KR101826048B1 - Non-silicon plastic based bonding substrate and method of manufaturing the same - Google Patents

Abstract

A non-silicon-based plastic bonded substrate and a manufacturing method thereof are disclosed. The bonded substrate according to one embodiment of the present invention is a silane compound containing a mercapto group and is coated with a bonding surface to form a first substrate having an alkoxy group at its bonding surface and a second substrate having a hydroxyl group ), Wherein the first substrate and the second substrate are plastic substrates containing electrophiles and not containing silicon.

Description

TECHNICAL FIELD [0001] The present invention relates to a non-silicon-based plastic bonded substrate and a method of manufacturing the same. BACKGROUND ART [0002]

TECHNICAL FIELD The present invention relates to a bonded substrate and a method of manufacturing the same, and more particularly, to a non-silicon-based plastic bonded substrate formed by bonding plastic substrates not containing silicon and a method of manufacturing the same.

The micro total analysis system is a micro-analytical system that integrates sample preparation, separation, and detection systems on a small single chip. It is used in various fields of medicine, chemistry, biochemistry, biotechnology, It is attracting attention as a technology providing new analysis means.

Microcomputer analysis system is composed of several sub-systems such as microfluidic control system, chemical / biosensor, lab-on-a-chip, and element technology, among which chip manufacturing technology is the key. In chip manufacturing, poly (dimethylsiloxane) (PDMS) is the most widely used material. Because it can be easily bonded to PDMS or glass which is a silicon base material by a surface oxidation method.

In recent years, attempts have been made to utilize various materials in manufacturing microfluidic chips in addition to PDMS. For example, it is an attempt to bond a PDMS substrate, which is a silicon-based substrate, to a non-silicon-based substrate by an easier method or to bond non-silicon-based substrates by an easier method.

Patent Document 1: Korean Patent Laid-Open No. 10-2013-0141985 (published Dec. 21, 2013)

The present invention is intended to provide a bonded substrate which is formed by bonding plastic substrates that do not contain silicon.

The present invention also provides a method for producing a bonded substrate in which a plastic substrate not containing silicon is formed by mutual bonding.

According to one aspect of the present invention, a first substrate and a second substrate, which are formed by coating a bonding surface with a silane compound containing a mercapto group, wherein an alkoxy group is formed on the bonding surface, a hydroxyl group (-OH group) , Wherein the first substrate and the second substrate are provided with a bonded substrate which is a plastic substrate containing an electrophile and not containing silicon.

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The embodiments of the present invention can produce a non-silicon bonded substrate by coating a silane compound containing a mercapto group as a single chemical substance on a non-silicon based plastic substrate without a separate surface oxidation process, As a result, the entire manufacturing process can be simplified and manufacturing costs can be reduced.

1 is a schematic view illustrating a method of manufacturing a bonded substrate according to an embodiment of the present invention.
2 is a view showing a contact angle measurement result.
3 is an XPS analysis graph of PET.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The present invention can provide a bonded substrate in which a non-silicon based substrate and a non-silicon based substrate are bonded to each other. The present invention can further provide a bonded substrate in which a non-silicon based substrate and a PDMS (poly (dimethyl siloxane)) substrate are bonded to each other.

In the present specification, "non-silicon base material" means a plastic base material containing no silicon, a zirconia (3Y-ZrO ₂ ) base material or an alumina (α-Al ₂ O ₃ ) base material.

Here, the plastic substrate that does not contain silicon may be a polycarbonate (PC), a polyvinyl chloride (PVC), a polymethyl methacrylate (PMMA), a polyimide (PI), a polyethylene terephthalate (PET), a polyethersulfone ), Polyacrylate (PAR), polyetherimide (PEI), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyarylate (PAR), polyacrylonitrile PEK), polyetheretherketone (PEEK), poly (acrylonitrile-co-butadiene-co-styrene) (ABS), polyaramid, polybutylene terephthalate (PBT), polylactic acid (POM), polyurethane (PU), and nylon.

The non-silicon base material (plastic base material containing no silicon, zirconia base material or alumina base material) listed above may include an electrophile. For example, the non-silicon-based plastic substrates listed above contain a carbonate group or a carbonyl group as an electrophilic group, and the zirconia-based or alumina-based substrate includes an unsaturated outer electron or transition metal having an electrophilic property. The electrophile itself is positively polarized and has atoms lacking electrons to accept electrons from the nucleophile to form bonds.

On the other hand, the non-silicon base material constituting the bonded substrate may have a flat shape, but various fine patterns may be formed on at least one side of the surfaces of the two substrates (engraved pattern, relief pattern). For example, a fine indentation pattern is formed on one surface of one non-silicon based substrate and the other non-silicon based substrate is formed in a flat shape, so that the bonded substrate having the two non-silicon based substrates bonded together can have a fine channel. The same applies to the case where the non-silicon based substrate and the PDMS substrate constitute a bonded substrate.

