WO2008152744A1 - Bonding method, and biochemical chip and optical part produced using the method - Google Patents

Bonding method, and biochemical chip and optical part produced using the method Download PDF

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Publication number
WO2008152744A1
WO2008152744A1 PCT/JP2007/062547 JP2007062547W WO2008152744A1 WO 2008152744 A1 WO2008152744 A1 WO 2008152744A1 JP 2007062547 W JP2007062547 W JP 2007062547W WO 2008152744 A1 WO2008152744 A1 WO 2008152744A1
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Prior art keywords
covalently bonded
reactive functional
group
biochemical chip
functional group
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PCT/JP2007/062547
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French (fr)
Inventor
Kazufumi Ogawa
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Kazufumi Ogawa
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Priority to PCT/JP2007/062547 priority Critical patent/WO2008152744A1/en
Publication of WO2008152744A1 publication Critical patent/WO2008152744A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/22—Presence of unspecified polymer
    • C09J2400/226—Presence of unspecified polymer in the substrate

Definitions

  • the present invention relates to a bonding method of two members, and a biochemical chip and an optical part, which are produced using the bonding method. More particularly, the present invention relates to a biochemical chip produced by facing and bonding a pair of biochemical chip substrates processed to have a fine flow path or hole on the surface thereof, and a production method thereof, where the biochemical substrates are bonded without damaging the flow path or hole.
  • the biochemical chip includes a chemical chip, a biochip, a biochemical electrophoresis chip, a biochemical reactor, a biochemical fluidic system, a DAN chip and the like, which are used for a chemical experiment, a bio-experiment, medical diagnosis and the like.
  • the present invention relates to an optical part produced by facing and bonding a pair of optical members having flatness on the surface and optical characteristics on the bonding face as important properties, and a production method thereof, where the optical members are bonded without damaging the flatness and optical characteristics.
  • the optical part includes a lens, a prism, an optical fiber, an optical recording medium and the like.
  • An objective of the present invention is to provide a bonding method of a pair of biochemical chip substrates of which at least one is processed to have a fine hole and groove in a micron level, without damaging the fine hole and groove, that is, without covering those by adhesive, and without having gaps, and to provide a biochemical chip without a defect produced using the bonding method with low cost.
  • an objective of the present invention is to provide a bonding method without damaging optical characteristics on the bonding face, and to provide optical parts of which optical characteristics of bonding faces are not damaged with low cost.
  • a bonding method comprising: a step for producing a first member in which an organic thin film having a first reactive functional group is pre-formed; a step for producing a second member in which an organic thin film having a second reactive functional group enables to be reacted with the first reactive functional group is formed; and a step for contacting the first and second members so as to be bonded through the first and second organic thin films.
  • a 2nd invention is the bonding method in the 1st invention, in which at least the first reactive functional group is an epoxy group and the second reactive functional group is an imino group, or at least the first reactive functional group is an imino group and the second reactive functional group is an epoxy group.
  • a 3rd invention is the bonding method in the 1st and 2nd invention, in which at least the first or second reactive functional group is the epoxy group or the imino group, and the method comprises a step for: contacting a member to a chemisorption liquid produced by mixing an alkoxysilane compound containing the epoxy group or the imino group, a silanol condensing catalyst, and a non-aqueous solvent; reacting the surface of the member with the alkoxysilane compound containing the epoxy group or the imino group; and producing the first or second member having an organic thin film or a chemisorption monomolecular film which contains the epoxy group or the imino group as a reactive functional group.
  • a 4th invention is the bonding method in the 1st invention, in which when the first and second members are contacted and bonded, the first and second members are heated at the same temperatures.
  • a 5th invention is a biochemical chip, in which a first biochemical chip substrate and a second biochemical chip substrate are bonded by a covalent bond through at least an organic film covalently bonded to the surface of the first biochemical chip substrate and an organic film covalently bonded to the surface of the second biochemical chip substrate.
  • a 6th invention is the biochemical chip in the 5th invention, in which at least the organic film covalently bonded to the surface of the first biochemical chip substrate contains nitrogen, and the organic film covalently bonded to the surface of the second biochemical chip substrate contains oxygen.
  • a 7th invention is the biochemical chip in the 5th invention, in which at least the organic film covalently bonded to the surface of the first biochemical chip substrate and the organic film covalently bonded to the surface of the second biochemical chip substrate are a monomolecular film respectively.
  • a 8th invention is an optical part, in which a first optical member and a second optical member are bonded by a covalent bond through at least an organic film covalently bonded to the surface of the first optical member and an organic film covalently bonded to the surface of the second optical member.
  • a 9th invention is the optical part in the 8th invention, in which at least the organic film covalently bonded to the surface of the first optical member contains nitrogen, and the organic film covalently bonded to the surface of the second optical member contains oxygen.
  • a 10th invention is the optical part in the 8th invention, in which at least the organic film covalently bonded to the surface of the first optical member and the organic film covalently bonded to the surface of the second optical member are monomolecular films.
  • the present invention has the effect to bond a pair of biochemical chip substrates of which at least one is processed to have a fine hole and groove in a micron level without damaging the fine hole and groove, that is, without covering those by adhesive, and without having gaps, and to provide a biochemical chip without a defect with a high yield. Further, there is the effect to bond without damaging optical characteristics on the bonding face, and to provide an optical part having high characteristics by the high yield.
