JP2003222626A - Manufacturing method for pattern organizer - 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 μm or less. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a pattern-formed product which is capable of introducing a functional group onto the surface of the pattern-formed product and does not need to contain a photocatalyst in the pattern-formed product itself.

[0002]

2. Description of the Related Art Conventionally, there has been proposed a method of imparting a functional group in a pattern form to a surface of a polymer substrate or a laminate having a polymer thin film formed on the surface of the substrate and using it for various functional devices. . Graft polymerization is known as a method for introducing a functional group into such a polymer material, and γ-rays, electron beams, ultraviolet rays, etc. have been used as an energy source for carrying out the graft polymerization.

However, when γ-rays or electron beams are used, the polymer chains in the polymer material itself are cleaved or cross-linked or deteriorated. There was a problem that the width was narrow.

Further, in the case of graft-polymerizing on the surface of the polymer material using ultraviolet rays, the damage to the polymer material is low as compared with the case of using γ ray or electron beam,
In order to carry out uniform and good graft polymerization, it was 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, and depending on the type of base and the polymerization system. However, there is a problem that it becomes difficult to select an appropriate sensitizer. Further, after the polymerization treatment, on the surface of the base material, a sensitizer and a binder for supporting the sensitizer on the surface of the base material remain,
Depending on the application, the sensitizer may cause a problem of contaminating the system using the grafted polymer material, which may cause a problem that it is not suitable for the intended application.

No prior art document relating to the present invention has been found.

[0006]

PROBLEM TO BE SOLVED: To provide a method for producing a pattern-formed product, which is capable of efficiently imparting a functional group to the surface of the pattern-formed product and which does not require post-treatment such as post-exposure. Is desired.

[0007]

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 as described in claim 1. And a photocatalyst containing layer on the photocatalyst containing layer side substrate having a photocatalyst containing layer containing a photocatalyst and a substrate.
After arranging with a gap so as to be 0 μm or less, energy is irradiated from a predetermined direction to form a pattern forming step of imparting a functional group in a pattern on the surface of the characteristic changing layer made of the above-mentioned polymer material. A method for manufacturing a pattern-formed body, which is characterized by the above.

According to the present invention, in the energy-irradiated region, a reaction point is formed on the characteristic change layer made of a polymer material due to the action of the photocatalyst accompanying the energy irradiation, and for example, a substance existing in the atmosphere or the like. Reacts with and functional groups are added to the surface of the characteristic change layer. On the other hand, in a region which is not irradiated with energy, no reaction site is formed, and thus a functional group is not provided. As a result, it becomes possible to obtain a pattern-formed product in which the surface characteristics are changed by providing the functional group in a pattern. Further, in the pattern formation step, various functional groups can be imparted to the surface of the polymer material by changing the substance to be reacted, whereby a pattern having a functional group in a pattern can be formed especially after exposure. It can be easily formed in high definition without any treatment. Such a pattern forming body can be applied to various uses.

Further, since the distance between the photocatalyst-containing layer and the characteristic change layer is within the above-mentioned range, a pattern having a pattern whose characteristics are changed by providing a functional group on the surface with high efficiency and good accuracy. A formed body can be obtained.

In the invention described in claim 1, as described in claim 2, in the pattern forming step, a functional group-introducing substance can be introduced into the gap. This makes it possible to introduce a target functional group onto the characteristic change layer by the action of the photocatalyst associated with energy irradiation.

In the invention described in claim 1 or claim 2, as described in claim 3, the photocatalyst containing layer side substrate is formed on a base material and on the base material in a pattern. And a photocatalyst-containing layer. Thus, by forming the photocatalyst-containing layer in a pattern, it becomes possible to form a pattern having different characteristics by providing a functional group on the characteristic change layer without using a photomask. . Further, since only the surface corresponding to the photocatalyst containing layer is changed to the lyophilic region, the energy to be irradiated is not particularly limited to parallel energy, and the irradiation direction of energy is not particularly limited. This is because it has the advantage that the degree of freedom in the type and arrangement of energy sources is significantly increased.

In the invention described in claim 1 or claim 2, the photocatalyst containing layer side substrate may include a base material and a photocatalyst containing layer formed on the base material. It is preferable that the photocatalyst-containing layer side light-shielding portion is formed in a pattern, and the energy irradiation in the pattern forming step is performed from the photocatalyst-containing layer side substrate.

Since the photocatalyst-containing layer side light-shielding portion is provided on the photocatalyst-containing layer side substrate as described above, it is not necessary to use a photomask or the like at the time of exposure, so that alignment with the photomask is unnecessary and the process is simplified. It is possible to do so.

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 base material. The photocatalyst-containing layer may be further formed thereon, and the photocatalyst-containing layer may be further formed.
In the photocatalyst containing layer side substrate as described in, the photocatalyst containing layer is formed on the base material, the photocatalyst containing layer side light-shielding portion is formed on the photocatalyst containing layer in a pattern. Good.

It can be said that it is preferable that the photocatalyst-containing layer side light-shielding portion is arranged 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. Further, when the photocatalyst containing layer side light-shielding portion 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.

In the invention described in any one of claims 1 to 6, it is preferable that the photocatalyst-containing layer is a layer composed of a photocatalyst, as described in claim 7. . If the photocatalyst-containing layer is a layer consisting only of the photocatalyst, it is possible to improve the efficiency of changing the characteristics by providing a functional group on the characteristic changing layer, and it is possible to efficiently produce a pattern-formed body. Because you can.

In the invention described in claim 7, as described in claim 8, the photocatalyst containing layer comprises:
It is preferably a layer formed by forming a film of a photocatalyst on a substrate by a vacuum film forming method. By forming the photocatalyst-containing layer by the vacuum film-forming method in this manner, it is possible to obtain a uniform photocatalyst-containing layer having a uniform film thickness with less unevenness on the surface,
This is because it is possible to uniformly and highly efficiently form a pattern on the surface of the characteristic change layer.

On the other hand, in the invention described in any one of claims 1 to 6, as described in claim 9, the photocatalyst containing layer contains a photocatalyst and a binder. May be By using the binder as described above, the photocatalyst-containing layer can be formed relatively easily, and as a result, the pattern-formed body can be manufactured at low cost.

In the invention described in any one of claims 1 to 9, as described in claim 10, the photocatalyst is titanium oxide (Ti).
O ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ),
It is preferably one or more substances selected from strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide (Bi ₂ O ₃ ), and iron oxide (Fe ₂ O ₃ ). In particular, as described in claim 11, the photocatalyst is titanium oxide (TiO ₂ ).
Is preferred. This is because titanium dioxide is effective as a photocatalyst because of its high band gap energy, is chemically stable, has no toxicity, and is easily available.

Further, as described in claim 12, on the characteristic change layer of the pattern forming body obtained by the method for manufacturing the pattern forming body according to any one of claims 1 to 11. It is possible to provide a method for producing a biochip substrate, wherein the imparted functional group is a functional group having a biomaterial-binding property that binds to a biomaterial. Since the above-mentioned functional group has a biomaterial binding property, a high-definition biochip can be easily formed by binding the biomaterial to the functional group provided in a pattern.

