JP2003209340A - Method of manufacturing conductive-pattern forming body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a conductive pattern which forms a highly fine pattern in a simple process. <P>SOLUTION: The method comprises the steps of: preparing a substrate 3 having a photocatalyst containing layer 2 and a base material; preparing a substrate 6 for a pattern forming body which has a property varying layer 5 with the surface property varying by the action of the photocatalyst in the photocatalyst containing layer 2; forming a property varying pattern 9 where the property varies on the property varying layer 5 by radiating energy 8 from a predetermined direction after the photocatalyst containing layer 2 and the property varying layer 5 are placed in contact with each other; adhering a metallic colloidal solution to the pattern shape by coating the metallic colloidal solution on the surface of the substrate 6 for forming the pattern thereon; and forming a conductive pattern 11 by solidifying the metallic colloidal solution adhering to the pattern shape of the varying property. <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 conductive pattern forming body which can be used for various high definition electric circuits such as printed circuit boards.

[0002]

2. Description of the Related Art Conventionally, a highly precise conductive pattern forming body,
For example, when manufacturing a printed circuit board, in general, a copper clad laminate formed by plating the entire surface of the substrate with copper,
It is formed by laminating a photoresist such as a dry film, pattern exposure using a photomask or the like, and development.

However, in the method using such a photolithography method, metal plating on the substrate,
It is necessary to go through various steps such as formation of a photoresist layer, exposure, and development, the manufacturing method is complicated, and there may be a problem in terms of cost. Further, a large amount of waste liquid generated at the time of development is harmful, and there is also an environmental problem such that treatment is required to discharge it to the environment.

There is also a method of manufacturing a printed circuit board by a method using screen printing, but there is a problem in terms of accuracy and it cannot be applied to the manufacture of a highly precise conductive pattern.

[0005]

From the above, it is possible to form a high-definition pattern and a simple process, and to manufacture a conductive pattern without the problem of waste liquid treatment. A method is desired.

[0006]

According to a first aspect of the present invention, there is provided a photocatalyst containing layer side substrate preparing step of preparing a photocatalyst containing layer side substrate having a photocatalyst containing layer containing a photocatalyst and a base material, The photocatalyst-containing layer and the property-changing layer are in contact with the pattern-forming body substrate preparing step of preparing a pattern-forming body substrate having a property-changing layer whose surface properties are changed by the action of the photocatalyst in the photocatalyst-containing layer. After arranging in such a manner, a characteristic change pattern forming step of forming a characteristic change pattern with changed characteristics on the surface of the characteristic change layer by irradiating energy from a predetermined direction, and pattern formation in which the characteristic change pattern is formed A metal colloid solution coating step of applying the metal colloid solution to the surface of the body substrate by applying the metal colloid solution in a pattern. It provides a method for producing a conductive pattern formed body characterized by having a conductive pattern formation step of the conductive pattern by solidifying the metal colloid solution adhered in a pattern to the characteristic change pattern.

According to the present invention, it is possible to deposit a metal colloid solution in a pattern on a characteristic change pattern having changed characteristics by using, for example, a dip coating method or an inkjet method. A highly precise conductive pattern can be obtained. Therefore, since a highly precise conductive pattern can be formed with high precision by a simple process, a highly precise conductive pattern can be formed at low cost. In addition, for example, when the characteristic change layer is made of an insulating material, it is possible to form a highly accurate conductive pattern.

Further, according to the present invention, as described in claim 2, the photocatalyst containing layer side substrate having the photocatalyst containing layer containing the photocatalyst and the base material, and the characteristics are changed by the action of the photocatalyst in the photocatalyst containing layer. The photocatalyst-containing layer and the characteristic change layer having a characteristic change layer are arranged with a gap so that the photocatalyst-containing layer and the characteristic change layer have a thickness of 200 μm or less, and then energy is irradiated from a predetermined direction, A characteristic change pattern forming step of forming a characteristic change pattern having a changed characteristic on the surface of the characteristic change layer, and a metal colloid solution is applied to the substrate surface for a pattern forming body on which the characteristic change pattern is formed to form a pattern. The metal colloid solution coating step of depositing the metal colloid solution and the metal colloid solution deposited in a pattern in the above characteristic change pattern are performed. Provides a method for producing a conductive pattern formed body characterized by having a conductive pattern forming step of the reduction is allowed by the conductive pattern.

