JP2007031349A - 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. <P>SOLUTION: This silane derivative is represented by the general formula [1], wherein, n is an integer of 1 to 20; R<SP>1</SP>to R<SP>10</SP>are each H, an alkyl, or the like; X<SP>1</SP>to X<SP>3</SP>are a halogen or an alkoxy; Y is an ester bond, or the like. <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 there are still practical problems such as sensitivity 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 benzoinyl group can form an organic thin film on the substrate surface, and the benzoinyl group can be removed at a relatively low energy by irradiation with ultraviolet rays of 250 nm or more. It was found that it was separated and converted to hydrophilicity, and the present invention was completed.

（式中、ｎは１〜２０の整数を表し、R¹〜R¹⁰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、それぞれ独立してハロゲン原子、又は炭素数１〜５のアルコキシ基を表す。Yは、一般式［２］〜［７］で表される結合を示す。）

That is, the present invention provides a silane derivative characterized by containing a benzoinyl group, a halogen atom and / or an alkoxy group, and represented by the following general formula [1] It is.

(In the formula, n represents an integer of 1 to 20, and R ^{1 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, Represents an alkoxy group that may have a substituent, a phenyl group that may have a substituent, a benzyl group that may have a substituent, a nitro group, a cyano group, an amino group, an aryl group, and an adjacent group. And X ^{1 to} X ³ each independently represents a halogen atom or an alkoxy group having 1 to 5 carbon atoms, and Y represents a general formula [2 ] To [7].

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 formula, n represents the integer of 1-20.

R ^{1 to} R ¹⁰ 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, It 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 benzoinyl group include benzoinyl group, 3′-methoxybenzoinyl group, 3′-5′-dimethoxybenzoinyl group, 3,3 ′, 4,4′-dimethylenedioxybenzoinyl group, 3 , 3 ′, 4,4′-tetramethoxybenzoinyl group, 4′-perfluorooctylbenzoinyl group, and the like.

X ^{1 to} X ³ each independently represent a halogen atom such as a chlorine atom or a bromine atom, or 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 formulas [2] to [7].

In the present invention, the silane derivative can be synthesized by a known method. Reacting a double bond-containing compound represented by the general formula [8] with a silane compound represented by the general formula [9] in a hydrosilylation reaction using hexachloroplatinic acid (IV) hexahydrate as a catalyst. Can be manufactured.

When Y is an oxycarbonyl group represented by the general formula [2], the double bond-containing compound generates an ester using a carboxylic acid having a double bond and a benzoin derivative as raw materials. The esterification reaction can be produced by converting a carboxylic acid having a double bond into an acid chloride by a known method using thionyl chloride and the like, and reacting in the presence of a benzoin derivative and a tertiary amine. It can also be produced by reacting a carboxylic acid having a double bond and a benzoin derivative in the presence of carbodiimides.

Benzoin derivatives include benzoin, 3'-methoxybenzoin, 3'-5'-dimethoxybenzoin, 3,3 ', 4,4'-dimethylenedioxybenzoin, 3,3', 4,4'-tetramethoxybenzoin, Examples thereof include 4'-perfluorooctylbenzoin.

Examples of the carboxylic acid having a double bond include acrylic acid, methacrylic acid, 4-pentenoic acid, 5-hexenoic acid, and 10-undecenoic acid.

When Y is an oxysulfonyl group represented by the general formula [4], the double bond-containing compound is obtained by converting a sulfonic acid having a double bond into an acid chloride by a known method using thionyl chloride, etc. Can be produced by reacting with a benzoin derivative. Examples of the sulfonic acid having a double bond include 3-butenesulfonic acid, 5-hexenesulfonic acid, 7-octenesulfonic acid, 9-decenesulfonic acid, and 10-undecenesulfonic acid.

When Y is an oxyphosphonyl group represented by the general formula [5], the double bond-containing compound is obtained by converting a phosphonic acid having a double bond into an acid chloride by a known method using thionyl chloride or the like. It can be produced by reacting with a benzoin derivative in the presence of an amine.