Further, as described in claim 13, the substrate of the pattern forming body obtained by the method for manufacturing the pattern forming body according to any one of claims 1 to 11 is a fluid. For a microfluidic chip, which has a recess for flowing, and in which a predetermined functional group is provided in a pattern in the pattern forming step on at least the surface of the characteristic change layer made of a polymer material in the recess A method for manufacturing a substrate is provided. A base material for a microfluidic chip capable of easily controlling a fluid by providing a functional group for controlling the flow of the fluid on the surface of the concave portion of the base material for the microfluidic chip, which serves as a flow path for the fluid. can do.

Further, as described in claim 14, on the characteristic change layer of the pattern forming body obtained by the method for manufacturing the pattern forming body according to any one of claims 1 to 11. The functional group imparted is a functional group having electrocatalytic plating catalyst adhesion to an electroless plating catalyst, and the polymer is electrically insulating. A conductive pattern forming substrate. A method for manufacturing the same is provided. If the above functional group has electroless plating catalyst adhesion, by attaching a catalyst for electroless plating to the deprotection functional group formed in a pattern, it is possible to easily form a highly precise conductive pattern. Can be formed.

In the present invention, as described in claim 15, a biological substance is bound to a functional group of the biochip substrate obtained in the method for producing a biochip substrate according to claim 12. There is provided a method for producing a biochip, which comprises the step of: According to the method of the present invention, it is possible to obtain a high-density biochip relatively easily.

In the present invention, as described in claim 16, a microfluidic chip substrate obtained by the method for producing a microfluidic chip substrate according to claim 13 and a bonded substrate are provided. There is provided a method for manufacturing a microfluidic chip, which has a step of bonding. As described above, according to the manufacturing method of the present invention, it becomes possible to extremely easily introduce a functional group for controlling the fluid into the recess.

According to the present invention, further, claim 1
As described in 7, the catalyst adhesion for attaching the electroless plating catalyst to the functional group of the conductive pattern forming base material obtained by the method for manufacturing a conductive pattern forming base material according to claim 14. Provided is a method for producing a conductive pattern, which comprises an electroless plating step of performing electroless plating on a substrate on which a catalyst for electroless plating is attached in a pattern by the catalyst attaching step. . According to the method of the present invention, a highly precise conductive pattern can be easily obtained.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION First, a method for manufacturing a pattern-formed body of the present invention will be described. The method for producing a pattern-formed body of the present invention includes a pattern-formed body substrate preparing step of preparing a pattern-formed body substrate having a property changing layer made of a polymer material, and a photocatalyst containing a photocatalyst-containing layer and a substrate. The containing layer side substrate and the characteristic change layer are
After arranging so as to have a gap of not more than 00 μm, a pattern forming step of imparting a functional group in a pattern to the surface of the characteristic change layer made of the above-mentioned polymer material by irradiating energy from a predetermined direction is included. It is characterized by that.

Further, the present invention may include a photocatalyst containing layer side substrate adjusting step of adjusting a photocatalyst containing layer side substrate having a photocatalyst containing layer and a photocatalyst containing layer side substrate. A photocatalyst containing layer side substrate adjusting step of adjusting a photocatalyst containing layer side substrate having a photocatalyst containing layer and a base material to be contained, and pattern formation having a property changing layer whose surface characteristics are changed by the action of the photocatalyst in the photocatalyst containing layer. The pattern forming body substrate preparing step for preparing the body substrate and the photocatalyst containing layer and the property changing layer
A pattern forming step of forming a pattern with changed characteristics on the surface of the characteristic changing layer by irradiating energy from a predetermined direction after arranging so as to have a gap of not more than 00 μm. A method for manufacturing a pattern formed body, wherein the pattern formed body substrate comprises:
It is formed of a characteristic changing layer made of a polymer, and in the pattern forming step, a functional group is imparted in a pattern on the surface of the characteristic changing layer made of the polymeric material.

In the method for producing a pattern-formed 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 the photocatalyst in the photocatalyst-containing layer is irradiated with energy from a predetermined direction. By the action of, the reaction point is formed in the characteristic change layer of the exposed portion facing the photocatalyst containing layer, and by reacting with a substance in the atmosphere, a pattern having a functional group is formed on the surface of the characteristic change layer. To be done. Therefore, post-treatment such as development / washing after exposure is not required at the time of pattern formation, and thus it is possible to form a pattern having different characteristics by adding a functional group at a lower number of steps than before. Then, by selecting the material of the property changing layer and the functional group to be provided, it is possible to obtain a pattern formed body that can be used for various purposes.

Furthermore, in the present invention, after changing the characteristics on the characteristic changing layer 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. Therefore, it is not necessary that the obtained pattern-formed body contains a photocatalyst. Therefore, it is possible to prevent a problem that the obtained pattern-formed body is deteriorated with time due to the action of the photocatalyst.

The method for manufacturing the pattern-formed body of the present invention will be specifically described with reference to the drawings. Figure 1
Shows an example of a method for manufacturing a pattern-formed body of the present invention.

In this example, first, a photocatalyst containing layer side substrate 3 formed by forming a photocatalyst containing layer 2 on a base material 1,
The pattern forming body substrate 6 in which the characteristic change layer 5 is formed on the substrate 4 is adjusted (FIG. 1A).

Next, as shown in FIG. 1B, in the photocatalyst containing layer side substrate 3 and the pattern forming substrate 6, the photocatalyst containing layer 2 and the characteristic changing layer 5 have predetermined intervals. After arranging as described above, a photomask 7 on which a required pattern is drawn is used, and ultraviolet light 8 is irradiated from the photocatalyst containing layer side substrate 3 side through the photomask 7. As a result, as shown in FIG. 1C, a pattern composed of the regions 9 having different characteristics due to the functional group being provided on the surface of the characteristic changing layer 5 is formed (pattern forming step).

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, they may be physically adhered if necessary. You may make it contact.

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. As a result, it becomes possible to introduce a desired functional group onto the surface of the characteristic change layer, and by changing the type of the functional group-introduced substance, it is possible to form a pattern-formed product that can be used for various purposes. Is possible.

Further, the irradiation of the ultraviolet rays is carried out through the photomask 7 in the above example, but as will be described later, the photocatalyst containing layer is formed in a pattern, or the photocatalyst containing layer side substrate is shielded from light. A part (a photocatalyst containing layer side light-shielding part) may be used, and in this case, the entire surface is exposed without using the photomask 7 or the like.

Then, a step of removing the photocatalyst containing layer side substrate from the pattern forming substrate 6 is performed (FIG. 1).
(D)) It is possible to obtain the pattern-formed body 6 having a pattern whose characteristics are changed on the surface.

The method for manufacturing the pattern-formed body of the present invention will be described in detail for each step.

1. Pattern Forming Body Substrate Preparing Step First, the pattern forming body substrate adjusting step in the present invention will be described. The step for preparing a pattern-formed body substrate in the present invention is a step for preparing a pattern-formed body substrate having a characteristic change layer made of a polymer material.

The characteristic change layer used in the present invention is, for example, a film made of a polymer material, a molded product made of a polymer material, or the like serving as a substrate for the pattern forming body, and may be formed on the substrate as necessary. It may be a stack of molecular materials.

