JP2003223004A - Method of producing pattern-formed structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of producing a pattern-formed structure by which deprotection of functional groups can be carried out in a short time and post treatment or the like after the exposure is unnecessary. <P>SOLUTION: The method of producing a pattern-formed structure is characterized in that it includes the following processes, that is, a substrate preparation process for the pattern-formed structure to prepare the substrate for the pattern- formed structure, the substrate having a base body and a characteristic- modifiable layer which is formed on the base body and formed in a thin film state of molecules having functional groups protected by photosensitive protective groups and subjected to deprotection of the photosensitive protective groups by the effect of a photocatalyst; and a pattern forming process to dispose a photocatalyst-containing layer substrate having a photocatalyst-containing layer containing a photocatalyst and a base body in such a manner that the photocatalyst-containing layer is at ≤200 μm distance from the characteristics- modifiable layer and to irradiate the substrate with energy in a specified direction so as to form a pattern comprising the deprotected functional groups obtained by deprotecting the functional groups protected by the photosensitive protective groups on the surface of the characteristic-modifiable layer. <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 having a pattern of functional groups obtained by deprotecting a photosensitive protective group.

[0002]

2. Description of the Related Art Conventionally, as a base material for a microfluidic chip, one that rectifies the flow of fluid in a concave portion by a functional group arranged in the concave portion, performs analysis in the concave portion,
Those having various functions capable of performing synthesis have been manufactured. Some of the functional groups arranged in the recesses of such a microfluidic chip have extremely high reactivity, and it is common practice to form a film using a material in which such functional groups are not protected. In some cases, handling such as gelling of the coating liquid becomes extremely difficult.

From this point of view, a method using a molecule having a functional group protected by a photosensitive protective group is known, but in this case, a chemical substance derived from the eliminated protective group may be poor in volatility. In many cases, a cleaning step after exposure is generally unavoidable.

Further, as a method of attaching the electroless plating catalyst to the deprotection functional group having the electroless plating catalyst attachment property when forming the conductive pattern, for example, Charge
The Constrained Metallization (CCM) process is known, and this method forms a monomolecular film forming material without a photosensitive protective group, that is, a type with an exposed functional group, on the entire surface of the substrate, and In the ordinary photolithography method, that is, a step of forming a pattern in which a monomolecular film is exposed through resist coating, exposure, and development, and attaching a catalyst for electroless plating thereto (see, for example, Non-Patent Document 1). . However, the above method has a problem that a plurality of steps are required.

[0005]

[Non-Patent Document 1] Mu-San Chen et al., “Journal of Th
e Electrochemical Society '', vol. 146, p1421-1430,
1999; Mu-San Chen et al., Ibid, vol. 147, 2607-26
10, 2000

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and can deprotect functional groups in a short time and does not require post-treatment such as post-exposure. The main object of the present invention is to provide a method for manufacturing a pattern-formed body.

[0007]

In order to achieve the above-mentioned object, the present invention provides a substrate and a functional group formed on the substrate and protected by a photosensitive protective group, as described in claim 1. A pattern forming body substrate adjusting step of adjusting a pattern forming body substrate having a property changing layer formed by forming a thin film of a molecule in which a photosensitive protective group is deprotected by the action of a photocatalyst, and a photocatalyst. After arranging the photocatalyst containing layer and the characteristic change layer in the photocatalyst containing layer side substrate having the photocatalyst containing layer and the substrate contained therein with a gap of 200 μm or less, irradiating energy from a predetermined direction. And a pattern forming step of forming a pattern of a deprotected functional group obtained by deprotecting a functional group protected by a photosensitive protective group on the surface of the property changing layer. To provide a method of manufacturing a turn-forming body.

According to the present invention, in the step of preparing a substrate for a pattern-formed body, a characteristic change layer is formed by forming molecules having a functional group protected by a photosensitive protective group in a thin film on a substrate, In the pattern formation step, by irradiating with energy, a pattern comprising a deprotected functional group obtained by deprotecting a functional group protected by a photosensitive protective group on the surface of the characteristic change layer is formed with high precision. You can

By using a thin film of molecules having a functional group protected by a photosensitive protective group as the characteristic changing layer, the photocatalyst function associated with energy irradiation facilitates photosensitivity. It becomes possible to deprotect the protecting group. Therefore, it is possible to easily form a pattern of deprotected deprotected functional group, and by exposing the deprotected functional group, it is possible to apply it to various applications as a pattern-formed product having surface characteristics changed. It will be possible.

