JP2007031350A - Silane derivative and organic thin film-forming article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silane derivative for forming organic thin films which can selectively convert the surfaces of substrates from a hydrophobic property into a hydrophilic property by the irradiation of low energy ultraviolet rays obtained from a low cost general purpose ultraviolet ray source, and to provide an organic thin film-forming article containing the silane derivative on the surface of a substrate. <P>SOLUTION: This silane derivative comprises a β-nitrocinnamyl group, and a halogen atom and/or an alkoxy group. An organic thin film obtained from the silane derivative is hydrophobic, but can be changed into a hydrophilic property by irradiating the organic thin film with ultraviolet rays having wavelengths of ≥250 nm radiated from low cost mercury lamp light sources to photo-decompose the β-nitrocinnamyl group. The organic thin film is highly sensitive. Hence, the difference between the hydrophilic property and the hydrophobic property can be utilized to form various patterns on the surfaces of substrates. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a silane derivative that forms an organic thin film capable of selectively converting the surface of a substrate from hydrophobic to hydrophilic by irradiation with low-energy ultraviolet rays obtained from an inexpensive general-purpose ultraviolet light source in an electronic product, and the substrate The present invention relates to an organic thin film forming body containing the silane derivative on the surface.

  In an electronic product, the process of forming a pattern using a photolithographic method or the like is complicated, and a large amount of waste materials such as a photoresist material and a developer are discharged, and improvement is required in terms of environmental load. Therefore, development of a pattern forming method using a photosensitive organic thin film having a thickness of several nanometers and a photosensitive layer thickness of a single molecule has been performed.

  When a hydrophobic self-assembled monolayer formed on an arylsilane compound or alkylsilane compound such as phenyltrichlorosilane or benzyltrichlorosilane is irradiated with far-ultraviolet light having a wavelength of 193 nm, the silicon-carbon bond is broken. It is described that the substrate surface is hydrophilized. (Non-patent document 1) Further, it is disclosed that a hydrophobic monomolecular film formed from a silane derivative containing perfluorohydrocarbon can be converted to hydrophilic when irradiated with far-ultraviolet rays having a wavelength of 172 nm. (Patent Document 1)

  The above-described self-assembled monolayer can be converted from hydrophobic to hydrophilic by irradiating with far-ultraviolet rays, but irradiating with far-ultraviolet rays as a light source is necessary. However, the far ultraviolet light source is expensive, and an inexpensive light source is desired. Mercury lamps are generally widely used as light sources and are inexpensive. Therefore, a highly sensitive photosensitive silane derivative is desired for ultraviolet rays emitted from an inexpensive mercury lamp.

  Therefore, o-nitrobenzyl ester-containing silane derivatives (Patent Documents 2 and 3), benzylphenyl sulfide group-containing silane derivatives (Patent Document 4), o-nitroanilide group-containing silane derivatives (Patent Document 5), and the like are disclosed. . All of these change to hydrophilicity by irradiation with a mercury lamp, but still have problems such as sensitivity in practical use, and further improvement is required.

Science, 1991, 252, 551-554 JP 2000-282240 A Japanese Patent Laid-Open No. 2002-80481 JP 2003-321479 A Japanese Patent Laid-Open No. 2003-301059 JP 2004-231590 A

  An object of the present invention is to provide a silane derivative that converts a hydrophobic organic thin film on a substrate surface into hydrophilicity by low-energy ultraviolet irradiation obtained from an inexpensive general-purpose ultraviolet light source.

  As a result of intensive studies to solve the above problems, the present inventors have found that a silane derivative containing a β-nitrocinnamyl group can form an organic thin film on the surface of the substrate. -The inventors have found that the nitrocinnamyl group is photodetached and converted into hydrophilicity, and have completed the present invention.

