JP4201174B2 - Method for producing pattern forming body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To give a functional group to the surface of a pattern organizer, and to provide a manufacturing method for the pattern organizer that does not require any post treatment or the like after exposure to light. <P>SOLUTION: The manufacturing method for a pattern organizer has a substrate preparation process for the pattern organizer for preparing a substrate for the pattern organizer having a characteristic change layer made of a macromolecular material, and a pattern formation process for giving a functional group in a pattern to the surface of a characteristic change layer made of the macromolecular material, by applying energy from a specific direction after arranging a layer containing photo catalyst on a substrate at the side of a layer for containing photo catalyst having the layer for containing photo catalyst and the substrate, and the characteristic change layer at an interval of 200 &mu;m or less. <P>COPYRIGHT: (C)2003,JPO

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a pattern forming body in which a functional group can be introduced on the surface of the pattern forming body and the pattern forming body itself does not need to contain a photocatalyst.
[0002]
[Prior art]
Conventionally, a method has been proposed in which functional groups are imparted in a pattern to a polymer substrate or a laminate surface on which a polymer thin film is formed on a substrate surface and used for various functional elements. As a method for introducing a functional group into such a polymer material, for example, graft polymerization is known, and γ rays, electron beams, ultraviolet rays, and the like have been used as an energy source for performing the graft polymerization.
[0003]
However, when γ-rays or electron beams are used, polymer chain scission, cross-linking reaction, or degradation reaction occurs in the polymer material itself, so the range of selection of usable polymer materials is narrow. There was a problem.
[0004]
In addition, when graft polymerization is performed on the surface of a polymer material using ultraviolet rays, damage to the polymer material is lower than when γ rays or electron beams are used, but uniform and good graft polymerization is performed. In addition, it is necessary to carry the sensitizer by a method such as coating the surface of the substrate. In this case, it is necessary to determine an appropriate combination of sensitizers depending on the type of base polymer and the type of polymerizable monomer used for polymerization. There is a problem that it becomes difficult to select an appropriate sensitizer. Furthermore, after the polymerization treatment, a sensitizer and a binder for supporting the sensitizer on the substrate surface remain on the surface of the base material. Therefore, depending on the application, a system in which the sensitizer uses a grafted polymer material may be used. There was a possibility that a problem such as contamination would occur and a problem that it was not suitable for the intended use.
[0005]
In addition, the prior art document regarding this invention has not been discovered.
[0006]
[Problems to be solved by the invention]
It is desired to provide a method for producing a pattern forming body that can efficiently add a functional group to the surface of the pattern forming body and that does not require post-treatment after exposure.
[0007]
[Means for Solving the Problems]
In order to achieve the above object, the present invention provides a pattern forming body for preparing a substrate for a pattern forming body having a characteristic change layer made of a polymer material into which a functional group can be introduced by the action of a photocatalyst accompanying energy irradiation. After arranging the photocatalyst-containing layer and the property changing layer in the photocatalyst-containing layer side substrate having the photocatalyst-containing layer and the substrate containing the photocatalyst containing step with a gap of 200 μm or less, In the gap Contained in the gas phase By introducing a substance for introducing a functional group and irradiating the photocatalyst containing layer with energy from a predetermined direction, a pattern is formed on the surface of the characteristic change layer made of the polymer material by the action of the photocatalyst contained in the photocatalyst containing layer. And a pattern forming step for imparting a functional group.
[0008]
According to the present invention, in the region irradiated with energy, a reaction point is formed on the characteristic change layer made of the polymer material by the action of the photocatalyst accompanying the energy irradiation, and reacts with, for example, a substance present in the atmosphere. A functional group is imparted to the surface of the characteristic change layer. On the other hand, in a region where energy is not irradiated, no reactive point is formed, so that no functional group is added. Thereby, it is possible to obtain a pattern forming body in which the surface characteristics are changed by adding the functional group to the pattern. In the pattern formation step, it is possible to impart various functional groups to the surface of the polymer material by changing the substance to be reacted, etc., so that a pattern having functional groups in a pattern can be formed especially after exposure. No processing is required, and it can be easily formed with high definition. Such a pattern forming body can be applied to various uses.
[0009]
In addition, since the interval between the photocatalyst-containing layer and the characteristic change layer is within the above-described range, a pattern forming body having a pattern with a characteristic changed by the functional group being imparted to the surface with good efficiency and accuracy. Obtainable.
[0010]
In the present invention, In the pattern forming step, a functional group introducing substance can be introduced into the gap. This is because the target functional group can be introduced onto the property change layer by the action of the photocatalyst accompanying energy irradiation.
[0011]
In the invention described in claim 1 or claim 2, as described in claim 3, the photocatalyst-containing layer side substrate comprises a base material and a photocatalyst formed in a pattern on the base material. It is preferable to consist of a layer. Thus, by forming the photocatalyst-containing layer in a pattern, it is possible to form patterns having different characteristics by adding functional groups on the characteristic change layer without using a photomask. . Further, since only the surface corresponding to the photocatalyst-containing layer is changed to a lyophilic region, the energy to be irradiated is not particularly limited to parallel energy, and the energy irradiation direction is not particularly limited. This is because there is an advantage that the type of energy source and the degree of freedom in arrangement are greatly increased.
[0012]
In the invention described in claim 1 or claim 2, as described in claim 4, the photocatalyst-containing layer side substrate comprises a base material, and a photocatalyst-containing layer formed on the base material, The photocatalyst-containing layer side light-shielding portion is formed in a pattern, and the energy irradiation in the pattern forming step is preferably performed from the photocatalyst-containing layer side substrate.
[0013]
By having the photocatalyst-containing layer side light-shielding portion on the photocatalyst-containing layer side substrate in this way, it is not necessary to use a photomask or the like for exposure, so alignment with the photomask is not necessary, and the process can be simplified. This is because it becomes possible.
[0014]
In the invention described in claim 4, as described in claim 5, in the photocatalyst-containing layer side substrate, the photocatalyst-containing layer side light-shielding portion is formed in a pattern on the substrate, and further The photocatalyst-containing layer may be formed on the photocatalyst-containing layer side substrate as described in claim 6, wherein the photocatalyst-containing layer is formed on the base material, and the photocatalyst-containing layer is formed. The photocatalyst containing layer side light-shielding part may be formed in a pattern on the layer.
[0015]
It can be said that the photocatalyst-containing layer-side light-shielding portion is preferably disposed at a position close to the characteristic change layer in terms of accuracy of the obtained characteristic pattern. Therefore, it is preferable to dispose the photocatalyst containing layer side light shielding portion at the position described above. Moreover, when the photocatalyst containing layer side light-shielding part is formed on the photocatalyst containing layer, it has an advantage that it can be used as a spacer when arranging the photocatalyst containing layer and the characteristic change layer in the pattern forming step.
[0016]
In the invention described in any one of claims 1 to 6, as described in claim 7, the photocatalyst-containing layer is preferably a layer made of a photocatalyst. If the photocatalyst-containing layer is a layer composed only of a photocatalyst, it is possible to improve the efficiency of changing properties by adding a functional group on the property-changing layer, and it is possible to efficiently produce a pattern forming body. Because it can.
[0017]
In the invention described in claim 7, as described in claim 8, the photocatalyst-containing layer is preferably a layer formed by forming a photocatalyst on a substrate by a vacuum film forming method. By forming the photocatalyst-containing layer by vacuum film formation in this way, it is possible to obtain a uniform photocatalyst-containing layer having a uniform film thickness with less surface irregularities, and forming a pattern on the surface of the characteristic change layer. It is because it can carry out uniformly and highly efficiently.
[0018]
On the other hand, in the invention described in any one of claims 1 to 6, as described in claim 9, the photocatalyst-treated layer is a layer having a photocatalyst and a binder. Also good. By using the binder in this manner, it becomes possible to form the photocatalyst-containing layer relatively easily, and as a result, the pattern formed body can be manufactured at a low cost.