  • FIG.1 is a schematic view for explaining a process for bonding a pair of glass biochemical chip substrates in Example 1 of the present invention, where the process is expanded to the molecular level
  • FIG. 1A is a view of the surface of a first glass substrate before the reaction
  • FIG. 1 B is a view after forming a monomolecular film containing an epoxy group.
  • FIG.2 is a schematic view for explaining a process for bonding a pair of glass biochemical chip substrates in Example 1 of the present invention, where the process is expanded to the molecular level
  • FIG. 2A is a view of the surface of a second glass substrate before the reaction
  • FIG. 2B is a view after forming a monomolecular film containing an amino group.
  • FIG.3 is a schematic view for explaining a process for bonding a pair of glass biochemical chip substrates in Example 1 of the present invention, where the process is expanded to the molecular level, and schematic view illustrates a cross sectional state in which the first and second glass substrates are bonded.
  • the present invention is to produce and provide a biochemical chip and an optical member by: a step for producing a first member in which an organic thin film having a first reactive functional group is pre-formed; a step for producing a second member in which an organic thin film in the monomolecular film state having a second reactive functional group reacted with the first reactive functional group is formed; and a step for contacting the first and second members so as to be bonded through the monomolecular films.
  • a pair of biochemical chip substrates of which at least one is processed to have a fine hole and groove in a micron level can be bonded without damaging the fine hole and groove, that is, without covering those by adhesive, and without having gaps, and thus, a biochemical chip without a defect can be provided with high yield.
  • the optical parts can be bonded to have uniform thickness without damaging optical characteristics on the bonding face, and the optical parts having high characteristics can be provided with high yield.
  • the biochemical chip according to the present invention includes a chemical chip, a biochip, a biochemical electrophoresis chip, a biochemical reactor, a biochemical fluidic system, a DAN chip and the like, which are used for a chemical experiment, a bio-experiment, medical diagnosis and the like.
  • the optical part includes a lens, a prism, an optical fiber, an optical recording medium and the like.
  • the present invention will be described using a chemical chip and a lens as representative examples. [Example 1]
  • the first embodiment will be described in orders with FIGS. 1 , 2 and 3.
  • a pair of processed glass biochemical chip substrates 1 used for a chemical chip was prepared, well washed and dried (a plastic substrate such as an acrylic resin or the like might be used, but when the plastic substrate was used, it could be used like the glass substrate by thinly oxidizing the surface using corona treatment, excimer treatment, plasma treatment or the like, so as to have hydrophilicity).
  • the chemisorption liquid was prepared by the steps of: weighing 99 w.t.% of chemicals including a reactive functional group to a functional part as a chemical adsorbent, where the reactive functional group was the chemicals including, for example, the epoxy group at one end and an alkoxyl silyl group at another end, that is, for example, the chemicals shown in the following formula (1); weighing 1 w.t.% of dibutyl-tin diacetylacetonate as the silanol condensing catalyst; and solving the above-described weighed chemical materials in a silicone solvent, for example, a hexamethyldisiloxane solvent so as to have the total concentration of about 1 w.t.% (the concentration of the chemical adsorbent was preferably about 0.5 to 3%).
  • a silicone solvent for example, a hexamethyldisiloxane solvent
  • the chemisorption liquid was coated on the surfaces of the glass substrates, and reacted at a normal atmosphere (a relative humidity was 45%) for 2 hours.
  • a -Si(OCH 3 ) group in the chemical adsorbent and the hydroxyl groups 2 were dealcoholation-reacted (in this case, deCH 3 OH-reacted) under the existence of the silanol condensing catalyst, so as to form a bond shown in the following formula (2).
  • a chemisorption monomolecular film 3 containing the epoxy group was formed to have the film thickness of about 1 nm, where the film 3 was chemically bonded to the whole surfaces of the glass substrates.
  • the monomolecular film formed by the above-described treatment had the film thickness in a nano meter level and was remarkably thin, the thickness of the glass was not changed and the flow path and hole which were pre-processed were not damaged.
  • a glass biochemical chip substrate 5 which had been already processed, was prepared and well dried. Then, a chemisorption liquid was prepared by the steps of:; weighing 99 wt.% of chemicals including reactive functional group to the functional part as the chemical adsorbent, where the reactive functional group was the chemicals including the imino group (-NH), which was reacted with the epoxy group, at one end and the alkoxyl silyl group at another end.
  • a chemisorption liquid was prepared by the steps of:; weighing 99 wt.% of chemicals including reactive functional group to the functional part as the chemical adsorbent, where the reactive functional group was the chemicals including the imino group (-NH), which was reacted with the epoxy group, at one end and the alkoxyl silyl group at another end.
  • the chemicals shown in the following chemical formula (3) where the chemicals included an amino group at an end thereof; weighing 1 wt.% of acetic acid which was organic acid instead of the silanol condensing catalyst; and solving the above-described weighed chemical materials in a silicone solvent, for example, a mixing solvent of hexamethyldisiloxane and dimethylformamide (50:50).
  • a silicone solvent for example, a mixing solvent of hexamethyldisiloxane and dimethylformamide (50:50).