According to the present invention, the photocatalyst-containing layer and the characteristic change layer are arranged at a predetermined distance from each other and are irradiated with energy, so that the characteristic of the characteristic change layer in the portion efficiently irradiated with energy is changed to form a pattern. It is possible to manufacture a conductive pattern forming body having a high-definition pattern with changed characteristics without forming a post-treatment after energy irradiation. In addition, for example, when the characteristic change layer is made of an insulating material, it is possible to form a highly accurate conductive pattern.

Further, in the invention described in claim 1 or 2, as described in claim 3, the characteristic change layer is formed on the surface of the pattern forming substrate after the conductive pattern forming step. You may have the non-image area removal process which removes the non-image area which is the exposed part. Thus, when the characteristic changing layer is formed of a conductive material, the characteristic changing layer is removed and the insulating base is exposed, whereby a conductive pattern forming body can be obtained. Because.

Further, in the invention described in claim 3, as described in claim 4, it is preferable that the non-image area removing step is a step of removing the characteristic change layer with an alkaline solution. . This is because it is possible to easily remove the characteristic change layer, which is preferable in terms of manufacturing efficiency and cost.

In the invention according to any one of claims 1 to 4, as described in claim 5, the photocatalyst-containing layer side substrate is a base material and a base material on the base material. It is preferable that the photocatalyst-containing layer is formed in a pattern. 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. Further, since the characteristics are changed only in the surface contacting or facing the photocatalyst containing layer, 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.

Further, in the invention according to any one of claims 1 to 4, as described in claim 6, a base material and a photocatalyst-containing material formed on the base material are contained. It is preferable that the photocatalyst-containing layer side light-shielding portion is formed in a layered pattern, and the energy irradiation in the characteristic 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, since it is not necessary to use a photomask or the like for energy irradiation, alignment with the photomask is unnecessary, and the process is simplified. This is because it is possible to realize

In the invention described in claim 6, as described in claim 7, 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 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 the photocatalyst-containing layer side light-shielding portion is preferably placed in contact with or close to the characteristic change layer in terms of accuracy of the obtained characteristic change 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, there is an advantage that it can be used as a spacer when the photocatalyst containing layer and the property changing layer are brought into contact with or facing each other in the property changing pattern forming step. It is a thing.

According to the invention described in any one of claims 1 to 8, claim 9
As described in, the photocatalyst-containing layer is preferably a layer made of a photocatalyst. 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 9, as described in claim 10, the photocatalyst-containing layer is a layer formed by forming a photocatalyst on a substrate by a vacuum film-forming method. Is preferred. By forming the photocatalyst-containing layer by the vacuum film formation method as described above, it is possible to obtain a uniform photocatalyst-containing layer having a uniform film thickness with less unevenness of the surface, and a characteristic change pattern of the characteristic change layer surface can be formed. This is because the formation can be performed uniformly and with high efficiency.

On the other hand, in the invention described in any one of claims 1 to 8, as described in claim 11, 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 11
In the invention described in those claims,
As described above, the photocatalyst contains titanium oxide (Ti
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
The above substances are preferable, and in particular, in Claim 13.
As described, the photocatalyst is titanium oxide (TiO 2). _Two)
Is preferred. This is a band of titanium dioxide
Effective as a photocatalyst due to high gap energy
Is it stable, chemically stable, non-toxic, and easily available?
It is.

In the invention described in any one of claims 1 to 13, as described in claim 14, in the substrate for preparing a pattern-formed body, the characteristics on the substrate are obtained. It is preferable that the pattern forming substrate is prepared by forming the change layer. This is because it is preferable that the characteristic changing layer is formed on the substrate when the characteristic changing layer has low strength and does not have self-supporting property.