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.

In the invention described in claim 1, as described in claim 2, the photocatalyst containing layer side substrate is a base material and a photocatalyst containing layer formed in a pattern on the base material. It is preferable that By thus forming the photocatalyst-containing layer in a pattern, it becomes possible to form patterns having different characteristics on the characteristic change layer without using a photomask. Also,
Since the deprotection reaction occurs only on the surface corresponding to the photocatalyst-containing layer, the irradiation energy is not particularly limited to parallel energy, and the energy irradiation direction 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, as described in claim 3, the photocatalyst containing layer side substrate is a base material, a photocatalyst containing layer formed on the base material, and a pattern. It is preferable that the photocatalyst-containing layer side light-shielding portion is formed in a shape, 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 3, as described in claim 4, 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 on the photocatalyst-containing layer.
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 5, it is preferable that the photocatalyst-containing layer is a layer composed of a photocatalyst, as described in claim 6. . This is because if the photocatalyst-containing layer is a layer composed only of a photocatalyst, the efficiency of changing the characteristics of the characteristic change layer can be improved, and the pattern-formed product can be efficiently produced.

In the invention described in claim 6, as described in claim 7, 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 5, as described in claim 8, 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.

Any of claims 1 to 8
In the invention described in the claim,
As described above, the photocatalyst has a titanium oxide (TiO 2_Two),
Zinc oxide (ZnO), tin oxide (SnO)_Two), Titanic acid
Strontium (SrTiO _Three), Tungsten oxide
(WO_Three), Bismuth oxide (Bi_TwoO_Three), And oxidation
Iron (Fe_TwoO_Three) One or more selected from
It is preferable that the substance is a substance.
As described above, the photocatalyst has a titanium oxide (TiO 2_Two) Is
It is preferable. This is a titanium dioxide band gap
Since it has a high energy, it is effective as a photocatalyst, and
It is chemically stable, non-toxic and easily available.
It

In the invention described in any one of claims 1 to 10, as described in claim 11, the molecule having a functional group protected by the photosensitive protecting group is Further, it may have a functional group capable of binding to a molecule constituting the substrate. This is because the property changing layer can be firmly bonded to the substrate by having the functional group capable of bonding to the molecule that constitutes the substrate.

The present invention also provides, as described in claim 12, the characteristics of the pattern-formed product obtained by the method for producing a pattern-formed product according to any one of claims 1 to 11. There is provided a method for producing a biochip substrate, wherein the deprotection functional group on the change layer is a deprotection functional group having a biomaterial-binding property of binding to a biomaterial. As described above, if the deprotection functional group has a biomaterial-binding property, it is possible to easily form a high-definition biochip by binding the biomaterial to the pattern-formed deprotection functional group. You can

According to a thirteenth aspect of the present invention, there is provided a substrate of a pattern-formed body obtained by the method for producing a pattern-formed body according to any one of the first to eleventh aspects. A molecule having a concave portion for flowing a fluid and having at least a functional group protected by a photosensitive protective group in the concave portion is deprotected in the pattern forming step and is a deprotected functional group. Provided is a method for producing a characteristic base material for a microfluidic chip. It is preferable that the surface of the concave portion of the base material for a microfluidic chip, which serves as a fluid channel, has a functional group for controlling the flow of fluid. When forming a film having such a functional group, if the film is formed with the functional group exposed, there may be a problem in handling such as gelation of the film forming liquid. Therefore, it is preferable to form a film using a material having a functional group protected by a protective group. In the present invention, since the property-changing layer in which a molecule having a functional group protected by a photosensitive protective group is formed in a thin film is used, there are few problems during film formation, and at least the inside of the recess after film formation is used. It is possible to easily obtain a state in which the functional group for controlling the fluid is exposed in the concave portion only by irradiating with energy so that the protective group can be deprotected.

The present invention further provides, as described in claim 14, a pattern-formed body obtained by the method for producing a pattern-formed body according to any one of claims 1 to 11. The deprotection functional group on the property change layer is a deprotection functional group having an electroless plating catalyst adhering property with the electroless plating catalyst, and the substrate is electrically insulating. Provided is a method for manufacturing a pattern forming substrate. As described above, if the deprotection functional group has a property of adhering the electroless plating catalyst, by attaching the catalyst for electroless plating to the deprotection functional group formed in a pattern, high-definition conductivity can be obtained. The pattern can be easily formed.