[0019]
In the invention described in any one of claims 1 to 9, as described in claim 10, the photocatalyst is made of titanium oxide (TiO 2). ₂ ), Zinc oxide (ZnO), tin oxide (SnO) ₂ ), Strontium titanate (SrTiO) ₃ ), Tungsten oxide (WO ₃ ), Bismuth oxide (Bi ₂ O ₃ ), And iron oxide (Fe ₂ O ₃ It is preferable that it is 1 type, or 2 or more types of substances selected from the above, and as described in claim 11, the photocatalyst is titanium oxide (TiO 2). ₂ ) Is preferable. This is because titanium dioxide has a high band gap energy and is effective as a photocatalyst, and is chemically stable, non-toxic and easily available.
[0020]
In addition, as described in claim 12, applied to the characteristic change layer of the pattern formed body obtained by the method for producing a pattern formed body according to any one of claims 1 to 11. It is possible to provide a method for producing a biochip substrate, wherein the functional group is a functional group having a biological substance binding property that binds to a biological substance. Since the functional group has a biological substance binding property, a high-definition biochip can be easily formed by binding the biological substance to the functional group provided in a pattern.
[0021]
Further, as described in claim 13, a substrate of the pattern forming body obtained by the method for manufacturing a pattern forming body according to any one of claims 1 to 11 is used for flowing a fluid. A substrate for a microfluidic chip, characterized in that a predetermined functional group is provided in a pattern shape in the pattern forming step on the surface of the property change layer made of a polymer material in the recess at least. A manufacturing method is provided. A microfluidic chip base material capable of easily controlling the fluid by adding a functional group that controls the flow of the fluid to the surface of the concave portion serving as a fluid flow path of the microfluidic chip base material; can do.
[0022]
Furthermore, as described in claim 14, applied to the characteristic change layer of the pattern forming body obtained by the method for manufacturing a pattern forming body according to any one of claims 1 to 11. A method for producing a substrate for forming a conductive pattern, wherein the functional group is a functional group having an electroless plating catalyst adhesion property that adheres to an electroless plating catalyst, and the polymer is electrically insulating. I will provide a. If the functional group has electroless plating catalyst adhesion, a high-definition conductive pattern can be easily created by attaching the electroless plating catalyst to the deprotected functional group formed in a pattern. Can be formed.
[0023]
In the present invention, as described in claim 15, the step of binding a biological substance to the functional group of the biochip substrate obtained in the method for producing a biochip substrate according to claim 12. A method for producing a biochip is provided. According to the method of the present invention, a high-density biochip can be obtained relatively easily.
[0024]
In this invention, as further described in Claim 16, the process of bonding the base material for microfluidic chips obtained by the manufacturing method of the base material for microfluidic chips of Claim 13, and a bonding base material. A method of manufacturing a microfluidic chip is provided. As described above, according to the production method of the present invention, it is possible to introduce the functional group for controlling the fluid into the recess very easily.
[0025]
Furthermore, in the present invention, as described in claim 17, with respect to the functional group of the substrate for forming a conductive pattern obtained by the method for manufacturing a substrate for forming a conductive pattern according to claim 14, A catalyst attaching step for attaching an electroless plating catalyst; and an electroless plating step for performing electroless plating on a substrate on which the electroless plating catalyst is attached in a pattern by the catalyst attaching step. A method for manufacturing a conductive pattern is provided. According to the method of the present invention, a high-definition conductive pattern can be easily obtained.
[0026]
DETAILED DESCRIPTION OF THE INVENTION
First, the manufacturing method of the pattern formation body of this invention is demonstrated. The method for producing the pattern forming body of the present invention comprises
A pattern forming body substrate preparation step of preparing a pattern forming body substrate having a characteristic change layer made of a polymer material;
A photocatalyst-containing layer containing a photocatalyst and a photocatalyst-containing layer side substrate having a substrate and the characteristic change layer are arranged with a gap of 200 μm or less, and then irradiated with energy from a predetermined direction, A pattern forming step of imparting functional groups in a pattern on the surface of the property change layer made of the polymer material
It is characterized by having.
[0027]
Moreover, in this invention, you may have the photocatalyst containing layer side board | substrate adjustment process which adjusts the photocatalyst containing layer side board | substrate which has a photocatalyst containing layer and base material containing a photocatalyst, In this case, the photocatalyst containing a photocatalyst is contained. A substrate for a pattern forming body having a photocatalyst containing layer side substrate adjusting step for adjusting a photocatalyst containing layer side substrate having a containing layer and a base material, and a property changing layer whose surface properties are changed by the action of the photocatalyst in the photocatalyst containing layer The pattern forming body substrate preparation step for preparing the layer, and the photocatalyst-containing layer and the characteristic change layer are arranged with a gap so as to be 200 μm or less, and then irradiated with energy from a predetermined direction, whereby the above characteristics are obtained. And a pattern forming process for forming a pattern with changed characteristics on the surface of the change layer. The substrate for forming the body is formed from a characteristic change layer made of a polymer temple, and in the pattern formation step, a functional group is imparted to the surface of the characteristic change layer made of the polymer material in a pattern. .
[0028]
In the method for producing a patterned body of the present invention, the photocatalyst-containing layer and the characteristic change layer are arranged so as to have a predetermined gap, and then irradiated with energy from a predetermined direction, thereby causing the action of the photocatalyst in the photocatalyst-containing layer. A reaction point is formed in the exposed property changing layer facing the photocatalyst-containing layer, and reacts with a substance in the atmosphere to form a pattern with a functional group on the surface of the property changing layer. Therefore, post-processing such as development and washing after exposure is not required for pattern formation, and patterns having different characteristics can be formed by adding functional groups at a lower cost and with fewer steps. And it can be set as the pattern formation body which can be used for various uses by selecting the material of this characteristic change layer, and the functional group to provide.
[0029]
Furthermore, in the present invention, after the characteristics on the characteristic change layer are changed by the action of the photocatalyst in the photocatalyst containing layer, the photocatalyst containing layer side substrate is removed and the pattern forming body side substrate is used as the pattern forming body. The obtained pattern forming body does not necessarily contain a photocatalyst. Therefore, it is possible to prevent a problem that the obtained pattern forming body deteriorates with time due to the action of the photocatalyst.
[0030]
Such a method for producing a pattern forming body of the present invention will be specifically described with reference to the drawings. FIG. 1 shows an example of a method for producing a pattern forming body of the present invention.
[0031]
In this example, first, a photocatalyst containing layer side substrate 3 in which a photocatalyst containing layer 2 is formed on a substrate 1 and a pattern forming body substrate 6 in which a characteristic change layer 5 is formed on a base 4 are provided. Adjust (FIG. 1 (a)).
[0032]
Next, as shown in FIG. 1B, the photocatalyst containing layer side substrate 3 and the pattern forming body substrate 6 are arranged so that the photocatalyst containing layer 2 and the characteristic change layer 5 have a predetermined interval. After that, a photomask 7 on which a required pattern is drawn is used, and ultraviolet light 8 is irradiated from the photomask-containing layer side substrate 3 side through the photomask 7. Thereby, as shown in FIG.1 (c), the pattern which consists of the area | region 9 from which a characteristic differs is formed by the functional group being provided to the characteristic change layer 5 surface (pattern formation process).
[0033]
At this time, the photocatalyst-containing layer 2 and the characteristic change layer 5 are arranged at a predetermined interval in FIG. 1, but in the present invention, if necessary, they are physically in close contact with each other. It may be.
[0034]
In the present invention, a functional group introducing substance for introducing a functional group into the gap may be introduced during the pattern forming step. This makes it possible to introduce the target functional group onto the surface of the property change layer, and to form a pattern forming body that can be used for various purposes by changing the type of the functional group-introducing substance. This is because it becomes possible.