  • the concentration of the chemical adsorbent was preferably about 0.5 to 3 %.
  • the glass substrate 5 was dipped in this chemisorption liquid and reacted for about 2 hours at a normal atmosphere (the relative humidity was 45%).
  • a -Si(OCH 3 ) group and the hydroxyl groups of the chemical adsorbent were dealcoholation-reacted (in this case, deCH 3 OH-reacted) under the existence of the acetic acid, so as to from the bond shown in the following chemical formula (4).
  • a chemisorption monomolecular film 7 containing the amino group was formed to have the film thickness of about 1 nm, where the film 7 was chemically bonded to the whole glass surface.
  • the glass substrate was washed with chloroform or n-methylpyrrolidinon, so that a second glass biochemical chip substrate 8 covered with a chemisorption monomolecular film having the reactive functional group, for example, the amino group on the surface thereof could be produced.
  • the organic acid such as acetic acid or the like was preferable since a tin-based catalyst was precipitated.
  • the amino group contained the imino group, a pyrrole derivative, an imidazol derivative or the like could be used as a material containing the imino group except the amino group.
  • a ketimine derivative the amino group could be easily induced by hydrolysis after forming the film.
  • th-e monomolecular film 7 formed by the above-described treatment had the film thickness in a nano meter level and was remarkably thin, the thickness of the glass was not changed, and the flow path and hole which were pre-processed were not damaged.
  • the solvent was vaporized and the chemical adsorbent remained on the surface of the glass substrate was reacted with moisture in the atmosphere, so as to form a remarkable-thin organic film (the polymer film in this case) including the chemical adsorbent on the surface thereof.
  • the film although the film thickness was thick a little, reactivity at the time of bonding was hardly changed.
  • the first glass biochemical chip substrate covered with the chemisorption monomolecular film having the epoxy group was contacted with the second glass biochemical chip substrate covered with the chemical adsorption monomolecular film having the amino group on the surface thereof, while facing each other, and these were heated at 100 degree C for 30 minutes from the both outsides.
  • a biochemical chip 9 was obtained by the reaction shown in the following chemical formula (5), where the epoxy group and the amino group were addition-reacted so as to bond the two glass biochemical chip substrates through the two monomolecular films.
  • a symbol 10 shows a bond generated by reacting the epoxy group with the amino group.
  • the total thickness of the film of the formed bonding layer was about 1 nm, so that transparency on the bonding face was not damaged at all. Further, since the bonding thickness was remarkably thinner than the wavelength of visible light, there is no loss of the light on the bonding interface.
  • a (CH 2 OCH) group is a functional group shown in the following formula (6)
  • a (CH 2 CHOCH) (CH 2 ) 2 ) CH group is a functional group shown in the following formula (7).
  • a metal carboxylate, a metal carboxylate ester, a metal carboxylate polymer, a metal carboxylate chelate, a titanic acid ester, a titanic acid ester chelate and the like can be used.
  • stannous acetic acid dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctanoate, dioctyltin diacetate, stannous dioctanate, lead naphthenate, cobalt naphthenate, 2-iron ethyl hexenoate, a dioctyltin bisoctylthioglycolate ester, a dioctyltin maleate ester, a dibutyltin maleate polymer, a dimethyltin mercapto propionate polymer, dibutyltin bisacetyl acetate, dioctyltin bisacetyl laurate, tetrabutyl titanate, tetranon
  • a solvent of the film forming solution an organic chlorine-based solvent not including aqueous, a hydrocarbon-based solvent, a carbon fluoride-based solvent, or a silicone-based solvent can be used.
  • a boiling point of the solvent is about 50 to 250 degree C.
  • non-aqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normalparaffin, decalin, industrial gasoline, nonane, deccan, kerosene, dimethylsilicone, phenylsilicone, alkyl-modified silicone, polyether silicone, dimethylformamide and the like can be used.
  • an alcohol-based solvent such as methanol, ethanol, propanol or the like, or a mixture of those can be used in addition to the above-described solvents.
  • carbon fluoride based solvent a chlorofluocarbon-based solvent
  • Fluorinate produced by 3M Corporation
  • Afroude produced by Asahi
  • Aluminum Corporation and the like can be used.
  • these solvent can be used independently or used by mixing two or more kinds if those enable to be mixed.
  • the organic chlorine-based solvent such as chloroform can be added.
  • the processing time could be shortened to about 1/2 to 2/3 although having the same concentration.
  • the silanol condensing catalyst when used by mixing with the ketimine compound, the organic acid, the aldimine compound, the enamine compound, the oxazolidine compound, or the aminoalkylalkoxy silane compound (although the mixing rate could be within the range of 1 :9 to 9:1 , the range of about 1 :1 was ordinary preferable), the processing time could be shortened more several times, and the time for forming the film could be shortened to one / several.
  • the ketimine compound, the organic acid, the aldimine compound, the enamine compound, the oxazolidine compound, and the aminoalkylalkoxy silane compound had higher activity than the silanol condensing catalyst.
  • the silanol condensing catalyst was used by mixing with one of the ketimine compound, the organic acid, the aldimine compound, the enamine compound, the oxazolidine compound, and the aminoalkylalkoxy silane compound, the reactivity became further higher.
  • the ketimine compound used in the present invention was not limited especially.
