formed was filtered off, the solvent was removed by a rotary evaporator to obtain a viscous liquid. 25.6 g of this liquid was placed in a pressure bottle type reaction vessel, and 32.9 g of monohydrogentriethoxysilane was added.
Was added and mixed and dissolved. Next, chloroplatinic acid (H ₂ PtC
The l ₆ · 6H ₂ 0) was heated in tetrahydrofuran, 0.
As a 02 mol% solution, a solution corresponding to 0.1 mmol of platinum was added to the above mixed solution, and the reaction vessel was heated to 80
Heated at ° C for 4 hours. After removing tetrahydrofuran, the solid substance was removed to obtain a viscous liquid. IR and NMR measurements showed that this liquid was an organosilicon compound represented by the formula (14).

[0030]

[Chemical formula 17]

[0031]

[Production Example 3] 4-pentenoic acid (20.0 g), propionic acid (14.8 g) and acetic anhydride (20.4 g) were weighed out and dissolved in a three-necked flask equipped with a reflux condenser, a stirrer and a gas introduction tube. After refluxing this solution for 2 hours, the acetic acid formed was removed by evaporation to obtain 4-pentenoic acid propionic acid complex anhydride. This 4-pentenoic acid propionic acid complex anhydride 2
0.7 g was put into another three-necked flask equipped with a reflux condenser, a stirrer and a gas introduction tube, 31.3 g of 3-mercaptopropylmethyldiethoxysilane and 300 ml of benzene were weighed and mixed with stirring. Further, a solution prepared by dissolving 0.2 g of azobisisobutyronitrile in 50 ml of benzene was added to this solution, and mixed by stirring. While continuing to stir
After bubbling with dry nitrogen gas for 1 hour at room temperature, the mixture was heated and refluxed near the boiling point of benzene for 12 hours. After completion of the reaction, the solvent was removed by a rotary evaporator to obtain a viscous liquid. IR and NMR measurements showed that this liquid was an organosilicon compound represented by the formula (15).

[0032]

[Chemical formula 18] (Where, Q is _{-CH 2 (CH 2) 2 CH} 2 SCH 2 CH 2 CH
Represents _2- . )

[0033]

[Production Example 4] 53.7 g of monohydrogenmethyldiethoxysilane and 34.4 g of 3-butenoic acid were weighed out and mixed and dissolved in a pressure-resistant bottle-type reaction vessel. Next, chloroplatinic acid (H ₂ PtCl ₆ · 6H ₂ 0) was heated in tetrahydrofuran to form a 0.02 mol% solution, and a solution corresponding to 0.2 mmol of platinum was added to the above mixed solution. ,
The reaction vessel was heated at 80 ° C. for 4 hours. After removing tetrahydrofuran, the solid substance was removed to obtain a viscous liquid. 66.1 g of the above liquid and 320 ml of tetrahydrofuran in a three-necked flask equipped with a reflux condenser, a stirrer and a gas introduction tube.
And 80 ml of triethylamine were weighed and mixed with stirring. While cooling with an ice bath and continuing stirring, add to this solution,
A solution of 27.8 g of propionic acid chloride in 100 ml of tetrahydrofuran was gradually added dropwise. After the addition was complete, stirring was continued for another 30 minutes.
After the white precipitate that had formed was filtered off, the solvent was removed by a rotary evaporator to obtain a viscous liquid. IR, NMR
Upon measurement, it was shown that this liquid was an organosilicon compound represented by the formula (16).

[0034]

[Chemical formula 19] (Where, Q is -CH ₂ CH ₂ CH ₂ - represents a.)

Metal-silicon composite alkoxides were prepared using the compounds of Production Examples 1 to 4.

[0036]

Example 1 Diethyl ether 10 dehydrated and purified by refluxing with sodium metal and distillation in a flask equipped with a reflux condenser and a stirrer, which was sufficiently dried and purged with argon.
0 ml was weighed out and 28.4 g of titanium tetraisopropoxide was dissolved therein. After thoroughly replacing the inside of the flask with argon, dehydrated and purified diethyl ether 10
A solution prepared by dissolving 47.0 g of the organosilicon compound of Production Example 1 was added to 0 ml, and the mixture was reacted at 30 ° C. for 20 hours while continuing stirring. After completion of the reaction, purification by vacuum distillation was performed to obtain a viscous liquid. IR, ₁ H-NMR, ₁₃ C-NMR, ₂₉ S
As a result of i-NMR measurement, this liquid was found to have the formula (17).
Was presumed to be a compound represented by

[0037]

[Chemical 20] (Where, Q is _{-CH 2 (CH 2) 8 CH} 2 SCH 2 CH 2 CH
Represents _2- . )

[0038]

Example 2 100 ml of diisopropyl ether dehydrated and purified by refluxing with sodium metal and distillation was weighed in a flask equipped with a reflux condenser and a stirrer, which was sufficiently dried and purged with argon, and zirconium tetraisopropoxy was added to this. 39.3 g of the solution was dissolved. Further, after thoroughly replacing the inside of the flask with argon, the organic silicon compound 3 of Production Example 2 was added to 100 ml of dehydrated and purified diisopropyl ether.
What melt | dissolved 9.0g was added, and it was made to react with the boiling point of diisopropyl ether for 20 hours, continuing stirring. After completion of the reaction, purification by vacuum distillation was performed to obtain a viscous liquid. IR, ₁ H-NMR, ₁₃ C-NMR, ₂₉ Si-NM
When R measurement was performed, it was estimated that this liquid was a compound represented by the formula (18).