In the present invention, there is no particular limitation as long as it is a polymer material capable of introducing various functional groups on the surface in the pattern forming step described later. Specifically, polyethylene, polycarbonate, polypropylene, polystyrene, polyester, polyvinyl fluoride, acetal resin, nylon, ABS, PTF
Examples thereof include E, methacrylic resin, phenol resin, polyvinylidene fluoride, polyoxymethylene, polyvinyl alcohol, polyvinyl chloride, polyethylene terephthalate, silicone, cellulose, rubber, polyvinyl alcohol and nylon.

The material used as the characteristic change layer when the characteristic change layer made of a polymer material is formed on the substrate is, for example, an alkanethiol monomolecular film having a 4-azidobenzoyloxy group. To be

The substrate on which such a characteristic changing layer is formed is a silicon wafer, metal, quartz, glass, diamond, diamond-like carbon (DL).
C), alumina, polymer materials, etc. can be used,
These are appropriately selected and used according to the applications described later.

Further, the shape of the substrate used is not particularly limited, and it may be a suitable shape according to the application described later. Specifically, the application is a biochip or the like. In the case of (1), a plate-shaped material is preferably used, and when the application is a microfluidic chip, a material having a predetermined concave portion can be used.

In the present invention, it is possible to use a substrate for a pattern-formed body on which a light-shielding portion on the substrate-side for the patterned body is formed in a pattern.

In this case, since it is necessary to perform energy irradiation in the pattern forming process described later from the side of the pattern forming body substrate, the pattern forming body substrate needs to be transparent.

The method of forming the light-shielding portion on the substrate for the pattern forming body is not particularly limited, and the characteristics of the surface on which the light-shielding portion for the substrate for the pattern forming body is formed, the shielding ability for the required energy, and the like. It is appropriately selected and used accordingly.

For example, it may be formed by forming a thin metal film of chromium or the like having a thickness of about 1000 to 2000 Å by a sputtering method, a vacuum deposition method or the like, and patterning this thin film. As a method of this patterning,
A usual patterning method such as sputtering can be used.

Further, carbon fine particles in the resin binder,
A method may be used in which a layer containing light-shielding particles such as metal oxides, inorganic pigments, and organic pigments is formed in a pattern.
As the resin binder used, one or a mixture of two or more resins such as polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, and cellulose, a photosensitive resin, and O / It is possible to use a W emulsion type resin composition, for example, an emulsion of reactive silicone. The thickness of such a resin light-shielding portion can be set within the range of 0.5 to 10 μm. As a method of patterning the resin light-shielding portion, a generally used method such as a photolithography method or a printing method can be used.

2. Pattern Forming Step Step Next, the pattern forming step in the present invention will be described. In the pattern forming step of the present invention, the photocatalyst containing layer containing the photocatalyst and the photocatalyst containing layer and the characteristic change layer in the photocatalyst containing layer side substrate having the substrate are arranged with a predetermined gap and then in a predetermined direction. Is a step of applying a functional group in a pattern to the surface of the characteristic change layer made of the above-mentioned polymer material by irradiating energy from the above.

Each component of this step will be described below.

(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. The photocatalyst containing layer side substrate used in the present invention is thus one having at least a photocatalyst containing layer and a base material, and usually a thin film photocatalyst containing layer formed by a predetermined method on the base material is a photocatalyst containing layer. It is formed. Further, as the photocatalyst containing layer side substrate, one having a photocatalyst containing layer side light shielding part formed in a pattern can be used. Hereinafter, each structure of the photocatalyst containing layer side substrate will be described.

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 property change layer, and the photocatalyst and the binder are not particularly limited. The photocatalyst alone may be used to form a film. The surface wettability may be lyophilic or liquid repellent.

The photocatalyst-containing layer used in the present invention may be formed on the entire surface of the base material 1 as shown in FIG. 1 (a) or the like, for example, as shown in FIG. In addition, the photocatalyst containing layer 2 may be formed on the substrate 1 in a pattern.

By thus forming the photocatalyst-containing layer in a pattern, the photocatalyst-containing layer is arranged at a predetermined distance from the characteristic change layer and is irradiated with energy, as will be described in a pattern forming step described later. At this time, it is not necessary to perform pattern irradiation using a photomask or the like, and by irradiating the entire surface, a pattern having changed characteristics can be formed by providing a functional group on the characteristic change layer.

The patterning method of this photocatalyst processing layer is as follows.
Although not particularly limited, for example, it can be performed by a photolithography method or the like.

Further, since the functional group is actually added only to the portion on the characteristic changing layer facing the photocatalyst containing layer to change the characteristic, the energy irradiation direction is the same as the photocatalyst containing layer and the characteristic changing layer. As long as the energy is applied to the part facing the surface, it may be applied from any direction, and the energy applied is not limited to parallel light such as parallel light. .

The mechanism of action of a photocatalyst represented by titanium dioxide as described below in such a photocatalyst-containing layer is not necessarily clear, but the carrier generated by irradiation with light directly interacts with a nearby compound. Depending on the reaction or reactive oxygen species generated in the presence of oxygen and water,
It is considered to change the chemical structure of organic substances. In the present invention, it is considered that this carrier acts on the compound in the characteristic change layer arranged in the vicinity of the photocatalyst containing layer.

As the photocatalyst used in the present invention, a light semiconductor
Known as the body, for example titanium dioxide (TiO 2_Two),acid
Zinc oxide (ZnO), tin oxide (SnO)_Two), Titanium titanate
Trontium (SrTiO_Three), Tungsten oxide (W
O_Three), Bismuth oxide (Bi _TwoO_Three), And iron oxide
(Fe_TwoO_Three), Choose from these
It is possible to use one kind or a mixture of two or more kinds.

In the present invention, especially titanium dioxide is
It is preferably used because it has a high band gap energy, is chemically stable, has no toxicity, and is easily available.
Titanium dioxide includes anatase type and rutile type, and both can be used in the present invention, but anatase type titanium dioxide is preferable. Anatase type titanium dioxide has an excitation wavelength of 380 nm or less.

Examples of such anatase-type titanium dioxide include hydrochloric acid peptization-type anatase-type titania sol (STB-02 (average particle size 7 nm) manufactured by Ishihara Sangyo Co., Ltd.)
Examples include ST-K01 manufactured by Ishihara Sangyo Co., Ltd. and a nitrate-deflocculating anatase-type titania sol (TA-15 manufactured by Nissan Chemical Co., Ltd. (average particle size 12 nm)).

The smaller the particle size of the photocatalyst is, the more effectively the photocatalytic reaction takes place. The average particle size is preferably 50 nm or less, and it is particularly preferable to use the photocatalyst having a particle size of 20 nm or less.

The photocatalyst containing layer in the present invention may be formed by the photocatalyst alone as described above, or may be formed by mixing with the binder.

In the case of the photocatalyst containing layer consisting of only the photocatalyst, the efficiency with respect to the change of the characteristics on the characteristic change layer is improved,
It is advantageous in terms of cost such as reduction of processing time. On the other hand, the photocatalyst-containing layer composed of the photocatalyst and the binder has an advantage that the photocatalyst-containing layer can be easily formed.

As a method of forming the photocatalyst-containing layer consisting of only the photocatalyst, there can be mentioned, for example, a method using a vacuum film forming method such as a sputtering method, a CVD method, or a vacuum vapor deposition method. By forming the photocatalyst-containing layer by the vacuum film formation method, it is possible to obtain a photocatalyst-containing layer that is a uniform film and contains only the photocatalyst, and this makes it possible to uniformly change the properties on the property change layer. Since it is possible and it consists only of a photocatalyst, it becomes possible to change the characteristic on a characteristic change layer more efficiently compared with the case where a binder is used.