In the invention according to any one of claims 1 to 14, as described in claim 15, the characteristic change layer is formed by the action of the photocatalyst in the photocatalyst containing layer. It is preferable that the wettability changing layer is such that the wettability changes so that the contact angle with the liquid decreases when the energy is applied. Since the property changing layer is the wettability changing layer, it is possible to make the energy-irradiated region a lyophilic region and the energy-unirradiated region a lyophobic region, and use this difference in wettability. Then, the metal colloid solution can be attached only to the lyophilic region, and the conductive pattern can be easily formed.

According to the invention of claim 15 above,
As described in claim 16, the contact angle with respect to the metal colloid solution on the wettability changing layer is 50 ° or more in a portion not irradiated with energy and 40 ° or less in an irradiated portion. preferable.
When the wettability between the liquid repellent region, which is a portion not irradiated with energy on the wettability changing layer, and the lyophilic region, which is an irradiated portion, is not within the range as described above, a metal is used. This is because when the colloidal solution is applied to the entire surface, it may not be possible to adhere the metal colloidal solution only to the lyophilic region.

Further, in the invention described in claim 15 or claim 16, as described in claim 17,
The wettability changing layer is preferably a layer containing an organopolysiloxane. In the present invention, the properties required for the wettability changing layer are liquid repellency when not irradiated with energy, and when the energy is irradiated, due to the action of the photocatalyst in the photocatalyst-containing layer that contacts or opposes. It has the property of becoming lyophilic. This is because it is preferable to use organopolysiloxane as a material that imparts such characteristics to the wettability changing layer.

In the invention described in claim 17, as described in claim 18, it is preferable that the organopolysiloxane is a fluoroalkyl group-containing organopolysiloxane. This is because if the fluoroalkyl group is contained, it is possible to increase the difference in wettability between the energy-irradiated portion and the unirradiated portion.

In the invention described in claim 17 or claim 18, as described in claim 19, the organopolysiloxane is Y _n SiX.
_(4-n) (wherein Y represents an alkyl group, fluoroalkyl group, vinyl group, amino group, phenyl group or epoxy group, and X represents an alkoxyl group or halogen.
n is an integer from 0 to 3. It is preferable that the organopolysiloxane is a hydrolysis-condensation product or a co-hydrolysis-condensation product of one or more silicon compounds represented by the formula (1). This is because by using such an organopolysiloxane, it is possible to exhibit the characteristics with respect to the change in wettability as described above.

In the invention described in any one of claims 15 to 19, as described in claim 20, the substrate for pattern forming body comprises a wettability changing layer having a self-supporting property. May be. This is because if the wettability changing layer has a self-supporting property, it is not necessary to use a substrate or the like, and if a commercially available resin plate is used, for example, the pattern formed body can be manufactured at low cost.

In the invention described in any one of claims 1 to 14, as described in claim 21, the characteristic changing layer is formed by the action of the photocatalyst in the photocatalyst containing layer. It is preferably a decomposition-removal layer that is decomposed and removed when irradiated with energy. Since the property changing layer is a decomposition and removal layer, it becomes possible to form irregularities on the surface by the energy irradiation, and therefore the metal colloid solution can be easily attached by, for example, an inkjet method. It is because

In the invention described in claim 21,
As described in claim 22, it is preferable that a contact angle of the liquid with respect to the decomposition and removal layer is different from a contact angle of the liquid with respect to the substrate exposed by decomposition and removal of the decomposition and removal layer. This makes it possible to make the substrate exposed by the above-mentioned energy irradiation a lyophilic region and the part where the energy-irradiated decomposition and removal layer remains as a liquid-repellent region, so that the above metal colloid solution can be easily attached. Is possible.

In the twenty-first or twenty-second aspect of the present invention, as described in the twenty-third aspect, the decomposition and removal layer is a self-assembled monolayer film, Langmuir-Blodgett film, or alternate adsorption film. It is preferable that either This is because when the decomposition and removal layer is the above film, it is possible to easily form a defect-free film having relatively high strength.

In the invention according to any one of claims 21 to 23, as described in claim 24, the contact angle of the decomposition and removal layer with respect to the metal colloid solution is 50 ° or more. It is preferable that the contact angle of the substrate with respect to the metal colloid solution is 40 ° or less. The wettability between the lyophobic region, which is a portion formed by the remaining decomposition and removal layer that is not irradiated with energy on the decomposition and removal layer, and the lyophilic region, which is a portion where the substrate is exposed by energy irradiation, is as described above. If it is not within such a range, it may not be possible to adhere the metal colloid solution only to the lyophilic region when the metal colloid solution is applied to the entire surface.