[0039]

[Chemical 21]

[0040]

Example 3 50 ml of benzene dehydrated and refined by refluxing with sodium metal and distillation was placed in a flask equipped with a reflux condenser and a stirrer, which had been sufficiently dried and purged with argon, and 18.2 g of titanium tetraethoxide was added thereto. Was dissolved. Further, after thoroughly replacing the inside of the flask with argon, a solution of 55.5 g of the organosilicon compound of Production Example 3 dissolved in 70 ml of dehydrated and purified benzene was added, and the mixture was reacted for 24 hours at the boiling point of benzene while continuing stirring. After the reaction,
Purification by vacuum distillation gave a viscous liquid. IR, ₁
H-NMR, ₁₃ C-NMR, and ₂₉ Si-NMR measurements were performed, and it was estimated that this liquid was a compound represented by the formula (19).

[0041]

[Chemical formula 22] (Where, Q is _{-CH 2 (CH 2) 2 CH} 2 SCH 2 CH 2 CH
Represents _2- . )

[0042]

Example 4 50 ml of toluene dehydrated and purified by refluxing with metal sodium and distillation was weighed in a flask equipped with a reflux condenser and a stirrer, which was sufficiently dried and purged with argon, and zirconium tetra-n- 19.2 g of butoxide was dissolved with stirring. Furthermore, after thoroughly replacing the inside of the flask with argon, a solution prepared by dissolving 27.6 g of the organosilicon compound of Production Example 4 in 50 ml of dehydrated and purified toluene was added, and the mixture was reacted at the boiling point of toluene for 20 hours while continuing stirring. After completion of the reaction, purification by vacuum distillation was performed to obtain a viscous liquid. IR, ₁ H-NMR, ₁₃ C-NMR, ₂₉ Si
When NMR measurement was performed, it was estimated that this liquid was a compound represented by the formula (20).

[0043]

[Chemical formula 23] (Where, Q is -CH ₂ CH ₂ CH ₂ - represents a.)

[0044]

[Primer performance test] The metal-silicon composite alkoxides of Examples 1 to 4 were used to evaluate the characteristics of the titanium oxide film and zirconium oxide film coatings as a primer. (Test Method) Each of the metal-silicon composite alkoxides of Examples 1 to 4 was dissolved in tetrahydrofuran so as to be 0.1 mol% by weight, and each solution was spray-coated on a commercially available slide glass by using a spray device. . After drying this slide glass at room temperature for 4 hours, it is vacuumed at 150 ° C for 12 hours.
Heat treated for hours. To a solution prepared by dissolving 56.8 g of titanium tetraisopropoxide and 20 g of acetylacetone in 100 ml of ethyl alcohol was added a solution of 15 g of water dissolved in 50 ml of ethyl alcohol with stirring, and the stirring was continued at room temperature. (Hereinafter, this solution is abbreviated as solution A.) Separately zirconium tetra-n-butoxide 76.
To a solution prepared by dissolving 7 g and 20 g of acetylacetone in 100 ml of ethyl alcohol, a solution prepared by dissolving 15 g of water in 50 ml of ethyl alcohol was added with stirring, and the stirring was continued at room temperature. (Hereinafter, this solution is abbreviated as solution B.)
The slide glass treated with the metal-silicon composite alkoxide of Examples 1 and 3 was used as the solution A, and the slide glasses prepared in Examples 2 and 4 were used as the solution B.
After immersing each slide glass treated with the metal-silicon composite alkoxide of 1., pulled up at a rate of 500 mm / min, dried at room temperature, and then heat-treated under vacuum at 150 ° C. for 24 hours to obtain a titanium oxide film and a zirconium oxide film, respectively. Membrane coating was performed. Further, as a comparative example, a titanium oxide film and a zirconium oxide film were coated by the same method using untreated glass. The slide glass thus coated with the titanium oxide film and the zirconium oxide film was rubbed with steel wool under a load of 500 g, and the number of frictions until the coating film was peeled off was measured to determine the abrasion resistance of the coating film. Was evaluated. The results are shown in Table 1.

[0045]

[Table 1]

As can be seen from the results in Table 1, after treating the glass surface with the metal-silicon composite alkoxide of the present invention,
It was revealed that coating with titanium oxide or zirconium oxide dramatically improves the wear resistance by about 2 to 3 times as compared with the untreated coating film.

[0047]

By using the metal-silicon composite alkoxide of the present invention, it is possible to coat glass with a titanium oxide or zirconium oxide coating film having excellent wear resistance.

[Chemical formula 24]

Claims (2)

(57) [Claims] 1. A metal represented by the following general composition formula (1):
Silicon composite alkoxide. 2. An organic silicon compound represented by the following general composition formula (2) and a metal alkoxide represented by the following general composition formula (3) are reacted to produce the compound.
7. The metal-silicon composite alkoxide according to. [Chemical 1] (However, in the formula, M represents Ti or Zr, R represents an alkyl group, may be different from each other or may contain the same ones, and R ^* represents an alkyl group having 4 or less carbon atoms, They may be different or the same as each other, Q represents a divalent hydrocarbon group or a divalent organic group containing a sulfur atom, and different from each other include the same one. And X represents a monovalent hydrocarbon group, which may be different from each other or may contain the same ones, a is an integer of 0 to 2, and n is 1 to 2.) 2] (However, in the formula, R represents an alkyl group, which may be different from each other or may include the same ones, and Q is a divalent group.
Hydrocarbon group or divalent organic group containing sulfur atom
Where R'has a carbon number less than Q and a carbon number of 3 or more.
Represents a monovalent hydrocarbon group below, and X represents a monovalent hydrocarbon group.
May represent the same or different from each other, and a represents an integer of 0 to 2. ) [Chemical 3] (However, in the formula, M represents Ti or Zr, and R ^* represents an alkyl group having 4 or less carbon atoms, which may be different from each other or may be the same as each other.)