[0035]
In the above example, the ultraviolet irradiation is performed through the photomask 7. However, as will be described later, the photocatalyst containing layer is formed in a pattern, or the photocatalyst containing layer side substrate has a light shielding portion (photocatalyst). In this case, the entire surface is exposed without using the photomask 7 or the like.
[0036]
Then, a step of removing the photocatalyst-containing layer side substrate from the pattern forming body substrate 6 is performed (FIG. 1D), and the pattern forming body 6 having a pattern whose characteristics are changed on the surface can be obtained.
[0037]
The manufacturing method of the pattern forming body of the present invention will be described in detail for each step.
[0038]
1. Pattern forming substrate preparation process
First, the substrate forming process for a pattern forming body in the present invention will be described. The pattern forming substrate preparing step in the present invention is a step of preparing a pattern forming substrate having a characteristic change layer made of a polymer material.
[0039]
The characteristic change layer used in the present invention is, for example, a film made of a polymer material or a molded article made of a polymer material, which becomes a substrate for a pattern forming body. It may be laminated.
[0040]
In the present invention, there is no particular limitation as long as it is a polymer material in which various functional groups can be introduced into the surface in the pattern forming step described later. Specifically, polyethylene, polycarbonate, polypropylene, polystyrene, polyester, polyvinyl fluoride, acetal resin, nylon, ABS, PTFE, methacrylic resin, phenol resin, polyvinylidene fluoride, polyoxymethylene, polyvinyl alcohol, polyvinyl chloride, Examples thereof include polyethylene terephthalate, silicone, cellulose, rubber, polyvinyl alcohol, and nylon.
[0042]
As the substrate on which such a characteristic change layer is formed, a silicon wafer, metal, quartz, glass, diamond, diamond-like carbon (DLC), alumina, a polymer material, or the like can be used, which will be described later. It is appropriately selected according to the use.
[0043]
Further, the shape of the substrate to be used is not particularly limited, and this can also be a suitable shape according to the use described later. Specifically, when the use is a biochip or the like, In the case where a plate-like material is suitably used and the application is a microfluidic chip, a material in which a predetermined recess is formed can be used.
[0044]
In this invention, it is possible to use what formed the pattern formation body board | substrate side light-shielding part in the pattern form in the pattern formation body board | substrate.
[0045]
In this case, since it is necessary to perform energy irradiation in the pattern forming process described later from the pattern forming body substrate side, the pattern forming body substrate needs to be transparent.
[0046]
The method for forming the pattern-forming substrate-side light-shielding portion is not particularly limited, and is appropriately determined according to the characteristics of the formation surface of the pattern-forming substrate-side light-shielding portion, the shielding property against the required energy, and the like. Selected and used.
[0047]
For example, it may be formed by forming a metal thin film of chromium or the like having a thickness of about 1000 to 2000 mm by a sputtering method, a vacuum deposition method, or the like, and patterning the thin film. As this patterning method, a normal patterning method such as sputtering can be used.
[0048]
Alternatively, a method may be used in which a layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a resin binder is formed in a pattern. As the resin binder to be used, polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, cellulose, or a mixture of one or more resins, photosensitive resin, or O / A W emulsion type resin composition, for example, an emulsion of a reactive silicone can be used. The thickness of such a resin light-shielding portion can be set within a range of 0.5 to 10 μm. As a method for patterning the resin light-shielding portion, a generally used method such as a photolithography method or a printing method can be used.
[0049]
2. Pattern formation process
Next, the pattern formation process in this invention is demonstrated. In the pattern forming step of the present invention, the photocatalyst-containing layer containing the photocatalyst and the photocatalyst-containing layer side substrate having the substrate are arranged in a predetermined direction after the photocatalyst-containing layer and the characteristic change layer are arranged with a predetermined gap. In this step, functional groups are imparted in a pattern to the surface of the property-changing layer made of the polymer material.
[0050]
Hereinafter, each structure of this process is demonstrated.
[0051]
(Photocatalyst containing layer side substrate)
First, the photocatalyst containing layer side substrate used in the present invention will be described. The photocatalyst-containing layer side substrate used in the present invention has a photocatalyst-containing layer containing a photocatalyst and a base material. Thus, the photocatalyst-containing layer side substrate used in the present invention has at least a photocatalyst-containing layer and a substrate, and usually a thin-film photocatalyst-containing layer formed by a predetermined method on the substrate. It is formed. Moreover, the thing in which the photocatalyst containing layer side light shielding part formed in pattern shape was formed can also be used for this photocatalyst containing layer side board | substrate. Hereinafter, each structure of the photocatalyst containing layer side substrate will be described.
[0052]
a. Photocatalyst containing layer
The photocatalyst-containing layer used in the present invention is not particularly limited as long as the photocatalyst in the photocatalyst-containing layer changes the characteristics of the target characteristic change layer, and includes a photocatalyst and a binder. It may be formed, or it may be a film formed of a photocatalyst alone. Further, the wettability of the surface may be particularly lyophilic or lyophobic.
[0053]
The photocatalyst-containing layer used in the present invention may be formed on the entire surface of the substrate 1 as shown in FIG. 1 (a), for example, but for example, as shown in FIG. The photocatalyst containing layer 2 may be formed on the pattern on the material 1.
[0054]
By forming the photocatalyst-containing layer in a pattern like this, as described in the pattern forming step described later, when the photocatalyst-containing layer is arranged at a predetermined interval from the characteristic change layer and irradiated with energy, It is not necessary to perform pattern irradiation using a photomask or the like, and by irradiating the entire surface, a pattern with changed characteristics can be formed by adding functional groups on the characteristic change layer.
[0055]
The patterning method of the photocatalyst processing layer is not particularly limited, but can be performed by, for example, a photolithography method.
[0056]
In addition, since the functional group is imparted only to the part on the characteristic change layer facing the photocatalyst containing layer and the characteristic changes, the direction of energy irradiation faces the photocatalyst containing layer and the characteristic change layer. As long as the portion is irradiated with energy, it may be irradiated from any direction. Further, the irradiated energy is not particularly limited to parallel light such as parallel light.
[0057]
The action mechanism of a photocatalyst represented by titanium dioxide as described later in such a photocatalyst-containing layer is not necessarily clear, but a carrier generated by light irradiation reacts directly with a nearby compound, or It is considered that the active oxygen species generated in the presence of oxygen and water change the chemical structure of organic matter. In the present invention, it is considered that this carrier acts on the compound in the property change layer disposed in the vicinity of the photocatalyst containing layer.
[0058]
As the photocatalyst used in the present invention, for example, titanium dioxide (TiO 2) known as an optical semiconductor. ₂ ), Zinc oxide (ZnO), tin oxide (SnO) ₂ ), Strontium titanate (SrTiO) ₃ ), Tungsten oxide (WO ₃ ), Bismuth oxide (Bi ₂ O ₃ ), And iron oxide (Fe ₂ O ₃ 1) or a mixture of two or more selected from these.
[0059]
In the present invention, titanium dioxide is particularly preferably used because it has a high band gap energy, is chemically stable, has no toxicity, and is easily available. Titanium dioxide includes an anatase type and a rutile type, and both can be used in the present invention, but anatase type titanium dioxide is preferred. Anatase type titanium dioxide has an excitation wavelength of 380 nm or less.
[0060]
Examples of such anatase type titanium dioxide include hydrochloric acid peptizer type anatase type titania sol (STS-02 manufactured by Ishihara Sangyo Co., Ltd. (average particle size 7 nm), ST-K01 manufactured by Ishihara Sangyo Co., Ltd.), nitric acid solution An anatase type titania sol (TA-15 manufactured by Nissan Chemical Co., Ltd. (average particle size 12 nm)) and the like can be mentioned.
[0061]
The smaller the particle size of the photocatalyst, the more effective the photocatalytic reaction occurs. The average particle size is preferably 50 nm or less, and it is particularly preferable to use a photocatalyst of 20 nm or less.
[0062]
The photocatalyst-containing layer in the present invention may be formed by a photocatalyst alone as described above, or may be formed by mixing with a binder.