The bonded substrate according to the present invention is formed by mutual bonding of the non-silicon based substrates, and the bonding can be performed by chemical bonding. Specifically, after the bonding surfaces of the non-silicone base materials are coated with a silane compound containing a mercapto group, a hydroxyl group (-OH) is formed on the bonding surfaces of the two non-silicone base materials and then bonded to form a siloxane bond Si-O-Si) can be formed. In addition, in the case of a bonded substrate in which a non-silicon based substrate and a PDMS substrate are bonded to each other, a bonding surface of the non-silicon based substrate is coated with a silane compound containing a mercapto group, (-OH) and bonding them to each other. This will be described later in detail.

Examples of the "mercapto group-containing silane compound" include 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, or 3-mercaptopropyltri But are not limited to, methoxysilane. For the sake of convenience of description, in the present specification, the case where the mercapto group-containing silane compound is 3-mercaptopropyltriethoxysilane (hereinafter referred to as 3-MPTES) will be mainly described.

The bonded substrate may be applied to a membrane, a microelectrode, a micro heater, a microfluidic chip, and the like, which are applied to a microfluidic system in a micro total analysis system.

Hereinafter, a method of manufacturing a bonded substrate according to an embodiment of the present invention will be described. 1 schematically shows a method of manufacturing a bonded substrate according to an embodiment of the present invention. Hereinafter, for convenience of description, the two non-silicon based substrates constituting the bonded substrate stack 100 will be referred to as a first substrate 110 and a second substrate 120, respectively.

Referring to FIGS. 1A and 1B, the first substrate 110, which is a non-silicon based substrate, includes an electrophile (in FIG. 1, δ + is an electrophilic site and δ- is a nucleophilic site). The mercapto group (to thiol group) of the silane compound (130) containing a mercapto group is negatively polarized as a strongest nucleophile among various organic compounds, and has an electron-rich atom, thereby giving electrons to the electrophile, And can easily form a bond with itself. Therefore, when the bonding surface (or the entire surface) of the first base material 110 is treated with the silane compound 130 containing a mercapto group, a chemical reaction (nucleophilic reaction) occurs between the terminal of the mercapto group and the electrophile of the first base material 110, the silane compound 130 containing a mercapto group may be coated on the surface of the first substrate 110 without a separate surface oxidation process after the nucleophilic reaction occurs (in FIG. 1, 3-MPTES is shown as an example of the silane compound And 3-MPTES is denoted by reference numeral 130 in the following). The nucleophilic reaction has the advantage that the reaction rate is relatively fast compared with the dehydration reaction and the like. On the other hand, the step of treating with the silane compound (130) containing a mercapto group can be carried out at room temperature. In addition, the coating may be performed by solution processes such as spin coating, dipping, spraying, and transferring after solving the silane compound 130 containing the mercapto group. For example, the first substrate 110 may be immersed in an aqueous solution of the silane compound (130) containing the mercapto group at room temperature for a certain period of time, followed by washing with distilled water, followed by drying.

The above-mentioned process will be described with reference to the accompanying drawings.

Referring to FIG. 1B, hydrolysis occurs at the alkoxy end of 3-MPTES 130 during the nucleophilic reaction between the mercapto group of 3-MPTES 130 and first substrate 110.

Referring next to FIG. 1C, the alkoxy end of the 3-MPTES 130 is hydrolyzed to produce ethanol molecules, which results in the crosslinking of adjacent 3-MPTES molecules 130.

Referring next to FIG. 1d, the 3-MPTES molecules 130 are grafted onto the first substrate 110 by a nucleophilic reaction between the mercapto group of the 3-MPTES 130 and the first substrate 110. That is, the bonding surface of the first substrate 110 is coated with the 3-MPTES 130.

As a result of coating the 3-MPTES 130 on the bonding surface of the first base material 110 through the above-described process, the alkoxy end is formed on the bonding surface of the first base material 110 as shown in FIG. 1E Fig. 1E is a more simplified view).

Next, referring to FIG. 1G, a -OH group (hydroxyl group) is formed on the bonding surface of the first substrate 110 coated with the 3-MPTES 130, and the surface is modified to have hydrophilicity. As the surface modification method, for example, oxygen plasma treatment, corona discharge treatment, plasma discharge treatment, high frequency discharge treatment, ion beam irradiation, electron beam irradiation, UV treatment, ozone treatment and the like can be used.

Next, referring to FIG. 1 (h), the second substrate 120, which is a non-silicon substrate to be bonded to the first substrate 110, is treated in the same manner as described above. That is, the bonding surface (or both surfaces) of the second substrate 120 is coated with the silane compound 130 containing a mercapto group, and the -OH group (hydroxyl group) is formed on the coated bonding surface, . As the surface modification method, for example, an oxygen plasma treatment may be used.