In the present invention, as described in claim 15, a biological substance is added to the deprotection 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 manufacturing a biochip, which comprises the step of binding 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 base material obtained by the method for producing a microfluidic chip base material according to claim 13 and a bonded base material. There is provided a method for manufacturing a microfluidic chip, which comprises a step of bonding together. As described above, according to the manufacturing method of the present invention,
It becomes possible to extremely easily introduce the functional group for controlling the fluid into the recess.

In the method for producing a microfluidic chip according to claim 16, as described in claim 17, the bonded base material is the same as in any one of claims 1 to 11. A substrate of a pattern-formed body obtained by the method for producing a pattern-formed body according to claim 1, wherein when the microfluidic chip base material and the bonding base material are bonded together, the recesses of the microfluidic chip base material are formed. It is preferable that the molecule having a functional group protected by the photosensitive protective group on the surface portion of the bonding base material corresponding to is deprotected in the pattern forming step to be a deprotected functional group. This is because the function of the microfluidic chip can be more effectively exhibited by further providing the deprotection functional group in the portion corresponding to the recess of the bonded base material.

According to the present invention, further, claim 1
As described in 8, the electroless plating catalyst is attached to the deprotection 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. A method for producing a conductive pattern, which comprises a catalyst adhesion step and an electroless plating step of performing electroless plating on a substrate on which a catalyst for electroless plating is adhered in a pattern by the catalyst adhesion step. provide. A highly precise conductive pattern can be easily obtained.

[0028]

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 product of the present invention comprises a substrate, a molecule formed on the substrate and having a functional group protected by a photosensitive protective group, and a molecule in which the photosensitive protective group is deprotected by the action of a photocatalyst. Pattern-forming body substrate adjusting step of adjusting a pattern-forming body substrate having a property changing layer formed in a thin film, and the photocatalyst containing layer in the photocatalyst containing layer side substrate having a photocatalyst containing layer containing a photocatalyst A layer and the characteristic change layer,
Deprotection obtained by disposing functional groups protected by a photosensitive protective group on the surface of the characteristic change layer by irradiating with energy from a predetermined direction after disposing them with a gap to be not more than μm. And a pattern forming step of forming a pattern composed of a functional group.

Further, the present invention may include a photocatalyst containing layer side substrate adjusting step of adjusting the photocatalyst containing layer side substrate having a photocatalyst containing layer and a photocatalyst containing layer containing a photocatalyst. 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, comprising forming a property-changing layer formed by forming a molecule having a functional group protected by a photosensitive protective group in a thin film on a substrate in the above-mentioned substrate preparation step for a pattern-formed body. In the pattern formation step, by irradiating with energy, a pattern comprising a deprotected functional group obtained by deprotecting a functional group protected by a photosensitive protective group is formed on the surface of the characteristic change layer. .

In the present invention, by using as the property changing layer a thin film of molecules having a functional group protected by a photosensitive protective group, it is possible to facilitate the action of the photocatalyst associated with energy irradiation. It becomes possible to deprotect the photosensitive protecting group. Therefore, it is possible to easily form a pattern of the deprotected functional group that has been deprotected, and it is possible to apply to various uses.

Further, 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 described in detail 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 having a photocatalyst containing layer 2 formed 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 change layer 5 have a predetermined interval. 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 including the regions 9 whose characteristics have changed due to the exposure of the deprotection functional group 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 changing 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.

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)) By exposing the deprotecting functional group on the surface, the pattern-formed product 6 having a pattern whose characteristics are changed can be obtained.

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 in the present invention refers to a pattern-forming body substrate preparing step, which comprises a substrate and a functional group formed on the substrate and protected by a photosensitive protective group, and which is exposed to light by the action of a photocatalyst. It is a step of preparing a substrate for a pattern forming body having a property changing layer formed by forming a molecule in which a sex protecting group is deprotected in a thin film shape.

In the present invention, a thin film of molecules having a functional group protected by a photosensitive protective group is used as the property changing layer, and such a property changing layer is exposed to a photocatalyst. By exposing with, it is possible to obtain a pattern consisting of deprotected functional groups that have been deprotected extremely efficiently.

That is, in general, in order to remove the photosensitive protective group from the functional group, a photoreaction which is not catalyzed by energy irradiation is used. However, by irradiating energy under the action of a photocatalyst, a usual photoreaction is performed. The photocatalytic reaction, which is much more efficient than the reaction by UV exposure, can be utilized, and as a result, the elimination reaction of the photosensitive protective group can be completed in a very short time. Furthermore, for the photocatalytic reaction,
There is also an effect of decomposing the removed chemical substance derived from the protective group into a highly volatile substance, which has an effect of enabling the omission of the cleaning step after exposure.