[0063]
In the case of a photocatalyst-containing layer composed only of a photocatalyst, the efficiency with respect to the change in characteristics on the characteristic change layer is improved, which is advantageous in terms of cost such as shortening the processing time. On the other hand, in the case of a photocatalyst-containing layer comprising a photocatalyst and a binder, there is an advantage that the formation of the photocatalyst-containing layer is easy.
[0064]
Examples of a method for forming a photocatalyst-containing layer composed only of a photocatalyst include a method using a vacuum film forming method such as a sputtering method, a CVD method, or a vacuum deposition method. By forming the photocatalyst-containing layer by a vacuum film-forming method, it is possible to obtain a photocatalyst-containing layer that is a uniform film and contains only the photocatalyst, which can uniformly change the characteristics on the characteristic change layer. Since it is possible and consists only of a photocatalyst, it is possible to change the characteristics on the characteristic change layer more efficiently than in the case of using a binder.
[0065]
Examples of a method for forming a photocatalyst-containing layer consisting of only a photocatalyst include a method in which amorphous titania is formed on a substrate and then phase-changed to crystalline titania by firing when the photocatalyst is titanium dioxide. . As the amorphous titania used here, for example, hydrolysis, dehydration condensation, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetrabutoxytitanium, titanium inorganic salts such as titanium tetrachloride and titanium sulfate, An organic titanium compound such as tetramethoxytitanium can be obtained by hydrolysis and dehydration condensation in the presence of an acid. Next, it can be modified to anatase titania by baking at 400 ° C. to 500 ° C. and modified to rutile type titania by baking at 600 ° C. to 700 ° C.
[0066]
Moreover, when using a binder, what has the high bond energy that the main frame | skeleton of a binder is not decomposed | disassembled by photoexcitation of said photocatalyst is preferable, for example, organopolysiloxane etc. can be mentioned.
[0067]
When organopolysiloxane is used as a binder in this way, the photocatalyst-containing layer is prepared by dispersing the photocatalyst and the binder organopolysiloxane in a solvent together with other additives as necessary. It can be formed by applying this coating solution on a substrate. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The coating can be performed by a known coating method such as spin coating, spray coating, dip coating, roll coating or bead coating. When an ultraviolet curable component is contained as a binder, the photocatalyst-containing layer can be formed by irradiating with ultraviolet rays and performing a curing treatment.
[0068]
An amorphous silica precursor can be used as the binder. This amorphous silica precursor has the general formula SiX ₄ X is preferably a silicon compound such as halogen, methoxy group, ethoxy group, or acetyl group, a hydrolyzate thereof, silanol, or a polysiloxane having an average molecular weight of 3000 or less.
[0069]
Specific examples include tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetrabutoxysilane, and tetramethoxysilane. In this case, the amorphous silica precursor and the photocatalyst particles are uniformly dispersed in a non-aqueous solvent, and hydrolyzed with moisture in the air on the substrate to form silanol, and then at room temperature. A photocatalyst-containing layer can be formed by dehydration-condensation polymerization. If dehydration condensation polymerization of silanol is performed at 100 ° C. or higher, the degree of polymerization of silanol increases and the strength of the film surface can be improved. Moreover, these binders can be used individually or in mixture of 2 or more types.
[0070]
When the binder is used, the content of the photocatalyst in the photocatalyst containing layer can be set in the range of 5 to 60% by weight, preferably 20 to 40% by weight. The thickness of the photocatalyst containing layer is preferably in the range of 0.05 to 10 μm.
[0071]
In addition to the photocatalyst and the binder, the photocatalyst containing layer can contain a surfactant. Specifically, hydrocarbons such as NIKKOL BL, BC, BO, BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Dainippon Megafac F-141, 144 manufactured by Ink Chemical Industry Co., Ltd., Footgent F-200, F251 manufactured by Neos Co., Ltd., Unidyne DS-401, 402 manufactured by Daikin Industries, Ltd., Fluorard FC-170 manufactured by 3M Co., Ltd. Fluorine-based or silicone-based nonionic surfactants such as 176 can be used, and cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.
[0072]
In addition to the above surfactants, the photocatalyst-containing layer includes polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate, Polyvinyl chloride, polyamide, polyimide, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, oligomers, polymers, etc. It can be included.
[0073]
b. Base material
In this invention, as shown to Fig.1 (a), the photocatalyst containing layer side board | substrate 3 has the base material 1 and the photocatalyst containing layer 2 formed on this base material 1 at least.
[0074]
Under the present circumstances, the material which comprises the base material used is suitably selected by the irradiation direction of the energy in the pattern formation process mentioned later, whether the pattern formation body obtained requires transparency, etc.
[0075]
That is, for example, in the case where an opaque pattern forming body is used as the substrate, the energy irradiation direction is necessarily from the photocatalyst containing layer side substrate side, and the photomask 7 contains the photocatalyst as shown in FIG. It is necessary to arrange it on the layer side substrate 3 side and irradiate energy. As will be described later, the photocatalyst-containing layer side light-shielding portion is formed in advance in a predetermined pattern on the photocatalyst-containing layer side substrate, and the photocatalyst-containing layer side light-shielding portion is used to form a pattern. It is necessary to irradiate energy from the side substrate side. In such a case, the base material needs to have transparency.
[0076]
On the other hand, if the pattern forming body is transparent, it is possible to arrange the photomask on the pattern forming body substrate side and irradiate energy. As will be described later, when the pattern forming body-side light-shielding portion is formed in the pattern forming body substrate, it is necessary to irradiate energy from the pattern forming body substrate side. In such a case, the transparency of the substrate is not particularly required.
[0077]
The base material used in the present invention may be a flexible material such as a resin film, or may be a non-flexible material such as a glass substrate. This is appropriately selected depending on the energy irradiation method in the pattern forming process described later.
[0078]
As described above, the material used for the photocatalyst-containing layer side substrate in the present invention is not particularly limited, but in the present invention, the photocatalyst-containing layer side substrate is used repeatedly. Therefore, a material having a predetermined strength and having a surface having good adhesion to the photocatalyst containing layer is preferably used.
[0079]
Specific examples include glass, ceramic, metal, and plastic.
[0080]
In addition, in order to improve the adhesiveness of the base-material surface and a photocatalyst content layer, you may make it form an anchor layer on a base material. Examples of such an anchor layer include silane-based and titanium-based coupling agents.
[0081]
c. Photocatalyst containing layer side shading part
As the photocatalyst containing layer side substrate used in the present invention, a substrate in which a photocatalyst containing layer side light shielding portion formed in a pattern is formed may be used. By using the photocatalyst containing layer side substrate having the photocatalyst containing layer side light shielding portion in this way, it is not necessary to use a photomask or perform drawing irradiation with a laser beam at the time of exposure. Therefore, since alignment between the photocatalyst-containing layer side substrate and the photomask is not necessary, it is possible to use a simple process, and an expensive apparatus necessary for drawing irradiation is also unnecessary, so that the cost is reduced. Has the advantage of being advantageous.
[0082]
Such a photocatalyst containing layer side light-shielding part having such a photocatalyst containing layer side light shielding part can be made into the following two embodiments depending on the formation position of the photocatalyst containing layer side light shielding part.
[0083]
For example, as shown in FIG. 3, the photocatalyst containing layer side light shielding part 12 is formed on the substrate 1, the photocatalyst containing layer 2 is formed on the photocatalyst containing layer side light shielding part 12, and the photocatalyst containing layer side is formed. In this embodiment, the substrate 3 is used. For example, as shown in FIG. 4, the photocatalyst-containing layer side substrate 3 is formed by forming the photocatalyst-containing layer 2 on the base material 1 and forming the photocatalyst-containing layer side light-shielding portion 12 thereon. It is.
[0084]
In any embodiment, compared to the case of using a photomask, the photocatalyst-containing layer side light-shielding portion is disposed in the vicinity of the portion where the photocatalyst-containing layer and the characteristic change layer are located with a gap. Since the influence of energy scattering in the substrate or the like can be reduced, energy pattern irradiation can be performed very accurately.