In the invention described in any one of claims 1 to 24, as described in claim 25, when the surface of the characteristic changing layer is irradiated with energy, The distance between the photocatalyst containing layer and the surface of the characteristic changing layer is preferably within the range of 0.2 μm to 10 μm. When irradiating the energy, by irradiating the energy at intervals within the above range,
This is because it becomes possible to change the characteristics of the surface of the characteristic changing layer more effectively.

In the invention described in any one of claims 1 to 25, as described in claim 26, it is preferable that the energy irradiation is performed while heating the photocatalyst-containing layer. . By heating the photocatalyst, the sensitivity of the photocatalyst is improved and it becomes possible to efficiently change the characteristics on the characteristic change layer.

In the invention described in any one of claims 1 to 26, as described in claim 27, it is preferable that the characteristic changing layer is a layer containing no photocatalyst. . This is because, in the present invention, the characteristic change layer is a layer that does not contain a photocatalyst as described above, so that it is possible to avoid the problem that the characteristic change layer is affected by the passage of time.

In the invention according to any one of claims 1 to 27, as described in claim 28, the metal colloid solution is a silver colloid aqueous solution or a gold colloid aqueous solution. Is preferred.

Further, in the invention described in any one of claims 1 to 28, as described in claim 29, the application of the metal colloid solution in the step of applying the metal colloid solution is performed. It may be a dip coating method or a spin coating method.

Further, in the invention according to any one of claims 1 to 27, as described in claim 30, the application of the metal colloid solution in the step of applying the metal colloid solution is carried out by nozzle discharge. Method, and among them, the inkjet method is preferable.

According to a thirty-second aspect of the present invention, the wettability changing layer whose wettability is changed by the action of the photocatalyst and the metal colloid solution in a pattern form are solidified on the wettability changing layer. There is provided a conductive pattern forming body having the formed metal composition. According to the present invention, by having the wettability changing layer, it becomes possible to easily form a metal composition,
Further, when the wettability changing layer is insulative, an excellent conductive pattern forming body can be obtained.

According to the invention of claim 32,
As described in claim 33, the wettability changing layer may be formed on a substrate. This is because it is preferable that the characteristic change layer is formed on the substrate in the case where the wettability change layer has low strength and does not have self-supporting property.

In the invention described in claim 32 or claim 33, as described in claim 34, the contact angle with respect to the metal colloid solution on the wettability changing layer is in a portion not irradiated with energy. 50 °
It is above, and it is preferable that it is 40 degrees or less in the irradiated portion. This makes it possible to make the portion irradiated with energy a lyophilic region and the portion not irradiated with energy a lyophobic region, so that it is possible to easily manufacture a conductive pattern forming body, This is because it is preferable in terms of manufacturing efficiency and cost.

In the invention described in any one of claims 32 to 34, as described in claim 35, the wettability changing layer is a layer containing an organopolysiloxane. Among them, it is preferable that the organopolysiloxane is a polysiloxane containing a fluoroalkyl group. This is because such a wettability changing layer can obtain a large change in wettability by irradiation with energy.

In the invention described in claim 35 or claim 36, as described in claim 37, the organopolysiloxane is Y _n SiX _(4-n) (wherein Y is an alkyl group, Fluoroalkyl group, vinyl group,
An amino group, a phenyl group or an epoxy group is shown, and X is an alkoxyl group or a halogen. n is an integer from 0 to 3. It is preferable that the organopolysiloxane is a hydrolysis-condensation product or a co-hydrolysis-condensation product of one or more silicon compounds represented by the formula (1). By forming the wettability changing layer using such an organopolysiloxane as a material, a conductive pattern forming body having a wettability pattern having a large difference in wettability can be obtained.

According to a thirty-eighth aspect of the present invention, a substrate, a decomposition and removal layer decomposed and removed by the action of a photocatalyst on the substrate, and a substrate exposed by the decomposition and removal of the decomposition and removal layer are exposed. And a metal composition formed by solidifying a metal colloid solution in a pattern.