By forming a pattern in which such characteristics are changed, that is, a pattern of deprotecting functional groups,
Various applications can be developed as described below.

In the present invention, the molecule may be a polymer material as long as it contains at least one functional group protected by a photosensitive protective group, and for example, a low molecular weight such that vapor deposition is possible. The material may be.

Examples of the functional group here include an amino group, an amide group, a carboxyl group, a carbonyl group, a hydroxyl group, and a 1,3-diol group.

Examples of the protecting group for protecting such a functional group include, for example, ortho- (o-) nitrobenzyl derivative, o-nitrobenzyloxycarbonyl derivative, aromatic amine N-oxide derivative, o-nitrobenzyl. Carbamate derivative, allylformamide derivative, N-benzylamide derivative, benzylcarbamate derivative, benzylsulfonamide derivative, bis (o-nitrophenyl) methyl ester derivative, S, S-dibenzylacetal derivative and ketal derivative, 3, 5-dimethoxybenzylcarbamate derivative, 4- (4 ', 8'-dimethoxynaphthylmethyl) benzenesulfonamide derivative, 3,4-dimethoxy-6-nitrobenzylcarbamate derivative, α- (3,5-dimethoxyphenyl) Phenacyl ester derivative, N, N-dimethylhydrazone derivative, di-2-nitroben Acetal derivatives, 2- (9,10-dioxo) anthrylmethyl ester derivative, 4,5-diphenyl-3-oxazolin-2-one derivatives,
1,3-dithiolene derivative, 9-fluorenecarboxylate ester derivative, p-methoxybenzyl ether derivative, phenacyl derivative, p-methoxyphenacyl ester derivative, N-methylamine derivative, 1-methyl-1- (3,
5-dimethoxyphenyl) ethyl carbamate derivative,
α-methylphenacyl ester derivative, nitrate ester derivative, nitramide derivative, o-nitroanilide derivative, N-o-nitrobenzylamine derivative, o-nitrobenzyl carbonate derivative, o-nitrobenzyl ester derivative, o-nitrobenzyl ether Derivatives, o-nitrobenzylidene acetal derivatives, N-7-nitroindolylamide derivatives, m-nitrophenyl carbamate derivatives, 4-o-nitrophenyl-1,3-dioxolane derivatives, N
-8-Nitro-1,2,3,4-tetrahydroquinolylamide derivative, 1,3-oxothiolane derivative, phenyl (o-nitrophenyl) methylcarbamate derivative, 1-pyrenylmethyl ester derivative, toluenesulfonamide Derivatives, toluenesulfonate derivatives, xanthenecarboxylate ester derivatives, nitrophenylsulfenyl derivatives, and the like. Specific examples include o-nitrobenzyl group, α-methyl-nitropiperonyl group, α-methyl-nitropiperolic group. Nyloxycarbonyl group, 1-pyrenylmethyloxycarbonyl group, α, α-dimethyl-3,5-dimethoxybenzyloxycarbonyl group, 4-nitropyridine N-oxide group, m-nitrophenylcarbamate group,
3,5-dimethoxybenzylcarbamate group, o-nitrobenzyloxycarbonyl group, 3,4-dimethoxy-6-nitrobenzylcarbamate group, phenyl (o-nitrophenyl)
Methyl carbamate group, p-methoxyphenacyl group, 1,3
-Dithiolene group, 1,3-oxathiolene group, p-methoxybenzyl group, tosyl group, benzenesulfonamide group and the like can be mentioned.

References relating to the functional group protected by such a photosensitive protective group include, for example, "Protective group".
s in organic synthesis ”(Second Edition), by Theo
doraW. Greene and Peter GM Wuts, John Wiley & S
ons, 1991) and Japanese Patent Laid-Open No. 2000-508542.

In the present invention, the material having a functional group protected by the above-mentioned photosensitive protective group may further have a functional group capable of binding to the material constituting the substrate.

This is effective, for example, when it is desired to firmly fix the thin film characteristic change layer formed on the substrate to the substrate.

Examples of the functional group capable of binding to the material constituting the substrate as used herein include an alkoxysilyl group, a halogenated silyl group and a thiol group.

In the present invention, the following method can be mentioned as a method for forming such a characteristic change layer on a substrate.