As a method of forming the photocatalyst-containing layer consisting of only the photocatalyst, for example, when the photocatalyst is titanium dioxide, a method of forming amorphous titania on the substrate and then changing the phase to crystalline titania by firing, etc. Is mentioned.
As the amorphous titania used here, for example, titanium tetrachloride, hydrolysis of inorganic salts of titanium such as titanium sulfate,
It can be obtained by dehydration condensation, hydrolysis and dehydration condensation of an organic titanium compound such as tetraethoxy titanium, tetraisopropoxy titanium, tetra-n-propoxy titanium, tetrabutoxy titanium and tetramethoxy titanium in the presence of an acid. Then, it is transformed into anatase-type titania by firing at 400 ° C to 500 ° C, and 600 ° C to
It can be modified into rutile type titania by firing at 700 ° C.

When a binder is used, it is preferable that the main skeleton of the binder has a high binding energy so as not to be decomposed by photoexcitation of the photocatalyst, and examples thereof include organopolysiloxane.

When the organopolysiloxane is used as the binder as described above, the photocatalyst-containing layer is prepared by dispersing the photocatalyst and the organopolysiloxane as the binder in a solvent together with other additives as necessary. Can be prepared, and this coating solution can be applied onto a substrate to form a film. As the solvent used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The coating can be carried out by a known coating method such as spin coating, spray coating, dip coating, roll coating or bead coating. When the binder contains an ultraviolet curable component, the photocatalyst-containing layer can be formed by irradiating ultraviolet rays to perform a curing treatment.

Further, an amorphous silica precursor can be used as the binder. This amorphous silica precursor is represented by the general formula SiX ₄ , where X is a silicon compound such as halogen, methoxy group, ethoxy group or acetyl group, silanol which is a hydrolyzate thereof, or an average molecular weight of 3,000 or less. Polysiloxane is preferred.

Specific examples thereof include tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetrabutoxysilane and tetramethoxysilane. Further, in this case, the amorphous silica precursor and the photocatalyst particles are uniformly dispersed in the non-aqueous solvent,
The photocatalyst-containing layer can be formed by hydrolyzing silanol on the base material with water in the air to form silanol, and then performing dehydration polycondensation at room temperature. Dehydration condensation polymerization of silanol 10
If it is carried out at 0 ° C. or higher, the degree of polymerization of silanol increases and the strength of the film surface can be improved. These binders can be used alone or in combination of two or more.

When the binder is used, the content of the photocatalyst in the photocatalyst containing layer is 5 to 60% by weight, preferably 20 to
It can be set in the range of 40% by weight. Further, the thickness of the photocatalyst-containing layer is preferably in the range of 0.05 to 10 μm.

Further, the photocatalyst-containing layer may contain a surfactant in addition to the above-mentioned photocatalyst and binder.
Specifically, NIKKOL B manufactured by Nikko Chemicals Co., Ltd.
Hydrocarbon series such as L, BC, BO, BB series, DuPont ZONYL FSN, FSO, Asahi Glass Co., Ltd.
Surflon S-141, 145, manufactured by Dainippon Ink and Chemicals, Inc., Megafac F-141, 144, Neos Co., Ltd., Futgent F-200, F251, Daikin Industries, Ltd., Unidyne DS-401, 402. , Fluorine-based or silicone-based nonionic surfactants such as Florade FC-170, 176 manufactured by 3M Co., Ltd., and cationic surfactants, anionic surfactants and amphoteric surfactants can be used. It can also be used.

Further, in the photocatalyst-containing layer, in addition to the above-mentioned surfactant, 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, oligomers such as polyisoprene, A polymer or the like can be included.

B. Base Material In the present invention, as shown in FIG. 1A, the photocatalyst containing layer side substrate 3 has at least a base material 1 and a photocatalyst containing layer 2 formed on the base material 1.

At this time, the material constituting the base material used is appropriately selected depending on the direction of energy irradiation in the pattern forming step described later and whether the obtained pattern formed body needs to be transparent.

That is, for example, when an opaque pattern forming body is used as the substrate, the energy irradiation direction is necessarily from the photocatalyst containing layer side substrate side,
As shown in FIG. 1B, it is necessary to dispose a photomask 7 on the side of the photocatalyst containing layer side substrate 3 for energy irradiation. Further, as will be described later, the photocatalyst-containing layer side light-shielding part is formed in advance in a predetermined pattern on the photocatalyst-containing layer side substrate, and even when the pattern is formed using this photocatalyst-containing layer side light-shielding part, the photocatalyst-containing layer It is necessary to irradiate energy from the side substrate side. In such a case, the base material needs to be transparent.

On the other hand, if the pattern forming body is transparent, it is possible to irradiate energy by disposing a photomask on the side of the pattern forming body substrate. Further, 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 base material is not particularly required.

The base material used in the present invention may be a flexible one, for example, a resin film, or a non-flexible one, for example, a glass substrate. . This is appropriately selected depending on the energy irradiation method in the pattern forming step described later.

As described above, the base material used for the photocatalyst containing layer side substrate in the present invention is not particularly limited in its material, but in the present invention, the photocatalyst containing layer side substrate is repeatedly used. Therefore, a material having a predetermined strength and having a surface having good adhesion to the photocatalyst-containing layer is preferably used.

Specifically, glass, ceramic, metal,
Examples thereof include plastics.

An anchor layer may be formed on the substrate in order to improve the adhesion between the substrate surface and the photocatalyst containing layer. Examples of such anchor layers include silane-based and titanium-based coupling agents.

C. Photocatalyst-containing layer-side light-shielding part The photocatalyst-containing layer-side light-shielding part used in the present invention may have a pattern-formed photocatalyst-containing layer-side light-shielding part. By using the photocatalyst-containing layer side substrate having the photocatalyst-containing layer side light-shielding portion as described above, it is not necessary to use a photomask or perform drawing irradiation with laser light at the time of exposure. Therefore, it is not necessary to align the photocatalyst containing layer side substrate and the photomask,
Since it can be a simple process, and an expensive device necessary for drawing irradiation is unnecessary, it has an advantage of cost advantage.

The photocatalyst-containing layer side substrate having such a photocatalyst-containing layer side light-shielding portion can be made into the following two embodiments depending on the formation position of the photocatalyst-containing layer side light-shielding portion.

One is, for example, as shown in FIG.
In this embodiment, the photocatalyst-containing layer side light-shielding portion 12 is formed on the photocatalyst-containing layer side light-shielding portion 12, and the photocatalyst-containing layer 2 is formed on the photocatalyst-containing layer side light-shielding portion 12. the other one is,
For example, as shown in FIG. 4, this is an embodiment in which the photocatalyst-containing layer 2 is formed on the base material 1 and the photocatalyst-containing layer side light-shielding portion 12 is formed thereon to form the photocatalyst-containing layer side substrate 3.

In any of the embodiments, as compared with the case where a photomask is used, the photocatalyst containing layer side light-shielding portion is arranged in the vicinity of the portion where the photocatalyst containing layer and the characteristic change layer are located with a gap. Therefore, it is possible to reduce the influence of energy scattering in the base material and the like, so that it becomes possible to perform energy pattern irradiation extremely accurately.