  • the followings could be used, that is, 2,5,8- triaza-1 ,8-nonadien, 3,11 -dimethyl-4,7, 10-triaza-3, 10-tridecadien,
  • organic acid used in the present invention was not limited especially.
  • formic acid, acetic acid, propionic acid, butyric acid, malonic acid or the like could be used, and approximately similar results could be obtained.
  • Example 1 An example of the glass biochemical chip was used in Example 1 , and an example of the optical lens was used in Example 2.
  • the present invention can be used for bonding general members.

Abstract

The present invention relates to a bonding method comprising: a step for producing a first member in which an organic thin film having a first reactive functional group is pre-formed; a step for producing a second member in which an organic thin film having a second reactive functional group which enables to be reacted with the first reactive functional group is formed; and a step for contacting the first and second members so as to be bonded through the first and second organic thin films.

Description

DESCRIPTION
BONDING METHOD, AND BIOCHEMICAL CHIPAND OPTICAL PART PRODUCED
USING THE METHOD
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a bonding method of two members, and a biochemical chip and an optical part, which are produced using the bonding method. More particularly, the present invention relates to a biochemical chip produced by facing and bonding a pair of biochemical chip substrates processed to have a fine flow path or hole on the surface thereof, and a production method thereof, where the biochemical substrates are bonded without damaging the flow path or hole.
In addition, the biochemical chip includes a chemical chip, a biochip, a biochemical electrophoresis chip, a biochemical reactor, a biochemical fluidic system, a DAN chip and the like, which are used for a chemical experiment, a bio-experiment, medical diagnosis and the like.
Further, the present invention relates to an optical part produced by facing and bonding a pair of optical members having flatness on the surface and optical characteristics on the bonding face as important properties, and a production method thereof, where the optical members are bonded without damaging the flatness and optical characteristics. In addition, the optical part includes a lens, a prism, an optical fiber, an optical recording medium and the like.
Description of Related Art
A technique for facing and bonding a pair of members using an instantaneous adhesive or an optical curing adhesive has been conventionally known (Japanese Patent Application Laid Open No. 2005-221478).
However, when at least one of a pair of members is processed to have a fine hole and groove in a micron level, it has been difficult to bond the members without damaging the fine hole and groove, that is, without covering those by adhesive, and without having gaps. Further, in a method using a conventional adhesive, since thickness nonuniformity of the adhesive or the like occurs on the bonding face, it has been very difficult to bond optical members such as a lens or the like without deteriorating optical characteristics.
An objective of the present invention is to provide a bonding method of a pair of biochemical chip substrates of which at least one is processed to have a fine hole and groove in a micron level, without damaging the fine hole and groove, that is, without covering those by adhesive, and without having gaps, and to provide a biochemical chip without a defect produced using the bonding method with low cost.
Further, an objective of the present invention is to provide a bonding method without damaging optical characteristics on the bonding face, and to provide optical parts of which optical characteristics of bonding faces are not damaged with low cost.
SUMMARY OF THE INVENTION Accordingly, it would be advantageous to provide a bonding method comprising: a step for producing a first member in which an organic thin film having a first reactive functional group is pre-formed; a step for producing a second member in which an organic thin film having a second reactive functional group enables to be reacted with the first reactive functional group is formed; and a step for contacting the first and second members so as to be bonded through the first and second organic thin films.
A 2nd invention is the bonding method in the 1st invention, in which at least the first reactive functional group is an epoxy group and the second reactive functional group is an imino group, or at least the first reactive functional group is an imino group and the second reactive functional group is an epoxy group. A 3rd invention is the bonding method in the 1st and 2nd invention, in which at least the first or second reactive functional group is the epoxy group or the imino group, and the method comprises a step for: contacting a member to a chemisorption liquid produced by mixing an alkoxysilane compound containing the epoxy group or the imino group, a silanol condensing catalyst, and a non-aqueous solvent; reacting the surface of the member with the alkoxysilane compound containing the epoxy group or the imino group; and producing the first or second member having an organic thin film or a chemisorption monomolecular film which contains the epoxy group or the imino group as a reactive functional group.
A 4th invention is the bonding method in the 1st invention, in which when the first and second members are contacted and bonded, the first and second members are heated at the same temperatures. A 5th invention is a biochemical chip, in which a first biochemical chip substrate and a second biochemical chip substrate are bonded by a covalent bond through at least an organic film covalently bonded to the surface of the first biochemical chip substrate and an organic film covalently bonded to the surface of the second biochemical chip substrate. A 6th invention is the biochemical chip in the 5th invention, in which at least the organic film covalently bonded to the surface of the first biochemical chip substrate contains nitrogen, and the organic film covalently bonded to the surface of the second biochemical chip substrate contains oxygen.
A 7th invention is the biochemical chip in the 5th invention, in which at least the organic film covalently bonded to the surface of the first biochemical chip substrate and the organic film covalently bonded to the surface of the second biochemical chip substrate are a monomolecular film respectively.
A 8th invention is an optical part, in which a first optical member and a second optical member are bonded by a covalent bond through at least an organic film covalently bonded to the surface of the first optical member and an organic film covalently bonded to the surface of the second optical member.