[0085]
Furthermore, in the embodiment in which the photocatalyst containing layer side light shielding part is formed on the photocatalyst containing layer, when the photocatalyst containing layer and the characteristic change layer are arranged with a predetermined gap, By making the film thickness coincide with the width of the gap, there is an advantage that the photocatalyst containing layer side light-shielding portion can be used as a spacer for making the gap constant.
[0086]
That is, when the photocatalyst containing layer and the characteristic change layer are arranged in contact with each other with a predetermined gap, the photocatalyst containing layer side light shielding portion and the characteristic change layer are arranged in close contact with each other. The predetermined gap can be made accurate, and by irradiating energy from the photocatalyst-containing layer side substrate in this state, a pattern can be accurately formed on the characteristic change layer.
[0087]
Since the formation method of the photocatalyst containing layer side light shielding part used for this invention is the same as the formation method of the light shielding part in the board | substrate for pattern formation bodies mentioned above, description here is abbreviate | omitted.
[0088]
In the above description, the two positions of the photocatalyst-containing layer side light-shielding portion are described between the base material and the photocatalyst-containing layer and on the surface of the photocatalyst-containing layer. It is also possible to adopt a mode in which the photocatalyst-containing layer side light-shielding portion is formed on the surface where no is formed. In this aspect, for example, a case where the photomask is brought into close contact with the surface so as to be detachable can be considered, and it can be suitably used when the pattern forming body is changed in a small lot.
[0089]
d. Primer layer
Next, the primer layer used for the photocatalyst containing layer side substrate of the present invention will be described. In the present invention, as described above, when the photocatalyst-containing layer side light-shielding portion is formed in a pattern on the substrate and the photocatalyst-containing layer is formed thereon to form a photocatalyst-containing layer side substrate, the photocatalyst-containing layer side substrate is formed. A primer layer may be formed between the layer side light shielding portion and the photocatalyst containing layer.
[0090]
The function and function of this primer layer are not always clear, but by forming a primer layer between the photocatalyst-containing layer side light-shielding part and the photocatalyst-containing layer, the primer layer can change the characteristics of the characteristic change layer due to the action of the photocatalyst. Impurities from the openings existing between the photocatalyst containing layer side light shielding part and the photocatalyst containing layer side light shielding part, which are factors that hinder the change, in particular, residues generated when patterning the photocatalyst containing layer side light shielding part, metal, metal It is considered that it has a function of preventing diffusion of impurities such as ions. Therefore, by forming the primer layer, the characteristic change process proceeds with high sensitivity, and as a result, a high-resolution pattern can be obtained.
[0091]
In the present invention, the primer layer prevents impurities existing in not only the photocatalyst containing layer side light shielding part but also the opening formed between the photocatalyst containing layer side light shielding parts from affecting the action of the photocatalyst. The primer layer is preferably formed over the entire surface of the photocatalyst containing layer side light shielding portion including the opening.
[0092]
The primer layer in the present invention is not particularly limited as long as the primer layer is formed so that the photocatalyst containing layer side light-shielding portion of the photocatalyst containing layer side substrate is not in contact with the photocatalyst containing layer.
[0093]
The material constituting the primer layer is not particularly limited, but an inorganic material that is not easily decomposed by the action of the photocatalyst is preferable. Specific examples include amorphous silica. When such amorphous silica is used, the precursor of amorphous silica is represented by the general formula SiX. ₄ X is a silicon compound such as halogen, methoxy group, ethoxy group, or acetyl group, and a hydrolyzate thereof, silanol, or polysiloxane having an average molecular weight of 3000 or less is preferable.
[0094]
The thickness of the primer layer is preferably in the range of 0.001 μm to 1 μm, particularly preferably in the range of 0.001 μm to 0.1 μm.
[0095]
(Pattern formation)
Next, formation of the pattern of the present invention will be described. In the pattern formation process of the present invention, the photocatalyst-containing layer and the characteristic change layer described above are arranged with a gap so as to be 200 μm or less, and then irradiated with energy from a predetermined direction to change the characteristic change made of the polymer material. Functional groups are provided in a pattern on the surface of the layer.
[0096]
In the present invention, the gap is preferably 100 μm or less, particularly in the range of 0.2 μm to 10 μm, in consideration of pattern accuracy and efficiency of property change on the property change layer.
[0097]
Thus, by disposing the photocatalyst-containing layer and the property change layer surface at a predetermined interval, oxygen, water, and active oxygen species generated by the photocatalytic action are easily desorbed. That is, if the interval between the photocatalyst containing layer and the characteristic change layer is narrower than the above range, it is difficult to desorb the active oxygen species, and as a result, the characteristic change rate may be slowed down. It is not preferable, and it is not preferable that the active oxygen species generated are difficult to reach the property change layer when arranged at a distance from the above range. is there.
[0098]
In the present invention, such an arrangement state with a gap need only be maintained at least during exposure.
[0099]
An example of a method for uniformly forming such an extremely narrow gap and arranging the photocatalyst-containing layer and the characteristic change layer is a method using a spacer. By using the spacer in this way, a uniform gap can be formed, and the portion in contact with the spacer is not affected by the photocatalyst action on the surface of the characteristic change layer. It is possible to form a predetermined pattern on the characteristic change layer. Here, the pattern may be formed on the entire surface.
[0100]
In the present invention, such a spacer may be formed as one member. However, for simplification of the process, as described in the column of the photocatalyst containing layer side substrate, the photocatalyst of the photocatalyst containing layer side substrate is used. It is preferable to form on the surface of the containing layer. In the description of the photocatalyst-containing layer side substrate preparation step, the photocatalyst-containing layer side light-shielding portion has been described. However, in the present invention, such a spacer has a surface so that the photocatalyst does not act on the surface of the property change layer. In particular, it may be formed of a material that does not have a function of shielding the irradiated energy.
[0101]
Next, in a state where the contact state as described above is maintained, energy irradiation is performed on the contacted portion. The energy irradiation (exposure) as used in the present invention is a concept including irradiation of any energy beam capable of changing the characteristics by adding a functional group to the surface of the characteristic change layer by the photocatalyst containing layer. It is not limited to irradiation with visible light.
[0102]
Usually, the wavelength of light used for such exposure is set in the range of 400 nm or less, preferably in the range of 380 nm or less. This is because, as described above, the preferred photocatalyst used in the photocatalyst-containing layer is titanium dioxide, and light having the above-described wavelength is preferable as the energy for activating the photocatalytic action by the titanium dioxide.
[0103]
Examples of light sources that can be used for such exposure include mercury lamps, metal halide lamps, xenon lamps, excimer lamps, and various other light sources.
[0104]
In addition to the method of performing pattern irradiation through a photomask using the light source as described above, it is also possible to use a method of drawing and irradiating in a pattern using a laser such as excimer or YAG.
[0105]
In addition, the irradiation amount of energy at the time of exposure is set to an irradiation amount necessary for the characteristic change layer surface to change the characteristic of the characteristic change layer surface by the action of the photocatalyst in the photocatalyst containing layer.
[0106]
At this time, it is preferable in that the photocatalyst-containing layer is exposed while being heated, so that the sensitivity can be increased and the characteristic can be changed efficiently. Specifically, it is preferable to heat within a range of 30 ° C to 80 ° C.
[0107]
The exposure direction in the present invention is a pattern formation method such as whether or not the photocatalyst-containing layer side light-shielding portion or pattern-forming substrate side light-shielding portion is formed, and the photocatalyst-containing layer side substrate or pattern-forming body substrate is transparent. It is determined by whether or not.