The first method is to form a thin film characteristic change layer on the substrate by a coating method such as spin coating, flexo coating, gravure coating, offset coating or the like. This method is generally performed by dissolving a molecule having a functional group protected by a photosensitive protective group as described above in a solvent to prepare a coating solution.

When the molecule having a functional group protected by the photosensitive protective group is a low molecular weight material, it may be formed into a thin film on the substrate by a vapor deposition method.

The second method is to form a self-assembled monolayer (SAM film) on the substrate. When this method is used, a molecule having a functional group protected by a photosensitive protective group as described above and further having a functional group capable of binding to a molecule constituting the substrate is used. Regarding the self-assembly method (self-assembled monolayer), for example, Abraham Ulman, “Formation and structu
re of self-assembled monolayers ”, Chemical Review,
Vol. 96, 1533-1554 (1996) can be referred to.

As a third method, a thin film (LB film) is formed on the substrate by the Langmuir-Blodgett method (LB method).
The method of forming can be mentioned.

When the molecule having a functional group protected by the above-mentioned photosensitive protective group is a polymer electrolyte, etc., a fourth method can form a thin film by an adsorption method or an alternate adsorption method. is there.

The substrate on which such a characteristic changing layer is formed includes silicon wafer, metal, quartz, glass, diamond, diamond-like carbon (DLC),
Alumina, polymer materials, etc. can be used, and these are appropriately selected and used according to the application described later.

The shape of the substrate used is not particularly limited, and it may be a suitable shape depending on 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.

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

In this case, since it is necessary to perform energy irradiation in the pattern forming step 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 substrate-side light-shielding portion for the pattern-forming body is not particularly limited, and may be selected depending on the characteristics of the surface on which the photocatalyst-containing layer-side light-shielding portion is formed, the shielding property against required energy, and the like. It is appropriately selected and used.

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 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 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 forming a pattern composed of a deprotected functional group obtained by deprotecting the functional group protected by the photosensitive protective group by irradiating energy from the.

Each component of this process 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 substrate 1 as shown in FIG. 1 (a) and the like, but 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 changing layer and is irradiated with energy, as will be described later in a pattern forming step. 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 with changed characteristics can be formed by exposing the deprotection 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 characteristics of only the portion on the characteristic changing layer which actually faces the photocatalyst containing layer changes, the energy irradiation direction is set to the portion where the photocatalyst containing layer and the characteristic changing layer face each other. Is irradiated,
Irradiation may be performed from any direction, and the energy to be irradiated is not limited to parallel light such as parallel light.

The action mechanism of the photocatalyst represented by titanium dioxide as described below in the photocatalyst containing layer is as follows.
Although not always clear, carriers generated by light irradiation change the chemical structure of organic substances by direct reaction with compounds in the vicinity or by active oxygen species generated in the presence of oxygen or water. It is believed that.
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 for 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 the method for 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 the 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 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 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, in the case where the pattern forming body is transparent, it is also possible to arrange a photomask on the substrate for the pattern forming body and irradiate energy. 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, such as a resin film, or one that is not flexible, such as 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 13, and the photocatalyst-containing layer 2 is formed on the photocatalyst-containing layer side light-shielding portion 13. the other one is,
For example, as shown in FIG. 4, the photocatalyst containing layer 2 is formed on the base material 1, and the photocatalyst containing layer side light-shielding portion 13 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 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. 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 base material and the photocatalyst containing layer and on the photocatalyst containing layer surface. 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 photocatalyst-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 portion 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,
A pattern forming step of irradiating energy from a predetermined direction is performed.

In the present invention, the above-mentioned gap may be in close contact with the photocatalyst containing layer and the characteristic change layer, but in view of pattern accuracy and efficiency of characteristic change on the characteristic change layer, it is 100 μm or less, particularly 0 μm or less. It is preferably within the range of 0.2 μm to 10 μm.

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 for uniformly forming such an extremely narrow gap and disposing 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.

In the present invention, such a spacer may be formed as one member, but for 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 ray capable of changing the characteristics of the characteristic change layer surface by the photocatalyst containing layer, and is not limited to irradiation of visible light. Not something.

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 the light source that can be used for such exposure include a mercury lamp, a metal halide lamp, a xenon lamp, an excimer lamp, 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.

Further, the irradiation amount of energy at the time of exposure is the irradiation amount necessary 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.