（式中、ｍは０又は１であり、ｎは１〜２０の整数を表す。R¹〜R⁵は、それぞれ独立して水素原子、ハロゲン原子、炭素数１〜２０のアルキル基、炭素数１〜２０のフルオロアルキル基、置換基を有しても良いアルコキシ基、置換基を有しても良いフェニル基、置換基を有しても良いベンジル基、ニトロ基、シアノ基、アミノ基、アリール基を表し、又、隣接して多核芳香族環又は多核複素環を形成しても良い。X¹〜X³は、それぞれ独立して炭素数１〜５のアルコキシ基を表す。R⁶は水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のフルオロアルキル基を表し、Yは、一般式［２］又は［３］で表される結合を示す。）

That is, the present invention is a silane derivative characterized by containing a β-nitrocinnamyl group, a halogen atom and / or an alkoxy group, and represented by the following general formula [1] Is to provide.

(In the formula, m is 0 or 1, and n represents an integer of ^{1 to} 20. Each of R ^{1 to} R ⁵ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number. 1 to 20 fluoroalkyl groups, optionally substituted alkoxy groups, optionally substituted phenyl groups, optionally substituted benzyl groups, nitro groups, cyano groups, amino groups, Represents an aryl group, and may be adjacent to form a polynuclear aromatic ring or polynuclear heterocycle, X ^{1 to} X ³ each independently represents an alkoxy group having 1 to 5 carbon atoms, R ⁶ is A hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, and Y represents a bond represented by the general formula [2] or [3].

The present invention also provides an organic thin film forming body in which an organic thin film containing the silane derivative of the present invention is formed on a substrate surface.

  Although the silane derivative of the present invention is hydrophobic, it can be photodecomposed and changed to hydrophilicity by irradiation with ultraviolet rays having a wavelength of 250 nm or more emitted from an inexpensive mercury lamp light source. Therefore, when a thin film is formed on the substrate surface with the silane derivative of the present invention, the substrate surface can be converted from hydrophobic to hydrophilic by ultraviolet irradiation. In addition, various materials can be patterned.

The silane derivative and organic thin film forming body of the present invention will be described in detail.
The silane derivative of the present invention is a compound represented by the general formula [1]. In the formula, m is 0 or 1, and n represents an integer of 1 to 20. R ⁶ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, Examples include heptyl group, octyl group, nonyl group, decyl group, dodecyl group, trifluoromethyl group, perfluorooctyl group and the like.

R ^{1 to} R ⁵ are each independently a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, C1-C20 alkyl groups such as heptyl, octyl, nonyl, decyl, dodecyl; fluoromethyl, trifluoromethyl, 2,2,2, -trifluoroethyl, heptafluoropropyl, C1-C20 fluoroalkyl group such as nonafluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorononyl group, perfluorodecyl group; methoxy group, ethoxy group, propoxy group, A substituent that may have a substituent such as isopropoxy group, butoxy group, t-butoxy group, trifluoromethoxy group, etc. Lucoxy group; may have a substituent such as phenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 2-nitrophenyl group, 3-methylphenyl group, 2,4-dimethoxyphenyl group, pentafluorophenyl group Good phenyl group; benzyl group, 4-chlorobenzyl group, 2-methylbenzyl group, 2,4-difluorobenzyl group, benzyl group which may have a substituent such as pentafluorobenzyl group; nitro group, cyano group, Represents an amino group, an aryl group, and is adjacent to a polynuclear aromatic ring such as 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group; quinolinyl group, isoquinolinyl group, A polynuclear heterocyclic ring such as an acridinyl group or anthronyl group may be formed.

Specific examples of the β-nitrocinnamyl group include β-nitrocinnamyl group, 4-methoxy-β-nitrocinnamyl group, 4-dodecyl-β-nitrocinnamyl group, 4-perfluorooctyl-β-nitrocinna Examples include a mill group.

X ^{1 to} X ³ each independently represents an alkoxy group having 1 to 5 carbon atoms such as a methoxy group, an ethoxy group, or a propoxy group.

Y represents a bond represented by the general formula [2] or [3].