Next, the bonding surfaces of the first and second substrates 110 and 120 are opposed to each other and are conformed to each other for a predetermined time (for example, about 1 hour) at a normal temperature to form a non-silicon bonded substrate 100 . This is because both substrates 110 and 120 can easily be bonded to each other via -OH (hydroxyl group) formed on the bonding surfaces of the first substrate 110 and the second substrate 120.

Although not shown in the drawing, a process of forming a fine pattern on at least one side of the surfaces of the first substrate 110 and the second substrate 120 may be added. The fine pattern may be a relief pattern or a relief pattern, and may be formed using photolithography or replica molding techniques.

On the other hand, a process for producing a bonded substrate in which a non-silicon based substrate and a PDMS substrate are bonded will be described. First, when the bonded surface (or the entire surface) of a non- silicon based substrate is treated with a silane compound containing a mercapto group, And an alkoxy group end is formed. At this time, the coating method and the process are the same as those described above, and therefore, duplicate explanation is omitted.

Subsequently, a -OH group (hydroxyl group) is formed on the bonding surface of the non-silicone base material to modify the surface to have hydrophilicity, and a -OH group (hydroxyl group) is similarly formed on the bonding surface of the PDMS substrate to have hydrophilicity Surface modification. In the case of the PDMS substrate, a process of coating with the silane compound containing the mercapto group is not required. This is because the PDMS substrate already has an alkoxy group at the bonding site (Si-O).

Next, a bonding substrate can be produced by disposing the non-silicon base material and the PDMS base material so as to face each other, adhering them to each other, and then bonding them at room temperature for a certain period of time. And the two substrates can easily bond to each other through -OH (hydroxyl group) formed on the bonding surface of the non-silicon base material and the PDMS base material.

The non-silicon bonded substrate manufacturing method as described above has the following advantages.

First, silane compounds containing a mercapto group can be coated on a non-silicon based substrate without a separate surface oxidation step, and the coating process is performed by a relatively quick reaction, thereby making it possible to simplify the manufacturing process of the bonded substrate as a whole.

Second, after a silane compound containing a mercapto group is coated on a non-silicon based substrate, it is possible to easily bond two non-silicon based substrates at room temperature through a simple surface modification (the same applies to the bonding of a non-silicon based substrate and a PDMS substrate). That is, no separate high-temperature process is required in the present method. Thus minimizing the possibility of deformation of the chip, which can be accompanied by a high temperature process intervention.

Third, since a single chemical is used as a silane compound (for example, 3-MPTES) mediating the bonding of the first and second non-silicon based substrates (the same applies to the bonding of the non-silicon based material and the PDMS based material) It is possible to simplify the process and reduce the manufacturing cost than using the material.

Fourth, the nucleophilic reaction used in the present method has a relatively strong bonding force, and enables bonding of non-silicon based materials (or non-silicon based materials and PDMS based) siloxane bonds, and thus it is possible to produce bonded substrates having excellent bonding strength.

Hereinafter, the present invention will be described in more detail with reference to test examples. However, the present invention is not limited by the following test examples.

Test Example

end. Contact angle measurement

A PVC base material and a PET base material were prepared with a non-silicone base material, and a water contact angle with respect to the above non-silicone base materials was measured. 2) Oxygen plasma treatment (1 minute treatment, 95W, Cute plasma system; Femto Science, Korea); 3) In the case of the PVC substrate and the PET substrate, 4) treatment with 2% (v / v) 3-MPTES solution at room temperature, 4) treatment with 2% (v / v) 3-MPTES solution at room temperature and oxygen plasma treatment And the contact angle was measured. The contact angle measurement was performed using a sessile drop method (Phoenix 300 contact angle measuring system, Surface Electro Optics, Korea) and analyzed using an Image Pro 300 S / W.

2 is a view showing a contact angle measurement result. Referring to FIG. 2, the contact angles of the PVC base material and the PET base material were 52.3 ° and 36.7 °, respectively, in the oxygen plasma treatment, and the water contact angle was lower than that in the state without any treatment. The decrease in water contact angle of the surface after the oxygen plasma treatment means that a hydroxyl group is formed on the surface of the substrate. That is, it was confirmed that a hydroxyl group was formed on the surface of the non-silicon base material, but the contact angle corresponds to a relatively high value.

On the other hand, when the non-silicon based substrates were treated with 3-MPTES and then subjected to oxygen plasma treatment, it was confirmed that the water contact angle of both the PVC substrate and the PET substrate was less than 10 °. It can be seen that the treatment of the substrate surface with 3-MPTES facilitates the oxidation more easily and can further lower the contact angle than the case of simply performing the oxygen plasma treatment.