A 9th invention is the optical part in the 8th invention, in which at least the organic film covalently bonded to the surface of the first optical member contains nitrogen, and the organic film covalently bonded to the surface of the second optical member contains oxygen.
A 10th invention is the optical part in the 8th invention, in which at least the organic film covalently bonded to the surface of the first optical member and the organic film covalently bonded to the surface of the second optical member are monomolecular films. As described above, the present invention has the effect to bond a pair of biochemical chip substrates of which at least one is processed to have a fine hole and groove in a micron level without damaging the fine hole and groove, that is, without covering those by adhesive, and without having gaps, and to provide a biochemical chip without a defect with a high yield. Further, there is the effect to bond without damaging optical characteristics on the bonding face, and to provide an optical part having high characteristics by the high yield.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG.1 is a schematic view for explaining a process for bonding a pair of glass biochemical chip substrates in Example 1 of the present invention, where the process is expanded to the molecular level, FIG. 1A is a view of the surface of a first glass substrate before the reaction, and FIG. 1 B is a view after forming a monomolecular film containing an epoxy group.
FIG.2 is a schematic view for explaining a process for bonding a pair of glass biochemical chip substrates in Example 1 of the present invention, where the process is expanded to the molecular level, FIG. 2A is a view of the surface of a second glass substrate before the reaction, and FIG. 2B is a view after forming a monomolecular film containing an amino group.
FIG.3 is a schematic view for explaining a process for bonding a pair of glass biochemical chip substrates in Example 1 of the present invention, where the process is expanded to the molecular level, and schematic view illustrates a cross sectional state in which the first and second glass substrates are bonded.
DETAILED DESCRIPTION
The present invention is to produce and provide a biochemical chip and an optical member by: a step for producing a first member in which an organic thin film having a first reactive functional group is pre-formed; a step for producing a second member in which an organic thin film in the monomolecular film state having a second reactive functional group reacted with the first reactive functional group is formed; and a step for contacting the first and second members so as to be bonded through the monomolecular films. Therefore, by using the method of the present invention, a pair of biochemical chip substrates of which at least one is processed to have a fine hole and groove in a micron level can be bonded without damaging the fine hole and groove, that is, without covering those by adhesive, and without having gaps, and thus, a biochemical chip without a defect can be provided with high yield. Further, the optical parts can be bonded to have uniform thickness without damaging optical characteristics on the bonding face, and the optical parts having high characteristics can be provided with high yield.
Hereinafter, the present invention will be described more particularly using Examples. However, the present invention is not limited to these examples. For example, a metallic material can be applied.
The biochemical chip according to the present invention includes a chemical chip, a biochip, a biochemical electrophoresis chip, a biochemical reactor, a biochemical fluidic system, a DAN chip and the like, which are used for a chemical experiment, a bio-experiment, medical diagnosis and the like. In addition, the optical part includes a lens, a prism, an optical fiber, an optical recording medium and the like. However, the present invention will be described using a chemical chip and a lens as representative examples. [Example 1]
The first embodiment will be described in orders with FIGS. 1 , 2 and 3. First, a pair of processed glass biochemical chip substrates 1 used for a chemical chip was prepared, well washed and dried (a plastic substrate such as an acrylic resin or the like might be used, but when the plastic substrate was used, it could be used like the glass substrate by thinly oxidizing the surface using corona treatment, excimer treatment, plasma treatment or the like, so as to have hydrophilicity). Then, the chemisorption liquid was prepared by the steps of: weighing 99 w.t.% of chemicals including a reactive functional group to a functional part as a chemical adsorbent, where the reactive functional group was the chemicals including, for example, the epoxy group at one end and an alkoxyl silyl group at another end, that is, for example, the chemicals shown in the following formula (1); weighing 1 w.t.% of dibutyl-tin diacetylacetonate as the silanol condensing catalyst; and solving the above-described weighed chemical materials in a silicone solvent, for example, a hexamethyldisiloxane solvent so as to have the total concentration of about 1 w.t.% (the concentration of the chemical adsorbent was preferably about 0.5 to 3%). [Formula 1] O OC H 3
/ \ I
C H 2- C H C H2O (CH2) 3 S i — O C H 3
I
O C H 3
The chemisorption liquid was coated on the surfaces of the glass substrates, and reacted at a normal atmosphere (a relative humidity was 45%) for 2 hours. At this time, since many hydroxyl groups 2 were contained on the surfaces of the glass substrates 1 (FIG.1A), a -Si(OCH3) group in the chemical adsorbent and the hydroxyl groups 2 were dealcoholation-reacted (in this case, deCH3OH-reacted) under the existence of the silanol condensing catalyst, so as to form a bond shown in the following formula (2). Thereby, a chemisorption monomolecular film 3 containing the epoxy group was formed to have the film thickness of about 1 nm, where the film 3 was chemically bonded to the whole surfaces of the glass substrates.
Then, the glass substrates were washed with a chlorine based solvent such as chloroform or the like, so that a first glass biochemical chip substrate 4 covered with a chemisorption monomolecular film having the reactive epoxy group on the surface thereof could be produced (FIG.1B). [Formula 2]
O O -
/ \ I
CH2-C H C H2O (CH2) 3S i — O -
I o-
In addition, since the monomolecular film formed by the above-described treatment had the film thickness in a nano meter level and was remarkably thin, the thickness of the glass was not changed and the flow path and hole which were pre-processed were not damaged.