Further, in the embodiment in which the photocatalyst containing layer side light-shielding portion 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 of the photocatalyst-containing layer side light-shielding portion coincide with the width of the gap, the photocatalyst-containing layer side light-shielding portion can be used also as a spacer for keeping the gap constant. Have.

That is, when the photocatalyst containing layer and the characteristic changing layer are arranged in contact with each other with a predetermined gap, the photocatalyst containing layer side light-shielding portion and the characteristic changing layer are arranged in close contact with each other. By doing so, it is possible to make the predetermined gap accurate, and by irradiating energy from the photocatalyst containing layer side substrate in this state, it becomes possible to form a pattern on the characteristic change layer with high precision. Of.

The method of forming the light-shielding portion on the photocatalyst containing layer side used in the present invention is the same as the method of forming the light-shielding portion in the above-mentioned substrate for a pattern forming body, and therefore the description thereof is omitted here.

In the above description, the photocatalyst containing layer side light-shielding portion is formed between the substrate 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 on the side where the photocatalyst containing layer is not formed. In this mode, for example, a case where a photomask is closely attached to this surface in a detachable manner can be considered, and it can be suitably used in a case where the pattern forming body is changed in a small lot.

D. Primer Layer Next, the primer layer used in the photocatalyst-containing layer side substrate of the present invention will be described. In the present invention, the photocatalyst containing layer side light-shielding portion is formed in a pattern on the substrate as described above, and in the case of forming the photocatalyst containing layer on the photocatalyst containing layer side substrate, the above photocatalyst containing You may form a primer layer between a layer side light-shielding part and a photocatalyst containing layer.

Although the function and function of the primer layer are not always clear, the primer layer is formed between the photocatalyst containing layer side light-shielding portion and the photocatalyst containing layer, so that the characteristics of the primer layer change due to the action of the photocatalyst. Impurities from the openings existing between the photocatalyst-containing layer side light-shielding portion and the light-catalyst-containing layer side light-shielding portion, which are factors that hinder the change in the characteristics of the layer, particularly residues generated when patterning the photocatalyst-containing layer side light-shielding portion, It is considered to have a function of preventing diffusion of impurities such as metals and metal ions. Therefore, by forming the primer layer, the process of characteristic change proceeds with high sensitivity, and as a result, it becomes possible to obtain a high-resolution pattern.

In the present invention, the primer layer prevents the impurities existing in not only the photocatalyst-containing layer side light-shielding portions but also the openings formed between the photocatalyst-containing layer side light-shielding portions from affecting the action of the photocatalyst. Therefore, the primer layer is preferably formed over the entire photocatalyst-containing layer side light-shielding portion including the opening.

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 and the photocatalyst containing layer are not in contact with each other.

The material forming the primer layer is not particularly limited, but an inorganic material that is not easily decomposed by the action of the photocatalyst is preferable. Specifically, amorphous silica can be mentioned. When such amorphous silica is used, the precursor of the amorphous silica is represented by the general formula SiX ₄ , where X is a silicon compound such as halogen, methoxy group, ethoxy group, or acetyl group, Silanol, which is a hydrolyzate thereof, or polysiloxane having an average molecular weight of 3000 or less is preferable.

The film thickness of the primer layer is 0.001
It is preferably in the range of μm to 1 μm, and particularly preferably in the range of 0.001 μm to 0.1 μm.

(Formation of Pattern) Next, formation of the pattern of the present invention will be described. In the pattern forming step of the present invention, after disposing the photocatalyst containing layer and the characteristic change layer described above with a gap of 200 μm or less,
By irradiating energy from a predetermined direction, a functional group is imparted in a pattern on the surface of the characteristic changing layer made of the above-mentioned polymer material.

In the present invention, the gap is preferably 100 μm or less, particularly 0.2 μm to 10 μm in view of the pattern accuracy and the efficiency of changing the characteristics on the characteristic changing layer.

By arranging the photocatalyst containing layer and the surface of the characteristic changing layer at a predetermined distance in this way, oxygen and water and active oxygen species generated by the photocatalytic action are easily desorbed. That is, when the distance between the photocatalyst containing layer and the characteristic change layer is narrower than the above range, it becomes difficult to desorb the active oxygen species, and as a result, the rate of change of the characteristics may slow down. If it is not preferable, and it is arranged at a distance from the above range, it becomes difficult for the generated active oxygen species to reach the characteristic change layer, and in this case as well, there is a possibility that the change rate of the characteristic may be slowed, which is not preferable. is there.

In the present invention, such an arrangement state with a gap may be maintained at least during the exposure.

As a method of uniformly forming such an extremely narrow gap and arranging the photocatalyst containing layer and the characteristic change layer, for example, a method using a spacer can be mentioned. And by using the spacer in this way,
Since it is possible to form a uniform gap and the photocatalyst does not act on the surface of the characteristic change layer at the portion where the spacer is in contact, the spacer has a pattern similar to the above-mentioned pattern. It becomes possible to form a predetermined pattern on the characteristic change layer.
Here, the pattern may be formed on the entire surface.

In the present invention, such a spacer may be formed as one member, but for the sake of simplification of the process, etc., as described in the section of the photocatalyst containing layer side substrate,
It is preferably formed on the surface of the photocatalyst containing layer of the photocatalyst containing layer side substrate. In the description of the photocatalyst-containing layer side substrate preparation step, the photocatalyst-containing layer side light-shielding portion has been described, but in the present invention, such a spacer is a surface so that the action of the photocatalyst does not affect the characteristic change layer surface. As long as it has a function of protecting the energy, it may be formed of a material that does not have a function of shielding the energy to be irradiated.

Next, in the state where the contact state as described above is maintained, energy is applied to the contacting portion.
The energy irradiation (exposure) in the present invention is a concept including irradiation of any energy beam capable of changing the characteristics by imparting a functional group to the surface of the characteristic changing layer by the photocatalyst containing layer. However, it is not limited to irradiation with visible light.

Usually, the wavelength of light used for such exposure is
It is set in the range of 400 nm or less, preferably in the range of 380 nm or less. This is because the preferred photocatalyst used in the photocatalyst-containing layer as described above is titanium dioxide,
This is because light having the above-mentioned wavelength is preferable as the energy for activating the photocatalytic action by this titanium dioxide.

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.

In addition to the method of performing pattern irradiation through a photomask using the above-mentioned light source, excimer,
It is also possible to use a method of drawing and irradiating in a pattern using a laser such as YAG.

The irradiation amount of energy at the time of exposure is set to the irradiation amount required for the surface of the characteristic changing layer to change the characteristics of the surface of the characteristic changing layer by the action of the photocatalyst in the photocatalyst containing layer.

At this time, the sensitivity can be increased by exposing the photocatalyst containing layer while heating,
It is preferable in that the characteristics can be efficiently changed.
Specifically, it is preferable to heat within the range of 30 ° C to 80 ° C.

In the present invention, the exposure direction is the pattern formation method such as whether or not the photocatalyst containing layer side light-shielding portion or the substrate for pattern forming body is formed, the photocatalyst containing layer side substrate or the pattern forming body. It is determined by whether or not the substrate is transparent.