The exposure direction in the present invention is the pattern formation method such as whether or not the photocatalyst containing layer side light-shielding portion or the pattern forming substrate substrate light shielding portion is formed, and the photocatalyst containing layer side substrate or pattern forming body is used. 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 carry out 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 portion where the photocatalyst containing layer and the characteristic change layer are in contact with each other, 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 separated from the contact position with the characteristic change layer, whereby the deprotection functional group is exposed as shown in FIG. 1 (d). Characteristic change area 9 where the characteristic has changed
Is formed on the characteristic change layer 5.

In the present invention, since the above-mentioned characteristic changing layer is formed into a thin film of molecules having a functional group protected by a photosensitive protective group, specifically, such a characteristic changing layer surface is formed. The change in properties due to the action of the photocatalyst associated with the energy irradiation is the deprotection of the photosensitive protective group, and the pattern of the deprotected functional group in which the photosensitive protective group is deprotected is obtained by irradiating energy in a pattern. It can be formed on the characteristic change layer.

In the present invention, it is possible to obtain a pattern-formed product having a pattern of deprotecting functional groups on the surface as described above. Such a pattern-formed product is, as will be described later, a biochip or a microchip. It can be used for various applications such as a fluid chip and a conductive pattern forming body.

3. Use The pattern-formed product obtained by the method for manufacturing a pattern-formed product of the present invention as described above can easily form various patterns due to changes in the characteristic change layer.

The pattern-formed product obtained in the present invention can be used for various purposes. In the present invention,
Molecules having a functional group protected by a photosensitive protective group as described above are formed into a thin film, and the kind of the molecule having a functional group protected by a photosensitive protective group and the photosensitive protective group It can be used for various purposes depending on the type of the functional group protected by.

A. Biochip For example, when the deprotected functional group deprotected 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 biochip substrate using the deprotection functional group on the property changing layer in the pattern forming body as the bioprotection functional group is prepared. Next, a biomaterial can be used as a biochip by binding, that is, immobilizing a biological substance to the deprotecting functional group of the biochip base material.

On the surface of such a biochip, the deprotection functional group functions as an immobilization layer, on which biological substances such as DNA and protein are immobilized and used for various purposes.

The immobilization technique of such a biological substance can be applied to the immobilization technique which has been extensively studied in the research and development of a bioreactor in which an enzyme is immobilized on an insoluble carrier. 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 immobilization by covalent bond, for example, the deprotection functional group on the substrate is a carbonyl group (aldehyde group).
In such a case, the so-called "Schiff base" can be formed by immobilization by directly reacting with the amino group of the biological substance. When the deprotecting functional group is an amino group, a "Schiff base" can be directly formed and immobilized by coexisting with a cross-linking 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 the deprotection functional group on the substrate or the functional group of the biological substance and then performing the immobilization reaction. At this time,
When the biological substance is a protein, it is generally preferable to activate the deprotecting functional group on the substrate, because the structure may be damaged during the activation treatment, which may have an adverse effect.

As the activation method, when the deprotecting functional group is an amino group, activation is carried out by diazotization, and when the deprotecting functional group is a carboxyl group, azidation, chloride, imidization, isocyanate formation, etc. How to activate by,
In the case of a hydroxyl group, a method of activating with cyanogen bromide, a method of activating with ethyl chloroformate and the like can be mentioned.

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.

Then, at least the molecule having a functional group protected by the photosensitive protective group in the concave portion is deprotected in the pattern forming step to prepare a microfluidic chip substrate. To do.

In such a microfluidic chip substrate, the deprotected deprotected functional group disposed in the recess as described above has a function of rectifying the flow of the fluid in the recess, or It has various functions that allow analysis and synthesis in the recess. In the present invention, by the action of the photocatalyst at the time of exposure, a photocatalytic reaction far more efficient than the reaction by ordinary UV exposure can be utilized, and as a result, the elimination reaction of the photosensitive protective group is completed in a very short time. It is possible.

The present invention has the advantage that by irradiating only the inside of the recess with a pattern of energy, only the inside of the recess can be deprotected and used as a deprotecting functional group.

Such a microfluidic chip base material is
It can be used as a microfluidic chip by bonding with a bonding base material. The bonded base material used here may have a concave portion at a portion corresponding to the concave portion of the microfluidic chip substrate, or may have a planar shape.