In the present invention, the silane derivative can be synthesized by a known method. When Y is an oxyamide group represented by the general formula [2], for example, it is produced by reacting a β-nitrocinnamyl alcohol derivative in the presence of NN′-disuccinimidyl carbonate and a tertiary amine. It can be produced by reacting a carbonate with an amino group-containing silane compound. β-nitrocinnamyl alcohol derivatives include β-nitrocinnamyl alcohol, 4-methoxy-β-nitrocinnamyl alcohol, 4-dodecyl-β-nitrocinnamyl alcohol, 4-perfluorooctyl-β-nitrocinnamyl Examples include alcohol. Examples of the amino group-containing silane compound include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 4-aminobutyltriethoxysilane, m-aminophenyltrimethoxysilane, p-aminophenyltrimethoxysilane, p- Examples include aminophenyltrimethoxysilane.

When Y is an oxysulfonyl group represented by the general formula [3], a sulfonyl chloride group-containing silane compound such as 2- (4-chlorosulfonylphenyl) ethyltrimethoxysilane, and β- It can be produced by reacting a nitrocinnamyl alcohol derivative.

The organic thin film forming body of the present invention is characterized in that an organic thin film containing the silane derivative of the present invention is formed on the surface of a substrate. The substrate is not particularly limited as long as it can form an organic thin film containing the silane derivative of the present invention. Examples thereof include a glass substrate such as a soda glass plate, a substrate such as ITO glass on which an electrode is formed, a substrate on which an insulating layer is formed on a surface, a silicon substrate such as a silicon wafer substrate, and a ceramic substrate. Further, before forming the organic thin film, it is desirable to use after cleaning with ozone; ultrasonic; cleaning agents such as distilled water, ion-exchanged water and alcohol.

The method for forming an organic thin film containing a silane derivative on the substrate surface is not particularly limited. For example, the method of apply | coating the solution of a silane derivative to a base | substrate by a well-known method, and heat-drying a coating film is mentioned. Examples of the coating method include a coating method using a known coating apparatus such as a dipping method, a spin coater, or a die coater. Moreover, the method of arrange | positioning under the vapor | steam of a silane derivative, and carrying out chemical vapor deposition can also be utilized.

The solvent for dissolving the silane derivative is not particularly limited as long as it is inert to the silane derivative and dissolves the silane derivative. For example, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane and hexane, esters such as methyl acetate and ethyl acetate, ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane , Acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, alcohols such as methanol, and chlorine solvents such as chloroform and dichloromethane.

After forming the coating film of the silane derivative, it is desirable to heat at about 100 to 200 ° C. in order to remove the solvent and complete the film formation. In addition, it is desirable to perform solvent washing in order to remove the organic molecular layer that is stacked in multiple layers. The thickness of the obtained organic thin film layer is not particularly limited, but is usually about 1 to 100 nm.

The resulting organic thin film has the property that the hydrophobicity of the surface is lost by irradiation with ultraviolet rays and the surface becomes hydrophilic. This change can be confirmed by measuring the water contact angle of the surface. Therefore, after forming the organic thin film layer containing the silane derivative, the hydrophobic surface can be changed to hydrophilic in a pattern by irradiating ultraviolet rays in a pattern using a mask.

The metal wiring board can be manufactured by selectively adsorbing the metal catalyst on the surface using the difference between hydrophilicity and hydrophobicity on the formed board. Further, an offset printing plate can be produced by utilizing the difference in ink affinity on the surface of the plate cylinder. Furthermore, in screen printing or ink jet printing, by forming an organic thin film with the silane derivative of the present invention on an ink-receiving substrate, it is possible to control the lateral diffusion of printed dots. Moreover, a polymer graft substrate can also be produced by activating an organic acid group generated by ultraviolet irradiation by chemical treatment and then reacting a polyvalent functional group-containing compound containing a nucleophilic functional group with an organic acid. As the substrate to be used, those used for producing electronic / electrical elements such as metal wiring, medical diagnostic elements such as DNA chips and biochips, and biological elements such as neural circuits can be used.

As a light source used for the irradiation device, a so-called low-pressure mercury lamp whose mercury vapor pressure is 1 to 10 Pa during lighting, or a high-pressure mercury lamp having a pressure higher than that, an ultra-high-pressure mercury lamp with higher pressure, or a phosphor is applied. Mercury lamps, lasers, fluorescent tubes, cold cathode tubes, other discharge tubes, etc. can be used, and mercury lamps are particularly preferred in practice. The emission spectrum of the mercury lamp is in the range of 184 to 450 nm, which is suitable for efficiently photoreacting the organic thin film containing the silane derivative of the present invention. As mercury lamps, metal halide lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, xenon flash lamps, deep UV lamps, UV lasers, etc. have been put into practical use. It can be appropriately selected depending on the shape and the like.