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 irradiated with energy. Need to be transparent. In this case, when the photocatalyst-containing layer side light-shielding portion is formed on the photocatalyst-containing layer and the photocatalyst-containing layer side light-shielding portion is used so as to have the function as the spacer as described above, the exposure direction is It may be from the photocatalyst containing layer side substrate side or the pattern forming substrate side.

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, the pattern forming body substrate is irradiated. It needs to be transparent to energy. In this case as well, when the pattern-forming-body substrate-side light-shielding portion is formed on the characteristic change layer and the pattern-forming-body substrate-side light-shielding portion is used so as to have a function as the spacer as described above, The exposure direction may be from the photocatalyst containing layer side substrate side or the pattern forming body substrate side.

Further, the exposure direction in the case where the photocatalyst containing layer is formed in a pattern is not limited to any direction as long as energy is applied to the contact portion between the photocatalyst containing layer and the characteristic change layer as described above. May be irradiated from.

Similarly, in the case of using the above-mentioned spacer, irradiation may be performed from any direction as long as the contacting portion is irradiated with energy.

When a photomask is used, energy is applied from the side where the photomask is arranged. In this case, the substrate on the side where the photomask is arranged, that is, either the photocatalyst containing layer side substrate or the pattern forming substrate needs to be transparent.

When the energy irradiation as described above is completed, the photocatalyst-containing layer side substrate is moved away from the contact position with the characteristic change layer, and as a result, as shown in FIG. A pattern of 9 is formed on the characteristic change layer 5.

In the present invention, the characteristic change layer is composed of a polymer material, and a photocatalyst action accompanying energy irradiation forms reaction points on the surface of the polymer material in the energy-irradiated area. Reacts with the substance in the atmosphere 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, the surface of the characteristic change layer. On the other hand, in the area not irradiated with energy, no reaction points are formed on the surface of the polymer material, and thus no reaction with the substance in the atmosphere occurs. Thus, a pattern having the functional groups of is formed.

In the present invention, it is possible to introduce a functional group-introducing substance into the gap during the energy irradiation. This is because it is possible to provide a desired functional group on the property changing layer.

Here, the introduction of the functional group-introducing substance means that the substance having a functional group to be provided on the characteristic changing layer is present between the photocatalyst containing layer and the characteristic changing layer. The substance may be contained in the gas phase or may be contained in the liquid phase. Further, 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 contained in the gas phase, Examples of the method include a method performed in a chamber having a gas phase atmosphere, a method of introducing a gas, and the like. Further, when the functional group-introducing substance is contained in the liquid phase, a method of interposing a thin film of water or a petroleum-based solvent in which the functional group-introducing substance is dissolved between the photocatalyst-containing layer and the property change layer Etc.

Examples of the functional group-introducing substance of the present invention include:
Oxygen is used, which makes it possible to introduce a carbonyl group, a hydroxyl group, a carboxyl group and the like.

Further, a liquid or gaseous vinyl monomer is also mentioned as a functional group-introducing substance, and graft irradiation is carried out by irradiating energy in a state of being brought into contact with the above-mentioned characteristic changing layer to introduce the above-mentioned vinyl monomer. Can be done.

Specifically, as the vinyl monomer, MAH, maleimide (MI), acenaphthylene, or the like can be used in a gas phase system. It is also possible to use a mixed monomer, specifically, styrene / acrylonitrile, allyl alcohol or glycidyl methacrylate, MAH, maleimide / styrene, N-vinylpyrrolidone, vinyl ether, benzyl methacrylate, or the like can be used. Is.

When an alkanethiol monomolecular film having a 4-azidobenzoyloxy group or the like is used as the characteristic change layer, energy is irradiated by introducing dialkylamine as a functional group-introducing substance. The irradiated area can be converted to hydrazine.

In the present invention, a pattern-formed product having a pattern of a specific functional group on the surface can be obtained in this way. Such a pattern-formed product can be used as a biochip, a microfluidic chip, a conductive material. It can be applied to uses such as a pattern forming body.

3. Uses The pattern-formed product obtained by the method for producing a pattern-formed product of the present invention as described above can easily form various patterns having a functional group provided on the property changing layer. In the present invention, as described above, by the action of this functional group, for example, the surface affinity, wettability, adhesiveness, etc. are changed, and various functional materials are added to the changed part or the unchanged part. It can be attached and used for various purposes.

In the present invention, depending on the type and concentration of the substance in the atmosphere during the pattern exposure, the pressure, the presence of the catalyst, etc.,
The desired functional group is applied to the surface of the characteristic change layer made of a polymer material, and the applied functional group is used to develop various applications. Hereinafter, applications of the pattern forming body will be described.

A. Biochip For example, when the functional group provided on the characteristic change layer by the action of a photocatalyst has a biomaterial-binding property of binding to a biomaterial, it can be used as a biochip.

In this case, a functional group having a biomaterial-binding property is introduced onto the characteristic change layer of the pattern forming body to prepare a biochip base material. Then, the biomaterial can be used as a biochip by binding, that is, immobilizing the biomaterial to the functional group having the biomaterial-binding property of the biochip substrate.

On such a biochip surface, the functional groups provided on the surface of the characteristic change layer act as an immobilization layer, and biological substances such as DNA and protein are immobilized on the immobilization layer and used for various purposes. .

As the immobilization technique for such a biological substance, the immobilization technique that has been extensively studied in the research and development of a bioreactor in which an enzyme is immobilized on an insoluble carrier can be applied. For the technical content, see, for example, “Immobilized Enzyme” edited by Ichiro Chibata, Kodansha Scientific, 19
75 and its references.

Immobilization methods can be roughly classified into three types: immobilization by covalent bond, immobilization by ionic bond (electrostatic interaction), and immobilization by physical adsorption. In the immobilization of the biomaterial according to the present invention, generally, the biomaterial is further immobilized on the substrate. Therefore, the biological material must not be desorbed, and the immobilization technique by physical adsorption is unsuitable in this respect. Therefore, it can be said that immobilization by covalent bond and immobilization by ionic bond (electrostatic interaction) are suitable as a method for immobilizing a biological substance according to the present invention.

In the immobilization by covalent bond, for example, when the functional group provided on the characteristic change layer is a carbonyl group (aldehyde group), the so-called "Schiff base" is directly reacted with the amino group of the biological substance. It can be formed and immobilized. Further, when the imparted functional group is an amino group, a "Schiff base" can be directly formed and immobilized by coexisting a crosslinking agent such as glutaraldehyde in the system together with the biological substance. However, there are various reports that can be referred to for the technique of activating either the functional group provided on the property changing layer or the functional group of the biological substance and then performing the immobilization reaction. At this time, when the biological substance is a protein, adverse effects such as damage to the structure may occur during the activation treatment. Therefore, it is generally preferable to activate the functional group provided on the property changing layer.

As the activation method, when the functional group provided on the characteristic change layer is an amino group, activation is carried out by diazotization, and when the provided functional group is a carboxyl group, azidation, chloride formation, Examples thereof include a method of activating by imidization and isocyanate, a method of activating with cyanogen bromide in the case of a hydroxyl group, a method of activating with ethyl chloroformate and the like.

In some cases, an electrical reading method is used for the biochip, and in such a case, it is necessary to form an electrode on the surface of the biochip base material. At this time, the electrodes may be formed by the method described in the section of the conductive pattern forming body described later, or may be formed by a general photoresist method or the like.