On the other hand, when the substrate was taken-out to the atmosphere without washing, the solvent was vaporized and the chemical adsorbent remained on the surface of the glass substrate was reacted with moisture in the atmosphere, so as to form a remarkable-thin organic film (the polymer film in this case) including the chemical adsorbent on the surface thereof.
As for this film, although the film thickness was thick a little, reactivity at the time of bonding was hardly changed.
Similarly, a glass biochemical chip substrate 5, which had been already processed, was prepared and well dried. Then, a chemisorption liquid was prepared by the steps of:; weighing 99 wt.% of chemicals including reactive functional group to the functional part as the chemical adsorbent, where the reactive functional group was the chemicals including the imino group (-NH), which was reacted with the epoxy group, at one end and the alkoxyl silyl group at another end. That is, for example, the chemicals shown in the following chemical formula (3), where the chemicals included an amino group at an end thereof; weighing 1 wt.% of acetic acid which was organic acid instead of the silanol condensing catalyst; and solving the above-described weighed chemical materials in a silicone solvent, for example, a mixing solvent of hexamethyldisiloxane and dimethylformamide (50:50). (Here, the concentration of the chemical adsorbent was preferably about 0.5 to 3 %.)
[Formula 3]
O C H3
1
H 2 N (C H2) a S i - O C H 3
I
O C H 3
T hen, the glass substrate 5 was dipped in this chemisorption liquid and reacted for about 2 hours at a normal atmosphere (the relative humidity was 45%). At this time, since many hydroxyl groups 6 were contained on the surface of the glass substrate 5 (Fig. 2A, a -Si(OCH3) group and the hydroxyl groups of the chemical adsorbent were dealcoholation-reacted (in this case, deCH3OH-reacted) under the existence of the acetic acid, so as to from the bond shown in the following chemical formula (4). Thereby, a chemisorption monomolecular film 7 containing the amino group was formed to have the film thickness of about 1 nm, where the film 7 was chemically bonded to the whole glass surface.
Then, the glass substrate was washed with chloroform or n-methylpyrrolidinon, so that a second glass biochemical chip substrate 8 covered with a chemisorption monomolecular film having the reactive functional group, for example, the amino group on the surface thereof could be produced. In addition, when the adsorbent containing the amino group was used, the organic acid such as acetic acid or the like was preferable since a tin-based catalyst was precipitated. Further, although the amino group contained the imino group, a pyrrole derivative, an imidazol derivative or the like could be used as a material containing the imino group except the amino group. Furthermore, by using a ketimine derivative, the amino group could be easily induced by hydrolysis after forming the film. [Formula 4]
O- i H 2 N ( C H2) 3 S i — O —
I
Figure imgf000009_0001
In addition, since th-e monomolecular film 7 formed by the above-described treatment had the film thickness in a nano meter level and was remarkably thin, the thickness of the glass was not changed, and the flow path and hole which were pre-processed were not damaged. On the other hand, when the substrate was taken-out to the atmosphere without washing, the solvent was vaporized and the chemical adsorbent remained on the surface of the glass substrate was reacted with moisture in the atmosphere, so as to form a remarkable-thin organic film (the polymer film in this case) including the chemical adsorbent on the surface thereof. As for the film, although the film thickness was thick a little, reactivity at the time of bonding was hardly changed.
Then, the first glass biochemical chip substrate covered with the chemisorption monomolecular film having the epoxy group was contacted with the second glass biochemical chip substrate covered with the chemical adsorption monomolecular film having the amino group on the surface thereof, while facing each other, and these were heated at 100 degree C for 30 minutes from the both outsides. As a result of this, a biochemical chip 9 was obtained by the reaction shown in the following chemical formula (5), where the epoxy group and the amino group were addition-reacted so as to bond the two glass biochemical chip substrates through the two monomolecular films. In the drawings, a symbol 10 shows a bond generated by reacting the epoxy group with the amino group. [Formula 5] o / \
- ( C H2) C H- C H2 + H 2 N CH2 -
→ - (CH2) C H C H2 -N H C H2 -
I O H
[Example 2]
Bonding similar to that of Example 1 was tried except an optical lens was used instead of the glass biochemical chip substrate.
In this case, the total thickness of the film of the formed bonding layer was about 1 nm, so that transparency on the bonding face was not damaged at all. Further, since the bonding thickness was remarkably thinner than the wavelength of visible light, there is no loss of the light on the bonding interface.