In the case where Y is a sulfonyl group represented by the general formula [6], the double bond-containing compound is obtained by converting a sulfinic acid having a double bond into an acid chloride by a known method using thionyl chloride or the like. It can be produced by reacting with a benzoin derivative in the presence. Examples of the sulfinic acid having a double bond include 3-butene sulfinic acid, 5-hexene sulfinic acid, 7-octene sulfinic acid, 9-desense sulfinic acid, and 10-unsense sulfinic acid.

In the case where Y is an oxyamide group represented by the general formula [3], for example, a benzoin derivative is reacted in the presence of NN′-disuccinimidyl carbonate and a tertiary amine to form a carbonate and an amino group. It can be directly produced by reacting with a silane compound without going through a hydrosilylation reaction.

When Y is a thioether group represented by the general formula [7], the corresponding silane compound having a thiol group is reacted with an α-bromobenzoylphenyl ketone derivative in the presence of sodium hydride without going through a hydrosilylation reaction. Can be manufactured directly. Examples of the corresponding silane compound having a thiol group include 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.

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. Moreover, before forming an organic thin film, it is desirable to use it after washing | cleaning with cleaning agents, such as distilled water, ion-exchange water, alcohol, ozone, and an ultrasonic wave.

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, in order to remove the organic molecular layer that overlaps the multilayer. It is desirable to wash with a solvent. 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, low-pressure mercury 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 and used according to the strength, lamp shape, and the like.

(Function)
The silane derivative of the present invention is a silane derivative containing a benzoinyl group and a halogen atom and / or an alkoxy group. The surface of an organic thin film formed body formed by forming an organic thin film containing the silane derivative of the present invention on a substrate is hydrophobic. However, the benzoinyl group in the organic thin film is photodetached with a relatively high sensitivity by irradiation with ultraviolet rays of 250 nm or more, and changes to hydrophilicity. 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 In a stirred solution of 5.05 g (50 mmol) of triethylamine, 12.11 g (50 mmol) of 3′-methoxybenzoin dissolved in 75 ml of benzene, 5.93 g (50 mmol) of silane derivative 1 was dissolved. 4-Pentenoic acid chloride was added. The mixture was stirred for an additional 4 hours. The mixture was evaporated to dryness under reduced pressure and the solid was placed in a mixture of ether and water. The ether layer was separated and dried over magnesium sulfate. Subsequently, the solid obtained by evaporating the ether was crystallized from absolute ethanol to obtain 12.97 g of 3'-methoxybenzoinyl-7-octenoate.
Next, 0.32 g (1 mmol) of 3′-methoxybenzoinyl-7-octenoate and 0.20 g (1.2 mmol) of triethoxysilane were dissolved in 10 ml of dioxane, and about 1 mg of chloroplatinic acid was added. And refluxed for 3 days under a nitrogen atmosphere. After the reaction solution was concentrated, chloroform was added to the concentrate, the platinum catalyst was removed by filtration, and the filtrate was concentrated to obtain silane derivative 1.

Synthesis example 2
Synthesis of Silane Derivative 2 10.12 g (50 mmol) in a stirred solution of 5.05 g (50 mmol) of triethylamine, 12.11 g (50 mmol) of 3′-methoxybenzoin dissolved in 75 ml of benzene. 10-Undecenoic acid chloride was added. The mixture was stirred for an additional 4 hours. The mixture was evaporated to dryness under reduced pressure and the solid was placed in a mixture of ether and water. The ether layer was separated and dried over magnesium sulfate. Subsequently, the solid obtained by evaporating ether was crystallized from absolute ethanol to obtain 15.91 g of 3′-methoxybenzoinyl-10-undecenoate.
Next, 0.41 g (1 mmol) of 3′-methoxybenzoinyl-10-undecenoate and 0.20 g (1.2 mmol) of triethoxysilane were dissolved in 10 ml of dioxane, and about 1 mg of chloroplatinic acid was added. And refluxed for 3 days under a nitrogen atmosphere. After the reaction solution was concentrated, chloroform was added to the concentrate, the platinum catalyst was removed by filtration, and the filtrate was concentrated to obtain silane derivative 2.