B. Microfluidic chip The pattern forming body of the present invention can also be used as a microfluidic chip. In this case, the base body for the pattern forming body needs to have a recess for flowing the fluid. When forming the recess, for example, when the substrate is made of an organic polymer material, a method of removing the property changing layer in the pattern forming body of the present invention and forming the recess may be used.

In the present invention, a substrate for a microfluidic chip is prepared in which the molecule in the recess is at least a functional group provided on the characteristic change layer.

In such a microfluidic chip substrate, as described above, the functional group provided in the recess has a function of rectifying the flow of the fluid in the recess, or the analysis is performed in the recess. Or, it has various functions capable of performing synthesis. Therefore, some of such functional groups have extremely high reactivity, and it is usually very difficult to form a film using a material having such a functional group, for example, gelation of a coating liquid. May be

The present invention has solved such a problem. After the characteristic change layer serving as the base material is formed, the pattern formation step is performed to irradiate only the inside of the recess with energy in a pattern to form the inside of the recess. Since only the functional group is provided, it has an advantage that it is easy to form and handle.

Further, such a microfluidic chip base material can be used as a microfluidic chip by being bonded to a bonding base material. The bonded base material used here may have a recess at a portion corresponding to the recess of the base material for a microfluidic chip,
Further, it may be flat.

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 characteristic change layer only on the bonded base material side. is there. Further, a recess may be formed on the side of the bonded base material, and in this case also, it is preferable that a functional group is provided on the characteristic change layer on the inner surface of the recess.

Further, although there is a case where an electrode needs to be formed on this microfluidic chip, formation of a conductive pattern by applying the method for manufacturing a pattern-formed body of the present invention as described below is also applied to the formation of this electrode. It may be formed by a body manufacturing method, or may be formed by using a normal photolithography method.

C. Conductive Pattern Formed Body The pattern formed body of the present invention can also be used as a conductive pattern formed body. In this case, the functional group provided on the characteristic change layer by the action of the photocatalyst is a functional group having an electroless plating catalyst adhesive property that adheres to the electroless plating catalyst, and the substrate has an electrically insulating conductive property. A substrate for a patterned product is prepared.

Here, the functional group having an electroless plating catalyst adhering property and the step of adhering the electroless plating catalyst to this functional group are described, for example, in Charge Constrained Met.
allization (CCM) process (eg Mu-San Chen et
al., Journal of The Electrochemical Society, vol.
146, 1421-1430, 1999; Mu-San Chen et al., Ibid, vo
l. 147, 2607-2610, 2000).

In the method of the above-mentioned document (hereinafter referred to as the CCM method), a monomolecular film forming material of a type in which a functional group is exposed is formed on the entire surface of a substrate, and then a conventional photolithography method, that is, resist coating is applied. The method includes a step of forming a pattern in which the monomolecular film is exposed through exposure and development, and attaching a catalyst for electroless plating thereto. Comparing such a CCM method with the method according to the present invention, the present invention has a great advantage in that a chemical that is consumed in ordinary resist work is not used, and the process is simple because resist work is free. Is to have.

A conductive pattern forming body substrate obtained by such a method for producing a conductive pattern forming substrate,
A catalyst for electroless plating is attached to the functional group provided on the characteristic change layer (see the above CCM document), and then electroless plating is performed in a state where the catalyst for electroless plating is attached in a pattern. By carrying out, a conductive pattern forming body having a conductive pattern on the surface can be obtained.

If the electroless plating layer alone is insufficient in conductivity, electrolytic plating of copper or the like is performed as necessary. In addition, electroless plating of gold or the like may be performed.

This conductive pattern has various uses, for example, a biochip for an electrical detection method such as a printed wiring board, a DNA chip for an electrical detection method, a protein chip for an electrical detection method, and a cell chip for an electrical detection method. For functional board,
A chemical chip (L
ab-on-a-Chip), functional chips for microfluidic chips such as analysis chips, and the like.

In the present invention, since the conductive pattern is formed on the surface, the substrate needs to have an insulating property. The degree of this insulating property depends on the conductive pattern forming body used. It is decided according to the use of.

The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, has substantially the same configuration as the technical idea described in the scope of the claims of the present invention, and has any similar effect to 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 Trimethoxymethylsilane (GE Toshiba Silicone Co., Ltd.)
Manufactured, TSL8113) 5g and 0.5N hydrochloric acid 2.5g
And were mixed and stirred for 8 hours. This was diluted 10 times with isopropyl alcohol to obtain a primer layer composition.

The composition for the primer layer is 100 μm thick.
A transparent primer layer (thickness: 0.2 μm) was applied by spin coating on the photomask substrate of the line & space of No. 1 and dried at 150 ° C. for 10 minutes.
Was formed.

Next, 30 g of isopropyl alcohol and trimethoxymethylsilane (GE Toshiba Silicone Co., Ltd.)
(Manufactured by TSL8113) and 20 g of ST-K03 (manufactured by Ishihara Sangyo Co., Ltd.), which is a photocatalytic inorganic coating agent, were mixed and stirred at 100 ° C. for 20 minutes. This was diluted 3 times with isopropyl alcohol to obtain a photocatalyst-containing layer composition.

The photocatalyst-containing layer composition was applied onto a photomask substrate having a primer layer by a spin coater and dried at 150 ° C. for 10 minutes to give a transparent photocatalyst-containing layer (having a thickness of 0). .15 μm) was formed.

2. Formation of Property Change Layer 2 g of Iupilon Z400 (manufactured by Mitsubishi Gas Chemical Co., Inc.) containing polycarbonate as a main component was dissolved in 30 g of dichloromethane and 70 g of 112 trichloroethane to obtain a composition for a decomposition layer removing layer.

The composition for characteristic changing layer was applied onto a glass substrate by a spin coater and dried at 100 ° C. for 60 minutes to form a transparent characteristic changing layer (thickness 1.0 μm).

3. Pattern formation step The photocatalyst containing layer side substrate and the polycarbonate layer are made to face each other with a gap of 50 μm provided by using a polyimide film as a spacer, and then ammonia gas is introduced into the space, and an ultrahigh pressure mercury lamp (wavelength 365n
m) was exposed for 300 seconds at an illuminance of 40 mW / cm ² .

4. Evaluation When the surface of this substrate was analyzed by X-ray photoelectron spectroscopy, introduction of amino groups in a mask pattern was recognized only in the exposed portion.

At this time, the contact angle between the unexposed portion and the exposed portion of water was measured by a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.).
Measurement using a liquid droplet (3
After 0 second), the results were 72 ° and 19 °, respectively.

[Comparative Example 1] The same patterning as in Example 1 was carried out except that a mask having no photocatalyst-containing layer was used. As a result, introduction of amino groups in the exposed area was not observed, and the contact angle was the same as that in the exposure. It was 71 ° even in part.

[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.

2. Formation of characteristic change layer A polypropylene film having a thickness of 200 μm was prepared.

3. Pattern forming step The photocatalyst containing layer side substrate and the polypropylene film are made to face each other with a gap of 50 μm using a polyimide film as a spacer, and then oxygen gas is introduced into the space,
From the photomask side, exposure was performed for 200 seconds with an illuminance of 40 mW / cm ² by an ultra-high pressure mercury lamp (wavelength 365 nm).