XPS analysis (X-ray photoelectron spectroscopy, Axis-His, Kratos Analytical, UK) was performed on the PET substrate to further confirm the surface modification. 3 is an XPS analysis graph of PET. Referring to FIG. 3, FIG. 3A is an XPS analysis graph before surface treatment with 3-MPTES aqueous solution, and FIG. 3B is an XPS analysis graph after surface treatment with 3-MPTES aqueous solution. Carbon and oxygen are the main elements of pure PET, with C1s and O1s peaks at 283.0 eV and 530.0 eV, respectively. On the other hand, as shown in FIG. 3B, it is confirmed that Si2s, Si2p, S2s, and S2p peaks are additionally detected after surface treatment with 3-MPTES aqueous solution. Among them, Si2s and Si2p can be detected by introducing alkoxysilane of 3-MPTES And S2s and S2p are the sulfur functional groups of 3-MPTES. Si2s, Si2p, S2s, and S2p peaks were about 151.0 eV, 100.0 eV, 226.0 eV, and 162.0 eV, respectively. That is, the detection of such additional peaks shows that the PET substrate reacted with 3-MPTES to surface modification.

I. Bond strength measurement

The bonding strength of the non-silicon bonded substrates was measured (using a texture analyzer, QTS25, Brookfield, Middleboro, Ma, USA). As the non-silicon bonded substrate, a PVC-PDMS bonded substrate and a PET-PDMS bonded substrate were prepared. Specifically, the PVC substrate and the PET substrate were each treated with 2% (v / v) 3-MPTES aqueous solution at room temperature, washed with distilled water and dried. The PVC substrate, the PET substrate, and the PDMS substrate were each treated with oxygen plasma for 1 minute (95 W, Cute plasma system; Femto Science, Korea). Subsequently, the PET substrate-PDMS substrate and the PVC substrate-PDMS substrate were placed facing each other with their bonding surfaces facing each other, and then bonded at room temperature for 1 hour to complete the non-silicon bonded substrate.

The bonding strength was measured by forming holes in the PVC substrate, the PET substrate, and the PDMS substrate, inserting the straps into the holes and bundling them, and pulling the non-silicon bonded substrates from both sides at a rate of 100 mm / Were measured.

As a result, the bond strengths of PVC-PDMS and PET-PDMS were measured to be 467.3 kPa and 476.4 kPa, respectively. These values are higher than those in the previously reported studies, and it can be confirmed that the bonding force of the non-silicon bonded substrate according to the embodiment of the present invention is excellent.

The embodiments of the present invention have been described above. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the inventive concept as defined by the appended claims. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the present invention.

110: first substrate
120: second substrate
130: Silane compound containing mercapto group

Claims (6)

A first substrate having an alkoxy group end formed on the bonding surface by coating a bonding surface with a silane compound containing a mercapto group, and a second substrate on which a second substrate is bonded by a hydroxyl group (-OH group) additionally formed on the bonding surface ego,
Wherein the first substrate and the second substrate are plastic substrates containing electrophiles and not containing silicon. The method according to claim 1,
The plastic substrate may be made of a material selected from the group consisting of polycarbonate (PC), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), polyimide (PI), polyethylene terephthalate (PET), polyethersulfone (PES) Polyetheretherketone (PEEK), polyetheretherketone (PEEK), polyetheretherketone (PEEK), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyarylate, polyacrylonitrile (ABS), polyaramid, polybutylene terephthalate (PBT), polylactic acid (PLA), polyoxymethylene (POM), polyurethane (PU) and nylon At least one selected from the group consisting of < RTI ID = 0.0 >
Wherein the mercapto group-containing silane compound is at least one compound selected from the group consisting of 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane or 3-mercaptopropyltrimethoxysilane Board. Coating a joint surface of two substrates to be mutually bonded with a silane compound containing a mercapto group at room temperature;
Forming a hydroxyl group (-OH group) on the bonding surface of the two substrates coated with the silane compound; And
And bonding and bonding the two substrates so that the bonding surfaces of the two substrates are opposed to each other at room temperature,
Wherein the two substrates are plastic substrates containing electrophiles and not containing silicon. The method of claim 3,
The plastic substrate may be made of a material selected from the group consisting of polycarbonate (PC), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), polyimide (PI), polyethylene terephthalate (PET), polyethersulfone (PES) Polyetheretherketone (PEEK), polyetheretherketone (PEEK), polyetheretherketone (PEEK), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyarylate, polyacrylonitrile (ABS), polyaramid, polybutylene terephthalate (PBT), polylactic acid (PLA), polyoxymethylene (POM), polyurethane (PU) and nylon At least one selected from the group consisting of < RTI ID = 0.0 >
Wherein the mercapto group-containing silane compound is at least one compound selected from the group consisting of 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane or 3-mercaptopropyltrimethoxysilane / RTI > delete delete

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