Further, the above-mentioned bonded base material is the pattern-formed body obtained by the method for manufacturing a pattern-formed body of the present invention, and when the above-mentioned microfluidic chip base material and the above-mentioned bonded base material are bonded together. In addition, the functional group protected by the photosensitive protective group on the surface portion of the bonding base material corresponding to the concave portion of the microfluidic chip base material is deprotected in the pattern formation step as described above, and the deprotection functional It is preferable that it is based. As described above, not only the microfluidic chip base material having the concave portion but also the bonded base material is obtained by the method for producing a pattern forming body of the present invention, and the functional group on the surface at the position corresponding to the concave portion However, by being a deprotected functional group that has been deprotected, the inner surface of the flow path of the microfluidic chip becomes a surface that has all the deprotected functional groups, which effectively moves the fluid and other functions of the microfluidic chip. Can be demonstrated.

In the present invention, there is no deprotected functional group on the microfluidic chip substrate side, and only the bonded substrate side has the deprotected functional group. Is also possible. Further, a recess may be formed on the side of the bonded base material, and in this case also, it is preferable that a thin film having a deprotecting functional group is formed on the inner surface of the recess.

Further, although there is a case where an electrode needs to be formed on this microfluidic chip, also regarding this electrode formation, a conductive pattern formation is applied by applying the method for manufacturing a pattern-formed body of the present invention as described later. 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 deprotection functional group deprotected by the action of the photocatalyst is a deprotection functional group having electroless plating catalyst adhesion that adheres to the electroless plating catalyst, and the above-mentioned substrate has an electrically insulating conductive property. A substrate for a patterned product is prepared.

In the present invention, the present invention has a great advantage in that a chemical which is consumed in a normal resist work is not used and the process is simple because the resist work is free.

A conductive pattern-forming substrate obtained by the method for producing a conductive pattern-forming substrate as described above,
A catalyst for electroless plating is attached to the deprotected functional group (see the literature of CCM described in the section of the above-mentioned prior art), and then electroless plating is performed with the catalyst for electroless plating attached in a pattern. By carrying out, it is possible to obtain a conductive pattern forming body having a conductive pattern on the surface.

If the electroless plating layer alone does not have sufficient conductivity, electrolytic plating of copper or the like is performed if necessary. In addition, electroless plating of gold or the like may be performed.

This conductive pattern has various uses, for example, a printed circuit board, a DNA chip for electrical detection, a protein chip for electrical detection, a cell chip for electrical detection, and a biochip for electrical detection. 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 a 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.

D. In addition, the above-mentioned deprotection functional group is a group capable of adhering to another substance by a chemical bond, so that the deprotection functional group is deprotected by irradiation with energy and has adhesiveness. It can also be used as.

Further, in the present invention, the function as a memory can be exhibited by using materials having different laser refractive indexes of the photosensitive protective group and the deprotective functional group.

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.

[0157]

EXAMPLES The present invention will be described more specifically by showing Examples and Comparative Examples below.

[Example] A chrome mask (opening pattern: φ200) using a Pyrex (registered trademark) glass substrate
The surface of the photocatalyst-containing layer was prepared by coating a titanium oxide coating agent TKC301 for photocatalyst manufactured by Teika Co., Ltd. on the surface (μm, pitch: 500 μm) and drying at 350 ° C. for 3 hours.

Next, a quartz slide coated with poly (γ-methyl L-glutamate) -co- (γ- (p-nitrobenzyl) L-glutamate) was prepared as a substrate to be exposed, and p-nitrobenzyl group-derived Absorption of about 2
Its presence in the range of 40 to 330 nm was confirmed by absorption spectrum measurement. The photocatalyst containing layer side substrate is soft-contacted with the substrate to be exposed, and the substrate is exposed to normal temperature and pressure for 30
Ultraviolet rays in the wavelength range of 0 to 400 nm were irradiated for 1 hour.
As a result, a p-nitrobenzyl group was decomposed and eliminated in the exposed area to generate a carboxyl group, and the exposed area was hydrophilized.

Here, generation of a carboxyl group was proved by the following experiment. That is, after using the photocatalyst containing layer side substrate having no chromium layer (the entire surface is an opening), the coated slide was exposed, and then the surface zeta potential was adjusted to pH 9, 10 mM NaCl under the conditions of LEZA-manufactured by Otsuka Electronics. It was measured using 600. as a result,
The average value of the zeta potential was −24.6 mV, which was a negative value. Also, when measured under conditions of pH 3 and 10 mM NaCl, the average zeta potential was -3.3 mV. From the pH dependence of this zeta potential, it was concluded that carboxyl groups were formed on the sample surface.