4. Evaluation The surface of this substrate was analyzed by X-ray photoelectron spectroscopy. As a result, introduction of a carboxyl group in a mask pattern was recognized only in the exposed portion.

At this time, the contact angle between the unexposed portion and the water in the exposed portion was measured by a contact angle measuring instrument (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.).
Measurement using a liquid droplet (3
After 0 seconds), the results were 88 ° and 14 °, respectively.

[Comparative Example 2] As a result of patterning in the same manner as in Example 2 except that a mask having no photocatalyst-containing layer was used, introduction of a carboxyl group in the exposed area was not observed, and the contact angle was the same. It was 87 ° even in part.

[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.

2. Formation of Characteristic Change Layer A polycarbonate layer was formed on a glass substrate as in Example 1.

3. Pattern formation process The photocatalyst containing layer side substrate and the polycarbonate layer are
A gap of 50 μm is provided using the film as a spacer.
On the opposite side, and then introduce chlorine gas into the space and
From the Tomask side with an ultra-high pressure mercury lamp (wavelength 365 nm)
40 mW / cm ²Exposure for 400 seconds.

4. Evaluation When the surface of this substrate was analyzed by X-ray photoelectron spectroscopy, introduction of chlorine groups in a mask pattern was recognized only in the exposed portion.

At this time, a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the contact angle between the unexposed portion and the exposed portion of water.
Measurement using a liquid droplet (3
After 0 second), the results were 72 ° and 24 °, respectively.

[Comparative Example 3] As a result of patterning in the same manner as in Example 3 except that a mask having no photocatalyst-containing layer was used, introduction of chlorine groups in the exposed area was not observed, and the contact angle was the same. It was 72 ° even in parts.

[0169]

According to the present invention, in the energy-irradiated region, reaction points are formed on the characteristic change layer made of a polymer material due to the action of the photocatalyst associated with the energy irradiation, and the reaction sites exist, for example, in the atmosphere. By reacting with a substance or the like, a functional group is provided on the surface of the characteristic change layer. On the other hand, in a region which is not irradiated with energy, no reaction site is formed, and thus a functional group is not provided. As a result, it becomes possible to obtain a pattern-formed product having a functional group provided in a pattern. Further, in the pattern formation step, various functional groups can be imparted to the surface of the polymer material by changing the substance to be reacted, whereby a pattern having a functional group in a pattern can be formed especially after exposure. It can be easily formed in high definition without any treatment. Such a pattern forming body can be applied to various uses.

Further, since the photocatalyst containing layer side substrate is removed from the pattern forming body after the exposure, the pattern forming body itself does not include the photocatalyst containing layer, and therefore the pattern forming body is deteriorated with time due to the action of the photocatalyst. Don't worry about Furthermore, since the distance between the photocatalyst-containing layer and the characteristic change layer is within the above range, it is possible to efficiently and accurately obtain a pattern formed body having a changed characteristic pattern.

[Brief description of drawings]

FIG. 1 is a process drawing showing an example of a method for manufacturing a pattern formed body of the present invention.

FIG. 2 is a schematic 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 (17)

[Claims] 1. A substrate for a pattern-forming body for preparing a substrate for a pattern-forming body having a property changing layer made of a polymer material, and a photocatalyst-containing layer side substrate having a photocatalyst containing layer containing a photocatalyst and a substrate. After arranging the photocatalyst containing layer and the characteristic changing layer with a gap so as to be 200 μm or less, energy is irradiated from a predetermined direction to form a pattern on the surface of the characteristic changing layer made of the polymer material. And a pattern forming step of imparting a functional group. 2. The method for producing a pattern formed body according to claim 1, wherein in the pattern forming step, a substance for introducing a functional group is introduced into the gap. 3. The pattern according to claim 1, wherein the photocatalyst-containing layer side substrate comprises a base material and a photocatalyst-containing layer formed in a pattern on the base material. Method for manufacturing formed body. 4. 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, wherein the pattern forming step. 3. The method for producing a pattern formed body according to claim 1, wherein the irradiation of energy in step 1) is performed from the photocatalyst containing layer side substrate. 5. The photocatalyst containing layer side substrate is characterized in that the photocatalyst containing layer side light shielding portion is formed in a pattern on the base material, and the photocatalyst containing layer is further formed thereon. The method for manufacturing the pattern formed body according to claim 4. 6. The photocatalyst containing layer side substrate, wherein a photocatalyst containing layer is formed on the base material, and the photocatalyst containing layer side light-shielding portion is formed in a pattern on the photocatalyst containing layer. The method for manufacturing a pattern formed body according to claim 4. 7. The method for producing a pattern-formed body according to claim 1, wherein the photocatalyst-containing layer is a layer made of a photocatalyst. 8. The method for producing a pattern-formed body according to claim 7, wherein the photocatalyst-containing layer is a layer formed by forming a photocatalyst on a substrate by a vacuum film-forming method. 9. The method for producing a pattern-formed body according to claim 1, wherein the photocatalyst-containing layer is a layer having a photocatalyst and a binder. 10. The titanium oxide (Ti) is used as the photocatalyst.
O_Two), Zinc oxide (ZnO), tin oxide (SnO)_Two),
Strontium titanate (SrTiO_Three), Oxide tongue
Stainless (WO_Three), Bismuth oxide (Bi_TwoO_Three), And
And iron oxide (Fe _TwoO_Three1 type or 2 types selected from
Claims 1 to 6, which are the above substances
Manufacturing of the pattern forming body according to any one of claims 9 to 9.
Build method. 11. The photocatalyst is titanium oxide (TiO ₂ ).
11. The method for manufacturing a pattern formed body according to claim 10, wherein: 12. The functional group provided on the characteristic change layer of the pattern-formed product obtained by the method for producing a pattern-formed product according to claim 1 is a biomaterial. A method for producing a biochip substrate, which is a functional group having a biomaterial-binding property that binds to 13. A substrate of a pattern-formed body obtained by the method for manufacturing a pattern-formed body according to any one of claims 1 to 11 has a recess for flowing a fluid, and at least A method for producing a base material for a microfluidic chip, wherein a predetermined functional group is provided in a pattern in the pattern forming step on the surface of the characteristic change layer made of a polymer material in the recess. 14. A functional group provided on a characteristic change layer of a pattern-formed body obtained by the method for producing a pattern-formed body according to any one of claims 1 to 11 is electroless. A method for producing a conductive pattern forming substrate, which is a functional group having an adhesive property for an electroless plating catalyst that adheres to a plating catalyst, wherein the polymer is electrically insulating. 15. A biochip comprising a step of binding a biological substance to a functional group of the biochip substrate obtained by the method for producing a biochip substrate according to claim 12. Production method. 16. A microfluidic chip comprising a step of bonding a microfluidic chip base material obtained by the method for manufacturing a microfluidic chip base material according to claim 13 and a bonding base material. Manufacturing method. 17. A catalyst for adhering a catalyst for electroless plating to a functional group provided on a substrate for conductive pattern formation obtained by the method for producing a substrate for conductive pattern formation according to claim 14. A method of manufacturing a conductive pattern, comprising: an attaching step; and an electroless plating step of performing electroless plating on a substrate on which a catalyst for electroless plating is attached in a pattern by the catalyst attaching step.