According to the present invention, it is possible to form a pattern having unevenness on the substrate by having the decomposition and removal layer, and it is possible to easily form a conductive pattern by utilizing this unevenness. it can. Further, when the decomposed and removed layer is insulative, it becomes possible to obtain an excellent conductive pattern forming body.

In the invention described in claim 38,
As described in claim 39, it is preferable that a contact angle of the liquid with respect to the decomposition / removal layer and a contact angle of the liquid with respect to the substrate exposed by decomposition of the decomposition / removal layer are different. As a result, not only the unevenness of the surface but also the substrate exposed by the energy irradiation can be used as the lyophilic region, and the portion where the decomposition and removal layer not irradiated with the energy remains can be used as the liquid repellent region. This is because it is possible to form a sex pattern.

Further, in the invention described in claim 38 or claim 39, as described in claim 40,
The decomposition and removal layer is preferably either a self-assembled monolayer film, a Langmuir-Blodgett film, or an alternate adsorption film. This is because when the decomposition and removal layer is the above film, it is possible to easily form a film having relatively high strength and no defects.

In the invention described in any one of claims 38 to 40, as described in claim 41, the contact angle of the decomposition and removal layer with respect to the metal colloid solution is 50 ° or more. It is preferable that the contact angle of the substrate with respect to the metal colloid solution is 40 ° or less. This makes it possible to make the portion exposed to the energy and exposed to the substrate the lyophilic region, and the portion not exposed to the energy to leave the decomposition and removal layer as the liquid-repellent region. This is because the formed body can be manufactured, which is preferable from the viewpoint of manufacturing efficiency and cost.

According to a 42nd aspect of the present invention, there is provided a substrate, a wettability changing layer formed in a pattern on the substrate, the wettability changing layer being changed by the action of a photocatalyst, and the wettability changing layer. And a metal composition formed by solidifying a metal colloid on the layer, and a conductive pattern forming body. By having the wettability changing layer on the substrate, a conductive pattern forming body can be easily manufactured, and when the substrate is insulating, an excellent conductive pattern forming body is obtained. Is possible.

[0049]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a method for producing a conductive pattern forming body and a conductive pattern forming body. Hereinafter, each will be described in detail.

A. Method for Manufacturing Conductive Pattern Formed Body First, a method for manufacturing the conductive pattern formed body of the present invention will be described.

The method for producing a conductive pattern forming body of the present invention comprises a photocatalyst containing layer side substrate preparing step of preparing a photocatalyst containing layer side substrate having a photocatalyst containing layer containing a photocatalyst and a base material, and the above photocatalyst containing layer. After the pattern forming body substrate preparing step of preparing a substrate for a pattern forming body having a characteristic changing layer whose surface characteristics are changed by the action of the photocatalyst, and placing the photocatalyst containing layer and the characteristic changing layer in contact with each other. , A characteristic change pattern forming step of forming a characteristic change pattern having changed characteristics on the surface of the characteristic change layer by irradiating energy from a predetermined direction, and a pattern forming body substrate surface on which the characteristic change pattern is formed. , A metal colloid solution applying step of applying the metal colloid solution in a pattern by applying the metal colloid solution, Is intended method characterized by having a conductive pattern formation step of solidifying the metal colloid solution adhered in a pattern to the conductive pattern to the change pattern.

In the method for producing a conductive pattern forming body of the present invention, the characteristics are changed by the action of the photocatalyst containing layer side substrate having the photocatalyst containing layer containing the photocatalyst and the base material, and the photocatalyst in the photocatalyst containing layer. The pattern-forming body substrate having a characteristic changing layer is arranged with a gap so that the photocatalyst-containing layer and the characteristic changing layer have a thickness of 200 μm or less, and then energy is irradiated from a predetermined direction to obtain the characteristic. A characteristic change pattern forming step of forming a characteristic change pattern having changed characteristics on the surface of the change layer, and a metal colloid solution is applied to the surface of the pattern forming substrate on which the characteristic change pattern is formed to form a metal pattern. The metal colloid solution coating process for depositing the colloid solution and the metal colloid solution deposited in a pattern according to the above characteristic change pattern It is characterized in that it has a conductive pattern formation step of solidifying the conductive pattern of.