Synthesis example 3
Triethylamine 5.05 g (50 mmol) in benzene Synthesis 75ml silane derivative 3 To a stirred solution were added and dissolved 12.11g (50 mmol) 3'-methoxy benzoin, 10.43 g (50 mmol) 7-octene sulfonic acid chloride was added. The mixture was stirred for an additional 4 hours. The mixture was evaporated to dryness under reduced pressure and the solid was placed in a mixture of ether and water. The ether layer was separated and dried over magnesium sulfate. Subsequently, the solid obtained by evaporating the ether was crystallized from absolute ethanol to obtain 17.19 g of 3′-methoxybenzoinyl-7-octenesulfonate.
Next, 0.41 g (1 mmol) of 3′-methoxybenzoinyl-7-octenesulfonate and 0.20 g (1.2 mmol) of triethoxysilane were dissolved in 10 ml of dioxane, and about 1 mg of chloroplatinic acid was dissolved. In addition, the mixture was refluxed for 3 days under a nitrogen atmosphere. After the reaction solution was concentrated, chloroform was added to the concentrate, the platinum catalyst was removed by filtration, and the filtrate was concentrated to obtain silane derivative 3.

Synthesis example 4
Synthesis of Silane Derivative 4 In a stirred solution of 5.05 g (50 mmol) triethylamine, 12.11 g (50 mmol) 3′-methoxybenzoin dissolved in 75 ml benzene, 9.63 g (50 mmol) was dissolved. 7-octenesulfinic acid chloride was added. The mixture was stirred for an additional 4 hours. The mixture was evaporated to dryness under reduced pressure and the solid was placed in a mixture of ether and water. The ether layer was separated and dried over magnesium sulfate. Subsequently, the solid obtained by evaporating the ether was crystallized from absolute ethanol to obtain 15.33 g of 3′-methoxybenzoinyl-7-octenesulfinate.
Next, 0.40 g (1 mmol) of 3′-methoxybenzoinyl-7-octene sulfinate, 0.20 g (1.2 mmol) of triethoxysilane was dissolved in 10 ml of dioxane, and about chloroplatinic acid was dissolved. 1 mg was added and refluxed for 3 days under a nitrogen atmosphere. After the reaction solution was concentrated, chloroform was added to the concentrate, the platinum catalyst was removed by filtration, and the filtrate was concentrated to obtain silane derivative 4.

Synthesis example 5
Under a nitrogen atmosphere, 0.07 g 60% sodium hydride (3.00 mmol) was added to a 100 ml eggplant flask, the flask was placed in an ice bath and 0.49 g (2.50 mmol) 3-mercaptopropyltrimethoxysilane was added to 20 ml. A solution dissolved in dry tetrahydrofuran was added dropwise over 30 minutes. Next, a solution prepared by dissolving 0.97 g (2.50 mmol) of 4′-n-octyl-α-phenylphenacyl bromide in 10 ml of dry tetrahydrofuran was added dropwise over 20 minutes. Then, after stirring at room temperature for 1 day under a nitrogen atmosphere, the reaction solution was concentrated, 30 ml of dichloromethane was added, and the mixture was stirred for 30 minutes. The precipitated solid was removed by filtration, and the filtrate was concentrated and separated and purified by column chromatography to obtain silane derivative 5.

Synthesis Example 6
2.91 g (8.97 mmol) 4′-n-octylbenzoin, 2.31 g (9.02 mmol) N, N-disuccinimidyl carbonate, 2.02 ml (27.0 mmol) triethylamine, 20 ml of N, N-dimethylformamide was placed 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 3.33 g of 4′-n-octylbenzoinyl-N-hydroxysuccinimidyl carbonate. It was. Next, 1.45 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 6.

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 with a low-pressure mercury lamp (manufactured by USHIO INC., 5 mW / cm ² ), and the contact angle was measured every certain time. The results are shown in Table 1.

Examples 2-6
An organic thin film was obtained in the same manner as in Example 1 except that silane derivatives 2 to 6 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 6 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 benzoinyl group and a halogen atom and / or an alkoxy group. A silane derivative represented by the following general formula [1].

(In the formula, n represents an integer of 1 to 20, and R ^{1 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, Represents an alkoxy group that may have a substituent, a phenyl group that may have a substituent, a benzyl group that may have a substituent, a nitro group, a cyano group, an amino group, an aryl group, and an adjacent group. And X ^{1 to} X ³ each independently represents a halogen atom or an alkoxy group having 1 to 5 carbon atoms, and Y represents a general formula [2 ] To [7].

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.