[0108]
That is, when the photocatalyst containing layer side light-shielding portion is formed, it is necessary to perform exposure from the photocatalyst containing layer side substrate side, and in this case, the photocatalyst containing layer side substrate is transparent to the energy irradiated. There must be. In this case, when the photocatalyst containing layer side light shielding part is formed on the photocatalyst containing layer and this photocatalyst containing layer side light shielding part is used so as to function as a spacer as described above, the exposure direction is It may be from the photocatalyst containing layer side substrate side or from the pattern forming body substrate side.
[0109]
On the other hand, when the pattern forming body substrate side light-shielding portion is formed, it is necessary to perform exposure from the pattern forming body substrate side, and in this case, with respect to the energy irradiated to the pattern forming body substrate Must be transparent. In this case as well, when the pattern forming body substrate-side light-shielding portion is formed on the characteristic change layer, and this pattern-forming body substrate-side light shielding portion is used so as to have the function as the spacer as described above, The exposure direction may be from the photocatalyst containing layer side substrate side or from the pattern forming body substrate side.
[0110]
In addition, the exposure direction when the photocatalyst-containing layer is formed in a pattern is irradiated from any direction as long as energy is applied to the portion where the photocatalyst-containing layer and the property change layer are in contact as described above. May be.
[0111]
Similarly, in the case of using the above-described spacer, irradiation may be performed from any direction as long as energy is applied to the contact portion.
[0112]
In the case of using a photomask, energy is irradiated from the side where the photomask is arranged. In this case, the substrate on which the photomask is arranged, that is, either the photocatalyst containing layer side substrate or the pattern forming body substrate needs to be transparent.
[0113]
When the energy irradiation as described above is completed, the photocatalyst-containing layer side substrate is separated from the contact position with the characteristic change layer, and thus comprises a characteristic change region 9 to which a functional group is added as shown in FIG. A pattern is formed on the characteristic change layer 5.
[0114]
In the present invention, the characteristic change layer is composed of a polymer material, and a reaction point is formed on the surface of the polymer material in the region irradiated with energy by the action of the photocatalyst accompanying energy irradiation. This substance reacts with this substance to give a functional group to the surface. As a result, a pattern having a predetermined functional group on its surface is formed on the surface of the polymer material, that is, on the surface of the property change layer. On the other hand, in a region where energy is not irradiated, since no reaction point is formed on the surface of the polymer material, no reaction is performed with a substance in the atmosphere. A pattern having the functional group is formed.
[0115]
In the present invention, it is possible to introduce a functional group-introducing substance into the gap during the energy irradiation. This is because the target functional group can be imparted on the property change layer.
[0116]
Here, the introduction of the functional group-introducing substance is to cause a substance having a functional group to be imparted on the characteristic change layer to exist between the photocatalyst-containing layer and the characteristic change layer. It may be contained in the gas phase or in the liquid phase. In addition, the introduction method and the like are appropriately selected depending on the type of the functional group introducing substance, and are not particularly limited. Specifically, for example, when the functional group introducing substance is included in the gas phase, , A method of performing in a gas phase atmosphere, a method of introducing a gas, and the like. Further, when the functional group introduction substance is contained in the liquid phase, a method in which water or a petroleum-based solvent in which the functional group introduction substance is dissolved is interposed between the photocatalyst containing layer and the property change layer as a thin film. Etc.
[0117]
Examples of the functional group-introducing substance of the present invention include oxygen, which makes it possible to introduce a carbonyl group, a hydroxyl group, a carboxyl group, and the like.
[0118]
Also, liquid or gaseous vinyl monomers can be cited as functional group-introducing substances, and by carrying out energy irradiation in the state of contact with the property change layer, graft polymerization can be performed and the vinyl monomers can be introduced. is there.
[0119]
Specifically, MAH, maleimide (MI), acenaphthylene and the like can be used as the vinyl monomer in the gas phase system. Mixed monomers can also be used. Specifically, styrene / acrylonitrile, allyl alcohol or glycidyl methacrylate, MAH, maleimide / styrene, N-vinylpyrrolidone, vinyl ether, benzyl methacrylate, or the like can be used. It is.
[0120]
For example, when an alkanethiol monomolecular film having a 4-azidobenzoyloxy group is used as the characteristic change layer, the energy irradiated region is obtained by irradiating energy while introducing dialkylamine as a functional group introducing substance. Can be hydrazine-modified.
[0121]
In the present invention, a pattern forming body having a specific functional group pattern on the surface can be obtained as described above. Such a pattern forming body can be obtained from a biochip, a microfluidic chip, and a conductive pattern forming body. It is possible to apply to such uses.
[0122]
3. Application
The pattern forming body obtained by the method for producing a pattern forming body of the present invention as described above can easily form various patterns having functional groups imparted on the characteristic change layer. In the present invention, as described above, for example, by the action of this functional group, the surface affinity, wettability, adhesiveness, etc. are changed, and various functional materials are applied to the changed part or the part that has not changed. It can be attached and used for various purposes.
[0123]
In the present invention, necessary functional groups are imparted to the surface of the characteristic change layer made of a polymer material depending on the type, concentration, pressure, presence of a catalyst, etc. in the atmosphere during pattern exposure. Various applications are developed using groups. Hereinafter, the use in the said pattern formation body is demonstrated.
[0124]
a. Biochip
For example, when the functional group imparted on the characteristic change layer by the action of the photocatalyst has a biological material binding property that binds to the biological material, it can be used as a biochip.
[0125]
In this case, a biochip base material is prepared by introducing a functional group having a biological substance binding property onto the characteristic change layer in the pattern forming body. Next, the biochip can be used as a biochip by binding, ie, immobilizing, the biomaterial to the functional group having the biomaterial binding property of the biochip substrate.
[0126]
On such a biochip surface, the functional group imparted to the surface of the characteristic change layer functions as an immobilization layer, and biological substances such as DNA and protein are immobilized thereon and used for various applications.
[0127]
As such a biological material immobilization technique, an immobilization technique that has been actively studied in research and development of a bioreactor in which an enzyme is immobilized on an insoluble carrier can be applied. The technical contents are detailed in, for example, edited by Ichiro Chibata, “Immobilized Enzyme”, Kodansha Scientific, 1975, and references thereof.
[0128]
Immobilization methods can be broadly classified into three types: immobilization by covalent bond, immobilization by ionic bond (electrostatic interaction), and immobilization by physical adsorption. In the immobilization of the biological material according to the present invention, the biological material is generally further immobilized on the substrate. For this reason, there should be no desorption of the biological material, and in this respect, the immobilization technique by physical adsorption is unsuitable. Therefore, it can be said that the immobilization by the covalent bond and the immobilization by the ionic bond (electrostatic interaction) are suitable as the method for immobilizing the biological substance according to the present invention.
[0129]
In the case of immobilization by covalent bond, for example, when the functional group provided on the property change layer is a carbonyl group (aldehyde group), it reacts directly with the amino group of the biological substance to form a so-called “Schiff base” and immobilize it. Can be When the functional group provided is an amino group, a “Schiff base” can be directly formed and immobilized in the system together with a biological material in the presence of a crosslinking agent such as glutaraldehyde. However, there are a variety of reports that can be referred to by a technique in which either a functional group imparted on the property change layer or a functional group of a biological substance is activated and then immobilized. At this time, when the biological substance is a protein, there is a possibility that the structure is damaged during the activation treatment, which may cause adverse effects. Therefore, it is generally preferable to activate the functional group provided on the property change layer.
[0130]
As the activation method, when the functional group imparted on the property change layer is an amino group, the method is activated by diazotization, and when the functional group imparted is a carboxyl group, azide, chloride, imidization, Examples of the method include activation by isocyanate formation, and in the case of a hydroxyl group, activation by cyanogen bromide, activation by ethyl chloroformate, and the like.
[0131]
In some cases, an electrical reading method is used for the biochip. In such a case, it is necessary to form electrodes on the surface of the biochip substrate. In this case, the electrode may be formed by a method described in the column of the conductive pattern forming body described later, or may be formed by a general photoresist method or the like.