In addition, in the above-described Examples 1 and 2, the chemicals shown in the formulas (1) and (3) were used as the chemical adsorbent including the reactive group. However, in addition to the above-described adsorbents, the chemicals shown the following (1) to (16) could be used. Further, when the flatness of the bonding face was insufficient, the chemicals having the long molecular length like the chemicals (7) or (13) was used so as to improve degree of bonding margin with respect to the gap and ununiformity. (1) (CH2OCH) CH2O(CH2)7Si(OCH3)3
(2) (CH2OCH) CH2O(CH2)11Si(OCH3)3
(3) (CH2CHOCH) (CH2)2)CH(CH2)2Si(OCH3)3
(4) (CH2CHOCH) (CH2)2)CH(CH2)4Si(OCH3)3
(5) (CH2CHOCH) (CH2)2) CH(CH2)6Si(OCH3)3 (6) (CH2OCH) CH2O(CH2)7Si(OC2H5)3
(7) (CH2OCH) CH2O(CH2)HSi(OC2Hs)3
(8) (CH2CHOCH) (CH2)2) CH(CH2)2Si(OC2H5)3 (9) (CH2CHOCH) (CH2)2) CH(CH2)4Si(OC2H5)3
(10) (CH2CHOCH) (CH2)2) CH(CH2)6Si(OC2H5)3
(11) H2N (CH2)5Si(OCH3)3
(12) H2N (CH2)7Si(OCH3)3 (13) H2N (CH2)9Si(OCH3)3
(14) H2N (CH2)5Si(OC2H5)3
(15) H2N (CH2)7Si(OC2H5)3
(16) H2N (CH2)9Si(OC2H5)3
In these formulas, a (CH2OCH) group is a functional group shown in the following formula (6), and a (CH2CHOCH) (CH2)2) CH group is a functional group shown in the following formula (7). [Formula 6]
O
/ \
C H 2- C H -
[Formula 7] O C H — C H 2
\ / \
C H C H -
\ /
C H 2-C H 2
In addition, in Examples 1 and 2, as the silanol condensing catalyst, a metal carboxylate, a metal carboxylate ester, a metal carboxylate polymer, a metal carboxylate chelate, a titanic acid ester, a titanic acid ester chelate and the like can be used. More particularly, the followings can be used, that is, stannous acetic acid, dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctanoate, dioctyltin diacetate, stannous dioctanate, lead naphthenate, cobalt naphthenate, 2-iron ethyl hexenoate, a dioctyltin bisoctylthioglycolate ester, a dioctyltin maleate ester, a dibutyltin maleate polymer, a dimethyltin mercapto propionate polymer, dibutyltin bisacetyl acetate, dioctyltin bisacetyl laurate, tetrabutyl titanate, tetranonyl titanate, and a bis(acetylacetonyl)dipropyl titanate.
Further, as a solvent of the film forming solution, an organic chlorine-based solvent not including aqueous, a hydrocarbon-based solvent, a carbon fluoride-based solvent, or a silicone-based solvent can be used. In addition, when the solvent is evaporated so as to increase the particulate concentration without washing, it is preferable that a boiling point of the solvent is about 50 to 250 degree C.
More particularly, non-aqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normalparaffin, decalin, industrial gasoline, nonane, deccan, kerosene, dimethylsilicone, phenylsilicone, alkyl-modified silicone, polyether silicone, dimethylformamide and the like can be used.
Further, when the adsorbent based on alkoxysilane is used and the solvent is evaporated so as to form the organic film, an alcohol-based solvent such as methanol, ethanol, propanol or the like, or a mixture of those can be used in addition to the above-described solvents.
Further, as the carbon fluoride based solvent, a chlorofluocarbon-based solvent, Fluorinate (produced by 3M Corporation), Afroude (produced by Asahi
Aluminum Corporation) and the like can be used. In addition, these solvent can be used independently or used by mixing two or more kinds if those enable to be mixed. Further, the organic chlorine-based solvent such as chloroform can be added.
On the other hand, instead of the above-described silanol condensing solvent, when the ketimine compound, an organic acid, the aldimine compound, the enamine compound, the oxazolidine compound, or the aminoalkylalkoxy silane compound were used, the processing time could be shortened to about 1/2 to 2/3 although having the same concentration.
Further, when the silanol condensing catalyst was used by mixing with the ketimine compound, the organic acid, the aldimine compound, the enamine compound, the oxazolidine compound, or the aminoalkylalkoxy silane compound (although the mixing rate could be within the range of 1 :9 to 9:1 , the range of about 1 :1 was ordinary preferable), the processing time could be shortened more several times, and the time for forming the film could be shortened to one / several.
For example, when the process was carried out under the same conditions except H3 which was the ketimine compound produced by Japan Epoxy Resin Corporation was used instead of the dibutyltin oxide which was the silanol catalyst, approximately similar results could be obtained except the reaction time could be shortened to about 1 hour. Further, when the process was carried out under the same conditions except a mixture (having the mixing ratio of 1 :1) of H3 which was the ketimine compound produced by Japan Epoxy Resin Corporation and the dibutyltin bisacetyl acetonate which was the silanol catalyst was used, approximately similar results could be obtained except the reaction time could be shortened to about 20 minutes. Therefore, it was clear that the ketimine compound, the organic acid, the aldimine compound, the enamine compound, the oxazolidine compound, and the aminoalkylalkoxy silane compound had higher activity than the silanol condensing catalyst.
Furthermore, when the silanol condensing catalyst was used by mixing with one of the ketimine compound, the organic acid, the aldimine compound, the enamine compound, the oxazolidine compound, and the aminoalkylalkoxy silane compound, the reactivity became further higher.