In the method for producing a conductive pattern forming body of the present invention, the photocatalyst containing layer side substrate preparing step and
Although it may have the substrate preparing step for the pattern formed body, the photocatalyst containing layer side substrate formed in the photocatalyst containing layer side substrate preparing step described later and the pattern formation formed in the pattern forming body substrate preparing step If the same substrate as the body substrate is used, it is not always necessary to have the above steps.

In the method for producing a conductive pattern forming body according to the present invention, the photocatalyst-containing layer and the characteristic change layer are arranged at predetermined positions, and then energy is irradiated from a predetermined direction to remove the photocatalyst in the photocatalyst-containing layer. By the action, a characteristic change pattern in which the characteristic of the portion irradiated with energy is changed is formed. In this pattern formation, post-treatment such as development and cleaning after energy irradiation is unnecessary, so that it is possible to form a pattern having different characteristics with fewer steps than before and at a low cost. Then, by applying a metal colloid solution to the characteristic change pattern on the characteristic change layer, the metal colloid solution can be adhered in a pattern, and by solidifying this, a conductive pattern is easily formed. be able to.

Further, in the present invention, after changing the characteristics on the characteristic change 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 a conductive pattern forming body. Since it was done,
The obtained electroconductive pattern forming body does not necessarily need to contain a photocatalyst. Therefore, it is possible to prevent a problem that the obtained conductive pattern forming body is affected by the action of the photocatalyst over time.

The method of manufacturing the conductive pattern forming body of the present invention will be described in detail with reference to the drawings. FIG. 1 shows an example of a method for manufacturing a conductive pattern forming 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,
A substrate 6 for a pattern-formed body having a characteristic change layer 5 formed on a substrate 4 is prepared (see FIG. 1A, photocatalyst containing layer side substrate preparation step and pattern-formed body substrate preparation step).

Next, as shown in FIG. 1 (b), the photocatalyst containing layer side substrate 3 and the pattern forming substrate 6 are arranged with the photocatalyst containing layer 2 and the characteristic changing layer 5 at predetermined positions. After that, a photomask 7 on which a required characteristic change pattern is drawn is used, and ultraviolet light 8 is emitted from the photocatalyst containing layer side substrate 3 side through the photomask 7. As a result,
As shown in (c), the characteristic change pattern including the characteristic change region 9 and the characteristic unchanged region 10 is formed on the surface of the characteristic change layer 5 (characteristic change pattern forming step).

At this time, the photocatalyst-containing layer 2 and the characteristic change layer 5 are arranged so as to be in complete contact with each other in FIG. In addition to the above case, the photocatalyst-containing layer 2 may be arranged such that a gap to the extent that the photocatalyst can act is present between the photocatalyst-containing layer 2 and the characteristic change layer 5.

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 irradiated with energy 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)), the characteristic changed region 9 and the characteristic unchanged region 10 on the surface
It is possible to obtain the substrate 6 for a pattern-formed body in which and are formed.

Then, the metal colloid solution is applied onto the pattern forming substrate 6 so that the metal colloid solution is adhered only to the characteristic change region (metal colloid solution applying step), and thereafter, this is cured. Due to
It is possible to obtain the conductive pattern forming body 12 in which the conductive pattern 11 is formed on the characteristic change layer 5.

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

(1) Photocatalyst-containing layer side substrate preparation step The photocatalyst-containing layer side substrate preparation step in the present invention is a step of preparing a photocatalyst-containing layer side substrate having a photocatalyst-containing layer containing a photocatalyst and a substrate.

The photocatalyst-containing layer side substrate produced in this step thus has at least the photocatalyst-containing layer and the base material, and is usually a thin film formed on the base material by a predetermined method. A photocatalyst containing layer is formed.
As the photocatalyst containing layer side substrate, a photocatalyst containing layer side light shielding part formed in a pattern or a primer layer may be used.