[0132]
b. Microfluidic chip
The pattern forming body in the present invention can also be used as a microfluidic chip. In this case, the base for the pattern forming body needs to have a recess for flowing a fluid. When forming the recess, for example, when the substrate is made of an organic polymer material, a method of forming the recess by removing the characteristic change layer in the pattern forming body of the present invention described above may be used.
[0133]
In the present invention, a substrate for a microfluidic chip is prepared in which the molecules in the recesses are at least functional groups provided on the property change layer.
[0134]
In such a microfluidic chip substrate, as described above, the functional group imparted in the recess has a function of rectifying the flow of fluid in the recess, or the analysis or synthesis is performed in the recess. It has various functions that can be performed. Accordingly, some of these functional groups are extremely reactive, and it is usually very difficult to handle a coating solution such as gelation by using a material having such a functional group. It may become.
[0135]
The present invention solves such a problem, and after forming a characteristic change layer as a base material, the pattern forming step irradiates only the inside of the recess with energy in a pattern so that only the inside of the recess is functional. Since the group is added, it has an advantage that it is easy to form and handle.
[0136]
Moreover, such a substrate for a microfluidic chip can be used as a microfluidic chip by being bonded to a bonded substrate. The bonded base material used here may have a concave portion in a portion corresponding to the concave portion of the microfluidic chip base material, or may be a planar one.
[0137]
In the present invention, it is possible not to introduce a functional group on the microfluidic chip base material side but to have a functional group on the property change layer only on the bonded base material side. Moreover, the recessed part may be formed in the bonding base material side, and it is preferable also in this case that the functional group is provided on the characteristic change layer of the recessed part inner surface.
[0138]
In addition, it may be necessary to form an electrode on this microfluidic chip. Regarding the formation of this electrode as well, the production of a conductive pattern forming body using the pattern forming body manufacturing method of the present invention as described later is applied. It may be formed by a method, or may be formed by using a normal photolithography method.
[0139]
c. Conductive pattern forming body
The pattern forming body in the present invention can also be used as a conductive pattern forming body. In this case, the functional group imparted on the characteristic change layer by the action of the photocatalyst is a functional group having an electroless plating catalyst adhesion property that adheres to the electroless plating catalyst, and the substrate has an electrically insulating conductive property. A substrate for a pattern forming body is prepared.
[0140]
Here, regarding a functional group having an electroless plating catalyst adhesion and a process of attaching an electroless plating catalyst to the functional group, for example, Charge Constrained Metallization (CCM) process (for example, Mu-San Chen et al., Journal of The Electrochemical Society, vol. 146, 1421-1430, 1999; Mu-San Chen et al., Ibid, vol. 147, 2607-2610, 2000).
[0141]
In the method of the above document (hereinafter referred to as CCM method), a monomolecular film-forming material of a type in which a functional group is exposed is formed on the entire surface of the substrate, and a normal photolithography method, that is, resist coating, exposure, This is a technique including a step of forming a pattern in which a monomolecular film is exposed through development and attaching an electroless plating catalyst thereto. Comparing such a CCM method with the method according to the present invention, the present invention has significant advantages in that it does not use chemicals consumed in normal resist work and the process is simple because it is free from resist work. It is what has.
[0142]
The electroless plating catalyst is attached to the functional group imparted on the characteristic change layer of the substrate for a conductive pattern forming body obtained by such a method for manufacturing a substrate for forming a conductive pattern (described above). Next, refer to the CCM literature), and then performing electroless plating with the electroless plating catalyst attached in a pattern, thereby obtaining a conductive pattern forming body having a conductive pattern on the surface.
[0143]
Moreover, when electroconductivity is inadequate only with an electroless-plating layer, electrolytic plating, such as copper, is performed as needed. Further, electroless plating such as gold may be performed.
[0144]
This conductive pattern is used for various purposes such as printed wiring boards, DNA chips for electrical detection methods, protein chips for electrical detection methods, biochips for electrical detection methods such as cell chips for electrical detection methods. It can be used for a functional substrate for a microfluidic chip such as a substrate, a chemical chip (Lab-on-a-Chip) that requires input of electric power such as an electrophoresis process, and an analysis chip.
[0145]
In the present invention, since a conductive pattern is formed on the surface, the base must be insulative, and the degree of insulation depends on the use of the conductive pattern forming body to be used. It is determined accordingly.
[0146]
The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.
[0147]
【Example】
[Example 1]
1. Formation of photocatalyst containing layer side substrate
5 g of trimethoxymethylsilane (GE Toshiba Silicone Co., Ltd., TSL8113) and 2.5 g of 0.5N hydrochloric acid were mixed and stirred for 8 hours. This was diluted 10 times with isopropyl alcohol to obtain a primer layer composition.
[0148]
The primer layer composition is applied onto a 100 μm line & space photomask substrate with a spin coater and dried at 150 ° C. for 10 minutes to form a transparent primer layer (thickness 0.2 μm). did.
[0149]
Next, 30 g of isopropyl alcohol, 3 g of trimethoxymethylsilane (manufactured by GE Toshiba Silicone Co., Ltd., TSL8113) and 20 g of ST-K03 (manufactured by Ishihara Sangyo Co., Ltd.), which is a photocatalytic inorganic coating agent, are mixed at 100 ° C. Stir for 20 minutes. This was diluted 3 times with isopropyl alcohol to obtain a composition for a photocatalyst-containing layer.
[0150]
A transparent photocatalyst-containing layer (thickness: 0.15 μm) is obtained by applying the composition for a photocatalyst-containing layer onto a photomask substrate on which a primer layer has been formed using a spin coater and performing a drying treatment at 150 ° C. for 10 minutes. Formed.
[0151]
2. Formation of characteristic change layer
2 g of Iupilon Z400 (manufactured by Mitsubishi Gas Chemical), whose main component is polycarbonate, was dissolved in 30 g of dichloromethane and 70 g of 112 trichloroethane to obtain a composition for a decomposition layer removal layer.
[0152]
The said characteristic change layer composition was apply | coated with the spin coater on the glass substrate, and the transparent characteristic change layer (thickness 1.0 micrometer) was formed by performing the drying process for 60 minutes at 100 degreeC.
[0153]
3. Pattern formation process
After the photocatalyst containing layer side substrate and the polycarbonate layer were opposed to each other with a polyimide film as a spacer with a gap of 50 μm, ammonia gas was introduced into the space and 40 mW / cm was applied from the photomask side by an ultrahigh pressure mercury lamp (wavelength 365 nm). ² For 300 seconds.
[0154]
4). Evaluation
When this substrate was subjected to surface analysis by X-ray photoelectron spectroscopy, introduction of amino groups in a mask pattern was observed only in the exposed portion.
[0155]
At this time, the contact angle between the unexposed part and the water in the exposed part was measured using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) (30 seconds after dropping a droplet from the microsyringe). As a result, they were 72 ° and 19 °, respectively.
[0156]
[Comparative Example 1]
As a result of patterning in the same manner as in Example 1 except that a mask without a photocatalyst-containing layer was used, the introduction of amino groups in the exposed area was not observed, and the contact angle was 71 ° in the exposed area.
[0157]
[Example 2]
1. Formation of photocatalyst containing layer side substrate
A photocatalyst containing layer side substrate was formed in the same manner as in Example 1.
[0158]
2. Formation of characteristic change layer
A polypropylene film having a thickness of 200 μm was prepared.
[0159]
3. Pattern formation process
After the photocatalyst containing layer side substrate and the polypropylene film face each other with a gap of 50 μm using a polyimide film as a spacer, oxygen gas was introduced into the space and 40 mW / cm was applied from the photomask side by an ultrahigh pressure mercury lamp (wavelength 365 nm). ² For 200 seconds.
[0160]
4). Evaluation
When this substrate was subjected to surface analysis by X-ray photoelectron spectroscopy, introduction of carboxyl groups in the form of a mask pattern was observed only in the exposed portion.