Comparative Example Simple Pyrex (registered trademark)
Using the substrate, the zeta potentials of the sample surface that was subjected to the exposure treatment and the unexposed sample surface were measured under the same conditions as in the example, in the same manner as in the example. As a result, the average value of zeta potential is pH
In the case of 9, the values were −6.1 mV and −4.8 mV, respectively. In the case of pH 3, the average zeta potentials of the exposed and unexposed sample surfaces are −
It was 3.0 mV and +2.2 mV.

[0162]

According to the present invention, in the step of preparing a substrate for a pattern forming body, a characteristic change layer is formed by forming molecules having a functional group protected by a photosensitive protective group in a thin film on a substrate. Then, in the pattern formation step, by irradiating with energy, a pattern comprising a deprotected functional group obtained by deprotecting the functional group protected by a photosensitive protective group is formed on the surface of the characteristic change layer with high precision. can do.

By using a thin film of molecules having a functional group protected by a photosensitive protective group as the characteristic changing layer, the photocatalyst function associated with energy irradiation facilitates photosensitivity. It becomes possible to deprotect the protecting group. Therefore, the pattern of the deprotected functional group which has been deprotected can be easily formed, and it 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 contain 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 (18)

[Claims] 1. A thin film is formed by forming a substrate and a molecule having a functional group formed on the substrate and protected by a photosensitive protective group, wherein the photosensitive protective group is deprotected by the action of a photocatalyst. And a photocatalyst containing layer and a photocatalyst containing layer in a photocatalyst containing layer side substrate having a photocatalyst containing layer containing a photocatalyst and a substrate. And 200 μm or less with a gap therebetween, and by irradiating with energy from a predetermined direction, the functional group protected by a photosensitive protective group is deprotected on the surface of the characteristic change layer to obtain And a pattern forming step of forming a pattern comprising a deprotected functional group. 2. The pattern-formed body according to claim 1, wherein the photocatalyst-containing layer side substrate is composed of a base material and a photocatalyst-containing layer formed in a pattern on the base material. Method. 3. 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. 2. The method for manufacturing 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. 4. 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 3. 5. The photocatalyst containing layer side substrate is characterized in that 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 3. 6. The method for producing a pattern-formed body according to claim 1, wherein the photocatalyst-containing layer is a layer made of a photocatalyst. 7. The method for producing a pattern-formed body according to claim 6, wherein the photocatalyst-containing layer is a layer formed by forming a photocatalyst on a substrate by a vacuum film-forming method. 8. The method for manufacturing a pattern-formed body according to claim 1, wherein the photocatalyst-containing layer is a layer having a photocatalyst and a binder. 9. The photocatalyst is titanium oxide (Ti
O ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ),
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 ). The method for manufacturing a pattern formed body according to any one of claims 1 to 8. 10. The photocatalyst is titanium oxide (TiO ₂ ).
10. The method for manufacturing a pattern-formed body according to claim 9, wherein 11. The molecule according to claim 1, wherein the molecule having a functional group protected by the photosensitive protective group further has a functional group capable of binding to a molecule constituting the substrate. A method for manufacturing a pattern-formed body according to any one of claims. 12. The deprotection functional group 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 11 is a biological substance. A method for producing a biochip substrate, which is a deprotected functional group having a binding property to a biomaterial. 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 molecule having a functional group protected by a photosensitive protective group in the recess is deprotected in the pattern forming step to be a deprotected functional group. . 14. A deprotection functional group on the characteristic change layer of the pattern-formed body obtained by the method for producing a pattern-formed body according to claim 1, wherein the deprotection functional group is electroless plated. A method for producing a substrate for forming a conductive pattern, which is a deprotecting functional group having an adhesive property for an electroless plating catalyst that adheres to a catalyst for use in electroplating, and wherein the substrate has an electrical insulating property. 15. A biotechnology comprising the step of binding a biological substance to a deprotected functional group of the biochip substrate obtained by the method for producing a biochip substrate according to claim 12. Chip manufacturing 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. The substrate for a pattern-formed body obtained by the method for producing a pattern-formed body according to claim 1, wherein the bonded base material is a substrate for a pattern-formed body,
When the microfluidic chip base material and the bonding base material were bonded together, the surface part of the bonding base material corresponding to the concave portion of the microfluidic chip base material was protected by a photosensitive protective group. The method for producing a microfluidic chip according to claim 16, wherein the molecule having a functional group is deprotected in the pattern forming step to be a deprotected functional group. 18. A catalyst attachment for attaching a catalyst for electroless plating to a deprotected functional group of a conductive pattern forming base material obtained by the method for producing a conductive pattern forming base material according to claim 14. A method for producing a conductive pattern, comprising: a 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.