(Function)
The silane derivative of the present invention is a silane derivative containing a β-nitrocinnamyl group and a halogen atom and / or an alkoxy group, and an organic thin film forming body formed by forming an organic thin film containing the silane derivative of the present invention on a substrate Although the surface is hydrophobic, the β-nitrocinnamyl group in the organic thin film is photodetached and changed to hydrophilicity with relatively high sensitivity when irradiated with ultraviolet rays of 250 nm or more. By irradiating the pattern with ultraviolet rays using a mask or the like, hydrophilic patterning can be formed.

Hereinafter, the present invention will be described in more detail with reference to examples.

Synthesis example 1
Synthesis of silane derivative 1 1.89 g (8.97 mmol) of 3-methoxy-β-nitrocinnamyl alcohol,
2.31 g (9.02 mmol) of N, N-disuccinimidyl carbonate, 2.02 ml (27.0 mmol) of triethylamine, 20 ml of N, N-dimethylformamide in a 50 ml eggplant flask purged with nitrogen And stirred at room temperature for 5 hours. Thereafter, N, N-dimethylformamide was distilled off, and the resulting crude product was purified by column chromatography to obtain 2.48 g of 3-methoxy-β-nitrocinnamyl-N-hydroxysuccinimidyl carbonate. It was. Next, 1.08 g (3.24 mmol) of this compound, 0.72 g (3.25 mmol) of 3- (triethoxysilyl) propylamine and 50 ml of dry tetrahydrofuran in a 100 ml eggplant-type flask purged with nitrogen. The mixture was stirred and stirred at room temperature for 3 hours. After the reaction, the solvent was distilled off, and the resulting crude product was purified by column chromatography to obtain silane derivative 1.

Synthesis example 2
Synthesis of silane derivative 2 1.89 g (8.97 mmol) of 3-methoxy-β-nitrocinnamyl alcohol,
2.31 g (9.02 mmol) of N, N-disuccinimidyl carbonate, 2.02 ml (27.0 mmol) of triethylamine, 20 ml of N, N-dimethylformamide in a 50 ml eggplant flask purged with nitrogen And stirred at room temperature for 5 hours. Thereafter, N, N-dimethylformamide was distilled off, and the resulting crude product was purified by column chromatography to obtain 2.48 g of 3-methoxy-β-nitrocinnamyl-N-hydroxysuccinimidyl carbonate. It was. Next, 1.08 g (3.24 mmol) of this compound, 0.77 g (3.25 mmol) of 4- (triethoxysilyl) butylamine, and 50 ml of dry tetrahydrofuran into a 100 ml eggplant-type flask purged with nitrogen. The mixture was stirred at room temperature for 3 hours. After the reaction, the solvent was distilled off, and the resulting crude product was purified by column chromatography to obtain silane derivative 2.

Synthesis example 3
Synthesis of silane derivative 3 1.89 g (8.97 mmol) of 3-methoxy-β-nitrocinnamyl alcohol,
2.31 g (9.02 mmol) of N, N-disuccinimidyl carbonate, 2.02 ml (27.0 mmol) of triethylamine, 20 ml of N, N-dimethylformamide in a 50 ml eggplant flask purged with nitrogen And stirred at room temperature for 5 hours. Thereafter, N, N-dimethylformamide was distilled off, and the resulting crude product was purified by column chromatography to obtain 2.48 g of 3-methoxy-β-nitrocinnamyl-N-hydroxysuccinimidyl carbonate. It was. Next, 1.08 g (3.24 mmol) of this compound, 0.83 g (3.25 mmol) of 1- (4-anilino) -propyltrimethoxysilane, 100 ml of eggplant with 50 ml of dry tetrahydrofuran substituted with nitrogen. The flask was placed in and stirred at room temperature for 3 hours. After the reaction, the solvent was distilled off, and the resulting crude product was purified by column chromatography to obtain silane derivative 3.