[0161]
At this time, the contact angle between the unexposed part and the water in the exposed part was measured using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) (30 seconds after dropping a droplet from the microsyringe). As a result, they were 88 ° and 14 °, respectively.
[0162]
[Comparative Example 2]
As a result of performing patterning in the same manner as in Example 2 except that a mask without a photocatalyst-containing layer was used, introduction of carboxyl groups in the exposed area was not observed, and the contact angle was 87 ° also in the exposed area.
[0163]
[Example 3]
1. Formation of photocatalyst containing layer side substrate
A photocatalyst containing layer side substrate was formed in the same manner as in Example 1.
[0164]
2. Formation of characteristic change layer
A polycarbonate layer was formed on a glass substrate in the same manner as in Example 1.
[0165]
3. Pattern formation process
After the photocatalyst containing layer side substrate and the polycarbonate layer were opposed to each other with a polyimide film as a spacer with a gap of 50 μm, chlorine gas was introduced into the space, and 40 mW / cm was applied from the photomask side by an ultrahigh pressure mercury lamp (wavelength 365 nm). ² For 400 seconds.
[0166]
4). Evaluation
When this substrate was subjected to surface analysis by X-ray photoelectron spectroscopy, introduction of chlorine groups in a mask pattern was observed only in the exposed portion.
[0167]
At this time, the contact angle between the unexposed part and the water in the exposed part was measured using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) (30 seconds after dropping a droplet from the microsyringe). As a result, they were 72 ° and 24 °, respectively.
[0168]
[Comparative Example 3]
As a result of patterning in the same manner as in Example 3 except that a mask without a photocatalyst-containing layer was used, introduction of chlorine groups in the exposed area was not observed, and the contact angle was 72 ° in the exposed area.
[0169]
【The invention's effect】
According to the present invention, in the region irradiated with energy, a reaction point is formed on the characteristic change layer made of the polymer material by the action of the photocatalyst accompanying the energy irradiation, and reacts with, for example, a substance present in the atmosphere. A functional group is imparted to the surface of the characteristic change layer. On the other hand, in a region where energy is not irradiated, no reactive point is formed, so that no functional group is added. Thereby, it becomes possible to set it as the pattern formation body by which the functional group was provided to pattern shape. In the pattern formation step, it is possible to impart various functional groups to the surface of the polymer material by changing the substance to be reacted, etc., so that a pattern having functional groups in a pattern can be formed especially after exposure. No processing is required, and it can be easily formed with high definition. Such a pattern forming body can be applied to various uses.
[0170]
Further, since the photocatalyst containing layer side substrate is removed from the pattern forming body after exposure, the pattern forming body itself does not include the photocatalyst containing layer, and therefore there is a concern about deterioration over time due to the action of the photocatalyst of the pattern forming body. Absent. Furthermore, since the distance between the photocatalyst-containing layer and the characteristic change layer is within the above-described range, it is possible to obtain a pattern forming body having a pattern with a change in characteristics with good efficiency and accuracy.
[Brief description of the drawings]
FIG. 1 is a process diagram showing an example of a method for producing a pattern-formed body of the present invention.
FIG. 2 is a schematic cross-sectional view showing an example of a photocatalyst-containing layer side substrate used in the present invention.
FIG. 3 is a schematic cross-sectional view showing another example of the photocatalyst-containing layer side substrate used in the present invention.
FIG. 4 is a schematic cross-sectional view showing another example of the photocatalyst containing layer side substrate used in the present invention.
[Explanation of symbols]
1 ... Base material
2 ... Photocatalyst containing layer
3 ... Photocatalyst containing layer side substrate
4 ... Base
5 ... Characteristic change layer
6 ... Substrate for pattern forming body
9 ... Characteristic change area

Claims (16)

Pattern forming body substrate preparation step for preparing a pattern forming body substrate having a characteristic change layer made of a polymer material into which a functional group can be introduced by the action of a photocatalyst accompanying energy irradiation, and a photocatalyst containing photocatalyst After the photocatalyst containing layer and the property change layer in the photocatalyst containing layer side substrate having a layer and a substrate are arranged with a gap so as to be 200 μm or less, a functional group contained in the gas phase is introduced into the gap By introducing a substance and irradiating the photocatalyst-containing layer with energy from a predetermined direction, functional groups are imparted in a pattern on the surface of the property-changing layer made of the polymer material by the action of the photocatalyst contained in the photocatalyst-containing layer. And a pattern forming step. A method for producing a pattern forming body, comprising: The said photocatalyst containing layer side board | substrate consists of a base material and the photocatalyst containing layer formed in the pattern form on the said base material, The manufacturing method of the pattern formation body of Claim 1 characterized by the above-mentioned. The photocatalyst-containing layer side substrate comprises a base material, a photocatalyst-containing layer formed on the base material, and a photocatalyst-containing layer side light-shielding portion formed in a pattern,
2. The method for producing a pattern forming body according to claim 1, wherein the irradiation of energy in the pattern forming step is performed from a photocatalyst containing layer side substrate. In the photocatalyst-containing layer side substrate, the photocatalyst-containing layer side light-shielding portion is formed in a pattern on the substrate, according to claim 3 that is characterized in being further the photocatalyst-containing layer is formed thereon The manufacturing method of the pattern formation body of this. In the photocatalyst-containing layer side substrate, the photocatalyst-containing layer is formed on the substrate, to claim 3, wherein the photocatalyst-containing layer side light-shielding portion in the photocatalyst-containing layer is characterized by being formed in a pattern The manufacturing method of the pattern formation body of description. The said photocatalyst containing layer is a layer which consists of photocatalysts, The manufacturing method of the pattern formation body in any one of Claim 1-5 characterized by the above-mentioned. The method for producing a pattern forming body according to claim 6 , wherein the photocatalyst-containing layer is a layer formed by depositing a photocatalyst on a substrate by a vacuum film-forming method. The said photocatalyst containing layer is a layer which has a photocatalyst and a binder, The manufacturing method of the pattern formation body in any one of Claim 1- Claim 5 characterized by the above-mentioned. The photocatalyst is composed of titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide (Bi ₂ O ₃ ), and oxide. The method for producing a pattern forming body according to any one of claims 1 to 8 , wherein the pattern forming body is one or more substances selected from iron (Fe ₂ O ₃ ). The method for producing a pattern forming body according to claim 9, wherein the photocatalyst is titanium oxide (TiO ₂ ). The biological material in which the functional group provided on the characteristic change layer of the pattern formed body obtained by the method for producing a pattern formed body according to any one of claims 1 to 10 is bonded to the biological material. A method for producing a biochip substrate, which is a functional group having binding properties. The substrate of the pattern forming body obtained by the method for manufacturing a pattern forming body according to any one of claims 1 to 10 has a recess for flowing a fluid, and at least a height in the recess is high. A method for producing a substrate for a microfluidic chip, wherein a predetermined functional group is provided in a pattern on the surface of a characteristic change layer made of a molecular material in the pattern forming step. The functional group provided on the characteristic change layer of the pattern forming body obtained by the method of manufacturing a pattern forming body according to any one of claims 1 to 10 adheres to the electroless plating catalyst. A method for producing a substrate for forming a conductive pattern, which is a functional group having catalyst adhesion for electroless plating and wherein the polymer is electrically insulating. A method for producing a biochip, comprising a step of binding a biological substance to a functional group of a biochip substrate obtained in the method for producing a biochip substrate according to claim 11 . A method for manufacturing a microfluidic chip, comprising the step of bonding a base material for a microfluidic chip obtained by the method for manufacturing a base material for a microfluidic chip according to claim 12 and a bonded base material. A catalyst adhering step for adhering an electroless plating catalyst to the functional group to which the conductive pattern forming substrate obtained by the method for producing a conductive pattern forming substrate according to claim 13 is attached, and A method for producing a conductive pattern, comprising: an electroless plating step for performing electroless plating on a substrate on which a catalyst for electroless plating is attached in a pattern by a catalyst attaching step.

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