In addition, in this case, the ketimine compound used in the present invention was not limited especially. For example, the followings could be used, that is, 2,5,8- triaza-1 ,8-nonadien, 3,11 -dimethyl-4,7, 10-triaza-3, 10-tridecadien,
2 , 10-d imethyl-3 , 6 , 9-triaza-2 , 9-u ndecad ien , 2,4, 12, 14-tetramethyl-5,8,11 -triaza-4, 11 -pentadecadien, 2,4,15, 17-tetramethyl-5,8, 11 , 14-tetraaza-4, 14-octadecadien, 2,4,20,22-tetramethyl-5,12,19-triaza-4,19-trieicosadien, and the like. Further, the organic acid used in the present invention was not limited especially. For example, formic acid, acetic acid, propionic acid, butyric acid, malonic acid or the like could be used, and approximately similar results could be obtained.
An example of the glass biochemical chip was used in Example 1 , and an example of the optical lens was used in Example 2. However, of course, the present invention can be used for bonding general members.

Claims

1. A bonding method comprising: a step for producing a first member in which an organic thin film having a first reactive functional group is pre-formed; a step for producing a second member in which an organic thin film having a second reactive functional group reacted with the first reactive functional group is formed; and a step for contacting the first and second members so as to be bonded through the first and second organic thin films.
2. The bonding method according to claim 1 , wherein at least the first reactive functional group is an epoxy group and the second reactive functional group is an imino group, or at least the first reactive functional group is an imino group and the second reactive functional group is an epoxy group.
3. The bonding method according to claim 2 in which at least the first or second reactive functional group is the epoxy group or the imino group, the method comprising, a step for contacting a member to a chemisorption liquid produced by mixing an alkoxysilane compound containing the epoxy group or the imino group, a silanol condensing catalyst, and a non-aqueous organic solvent; reacting the surface of the member with the alkoxysilane compound containing the epoxy group or the imino group; and producing the first or second member having an organic thin film or chemisorption monomolecular film which contains the epoxy group or the imino group as a reactive functional group.
4. The bonding method according to claim 1 , wherein when the first and second members are contacted and bonded, the first and second members are heated at the same temperatures.
5. A biochemical chip, wherein a first biochemical chip substrate and a second biochemical chip substrate are bonded by a covalent bond through at least an organic film covalently bonded to the surface of the first biochemical chip substrate and an organic film covalently bonded to the surface of the second biochemical chip substrate.
6. A biochemical chip according to claim 5, wherein at least the organic film covalently bonded to the surface of the first biochemical chip substrate contains nitrogen, and the organic film covalently bonded to the surface of the second biochemical chip substrate contains oxygen.
7. The biochemical chip according to claim 5, wherein at least the organic film covalently bonded to the surface of the first biochemical chip substrate and the organic film covalently bonded to the surface of the second biochemical chip substrate are monomolecular films respectively.
8. An optical part, wherein a first optical member and a second optical member are bonded by a covalent bond through at least an organic film covalently bonded to the surface of the first optical member and an organic film covalently bonded to the surface of the second optical member.
9. The optical part according to claim 8, wherein at least the organic film covalently bonded to the surface of the first optical member contains nitrogen, and the organic film covalently bonded to the surface of the second optical member contains oxygen.
10. The optical part according to claim 8, wherein at least the organic film covalently bonded to the surface of the first optical member and the organic film covalently bonded to the surface of the second optical member are monomolecular films.
PCT/JP2007/062547 2007-06-15 2007-06-15 Bonding method, and biochemical chip and optical part produced using the method WO2008152744A1 (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0425142A (en) * 1990-05-21 1992-01-28 Matsushita Electric Ind Co Ltd Manufacture of bonded material and connection of electronic component
JPH076938A (en) * 1993-04-23 1995-01-10 Canon Inc Solid phase bonding
JPH11335631A (en) * 1998-04-28 1999-12-07 Degussa Huels Ag Method for bonding two solids to each other and structural material
JP2003246971A (en) * 2002-02-25 2003-09-05 Kansai Tlo Kk Method for adhering foil or film, and target for measuring shock wave speed, obtained by the method
WO2004043853A1 (en) * 2002-11-13 2004-05-27 Nippon Soda Co., Ltd. Dispersoid having metal-oxygen bond, metal oxide film, and monomolecular film
JP2007033167A (en) * 2005-07-26 2007-02-08 Kagawa Univ Biochemical chip and its manufacturing method
JP2007161912A (en) * 2005-12-15 2007-06-28 Kagawa Univ Adhesion method and biochemical chip produced by the method and optical part

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0425142A (en) * 1990-05-21 1992-01-28 Matsushita Electric Ind Co Ltd Manufacture of bonded material and connection of electronic component
JPH076938A (en) * 1993-04-23 1995-01-10 Canon Inc Solid phase bonding
JPH11335631A (en) * 1998-04-28 1999-12-07 Degussa Huels Ag Method for bonding two solids to each other and structural material
JP2003246971A (en) * 2002-02-25 2003-09-05 Kansai Tlo Kk Method for adhering foil or film, and target for measuring shock wave speed, obtained by the method
WO2004043853A1 (en) * 2002-11-13 2004-05-27 Nippon Soda Co., Ltd. Dispersoid having metal-oxygen bond, metal oxide film, and monomolecular film
JP2007033167A (en) * 2005-07-26 2007-02-08 Kagawa Univ Biochemical chip and its manufacturing method
JP2007161912A (en) * 2005-12-15 2007-06-28 Kagawa Univ Adhesion method and biochemical chip produced by the method and optical part

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