Synthesis example 4
Synthesis of Silane Derivative 4 In a stirred solution of 5.05 g (50 mmol) of triethylamine, 10.51 g (50 mmol) of 3-methoxy-β-nitrocinnamyl alcohol dissolved in 75 ml of benzene, 16.24 g (50 mmol) of 2- (4-chlorosulfonylphenyl) ethyltrimethoxysilane was added. The mixture was stirred for an additional 4 hours. After the reaction, the solvent was distilled off, and the resulting crude product was purified by column chromatography to obtain silane derivative 4.

Synthesis example 5
In a stirred solution of 5.05 g (50 mmol) triethylamine, 14.56 g (50 mmol) 4-n-octyl-β-nitrocinnamyl alcohol dissolved in 75 ml benzene, 16.24 g (50 mmol) was dissolved. 2- (4-chlorosulfonylphenyl) ethyltrimethoxysilane was added. The mixture was stirred for an additional 4 hours. After the reaction, the solvent was distilled off, and the resulting crude product was purified by column chromatography to obtain silane derivative 5.

Example 1
The silane derivative obtained in Synthesis Example 1 was dissolved in anhydrous toluene to obtain a solution having a concentration of 0.5% by weight. After ultrasonic cleaning with a detergent, followed by sequential cleaning with ion exchange water and ethanol, drying at 60 ° C. and immersing soda lime glass cleaned in an ozone generator in this solution, the substrate was pulled out and 10 ° C. at 150 ° C. Then, the multilayer adsorbed component was removed by ultrasonic cleaning in toluene, and an organic thin film of the silane derivative 1 was formed.
5 microliters of water was dripped using the micro syringe at the substrate surface in which the obtained organic thin film was formed, and it measured using the contact angle measuring device (Kyowa Interface Science company make CA-Z type) 60 seconds later. The surface of the substrate was irradiated with ultraviolet rays of 254 nm (sterile lamp, mW / cm ² ), and the contact angle was measured every certain time. The results are shown in Table 1.

Examples 2-5
An organic thin film was obtained in the same manner as in Example 1 except that silane derivatives 2 to 5 were used instead of silane derivative 1. The change of the water contact angle measurement of each obtained organic thin film and the water contact angle measurement by ultraviolet irradiation was measured. The results are also shown in Table 1.

As is clear from Table 1, the organic thin film obtained from the silane derivatives 1 to 5 of the present invention has a contact angle with water that decreases with time due to ultraviolet irradiation, and changes from hydrophobic to hydrophilic.

Although the silane derivative of the present invention is hydrophobic, it can be photodecomposed and changed to hydrophilicity by irradiation with ultraviolet rays having a wavelength of 250 nm or more emitted from an inexpensive mercury lamp light source, and has high sensitivity. Further, when a thin film is formed on the substrate surface with the silane derivative of the present invention, the substrate surface can be converted from hydrophobic to hydrophilic by ultraviolet irradiation. In addition, various materials can be patterned. Utilizing this property, it can be used to produce electronic / electric elements such as printing plates and metal wirings, medical diagnostic elements such as DNA chips and biochips, biological elements such as neural circuits, and the like.

Claims (3)

A silane derivative containing a β-nitrocinnamyl group and a halogen atom or an alkoxy group. A silane derivative represented by the following general formula [1].

(In the formula, m is 0 or 1, and n represents an integer of ^{1 to} 20. Each of R ^{1 to} R ⁵ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number. 1 to 20 fluoroalkyl groups, optionally substituted alkoxy groups, optionally substituted phenyl groups, optionally substituted benzyl groups, nitro groups, cyano groups, amino groups, Represents an aryl group, and may be adjacent to form a polynuclear aromatic ring or polynuclear heterocycle, X ^{1 to} X ³ each independently represents an alkoxy group having 1 to 5 carbon atoms, R ⁶ is A hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, and Y represents a bond represented by the general formula [2] or [3].

An organic thin film forming body in which an organic thin film containing the silane derivative according to claim 1 is formed on a substrate surface.