(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 characteristic changing layer. And a binder, or a film formed of a photocatalyst alone. The surface property 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, a photomask or the like is used when the photocatalyst-containing layer is irradiated with energy, as will be described later in a characteristic change pattern forming step. It is not necessary to irradiate the pattern to be used, and by irradiating the entire surface, it is possible to form the characteristic change pattern including the characteristic change region and the characteristic unchanged region 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.

When the photocatalyst containing layer and the characteristic changing layer are closely contacted or faced to each other for energy irradiation, the characteristics of only the portion where the photocatalyst containing layer is actually formed are changed. The irradiation direction may be irradiation from any direction as long as the energy is applied to the portion where the photocatalyst containing layer and the characteristic change layer are in close contact with or opposite to each other. Further, the irradiation energy is particularly parallel light. It has the advantage that it is not limited to parallel ones.

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 photocatalyst-containing layer to the compound in the property change 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 above-mentioned photocatalyst. For example, the wettability changing layer in the characteristic changing layer described later will be described. Examples thereof include the organopolysiloxanes described in detail in the section.

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 manufactured by Dainippon Ink and Chemicals, Futergent F-200, F251 manufactured by Neos Co., Ltd., Unidyne DS-401, 402 manufactured by Daikin Industries, Ltd. Fluorine-based or silicone-based nonionic surfactants such as Fluorard 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.

(Base Material) In the present invention, as shown in FIG. 1, 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. is there.

At this time, the material constituting the base material used is appropriately selected depending on the direction of energy irradiation in the characteristic change pattern forming step, which will be described later, and whether the obtained conductive pattern forming body needs transparency. It

That is, for example, when the conductive pattern forming body uses an opaque material such as a paper-based phenolic resin laminate as a substrate, the energy irradiation direction is necessarily from the side of the photocatalyst containing layer side substrate, as shown in FIG. b)
As shown in FIG.
It needs to be placed on the side and irradiated with energy. Further, as will be described later, the photocatalyst-containing layer side light-shielding portion is formed in advance in a predetermined pattern on the photocatalyst-containing layer side substrate, and when the photocatalyst-containing layer side light-shielding portion is used to form the characteristic change pattern, the photocatalyst is also formed. It is necessary to irradiate energy from the containing layer side substrate side. In such a case, the base material needs to be transparent.

On the other hand, if the conductive pattern forming body is, for example, a transparent resin film, a photomask may be arranged on the substrate for the pattern forming body to apply 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 characteristic change 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.

(Photocatalyst-Containing Layer Side Light-Shielding Section) The photocatalyst-containing layer side light-shielding section used in the present invention may have a pattern-formed photocatalyst-containing layer side light-shielding section. By using the photocatalyst-containing layer-side substrate having the photocatalyst-containing layer-side light-shielding portion in this way, it is not necessary to use a photomask or to perform drawing irradiation with laser light at the time of energy irradiation. Therefore, since it is not necessary to align the photocatalyst containing layer side substrate with the photomask, a simple process can be performed, and an expensive device necessary for drawing irradiation is not required, which results in cost reduction. It has an advantage that it becomes advantageous.

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 13 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 contact portion between the photocatalyst-containing layer and the characteristic change layer or in the vicinity of the facing portion. 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 the 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 at predetermined positions, a predetermined gap is provided as described later. In the case where it is preferable that the photocatalyst-containing layer side light-shielding portion has a film thickness that matches the width of the gap, the photocatalyst-containing layer side light-shielding portion has a constant gap. It has the advantage that it can also be used as a spacer for

That is, when the photocatalyst containing layer and the characteristic changing layer are arranged in contact with or facing each other with a predetermined gap, the photocatalyst containing layer side light-shielding portion and the characteristic changing layer are in close contact with each other. By arranging with, it becomes possible to make the above-mentioned predetermined gap accurate, and by irradiating the energy from the photocatalyst containing layer side substrate in this state, the characteristic change pattern can be accurately formed on the characteristic change layer. Is possible.

The method for forming the photocatalyst-containing layer side light-shielding portion is not particularly limited, and may be appropriately selected depending on the characteristics of the surface on which the photocatalyst-containing layer side light-shielding portion is formed, the shielding ability against required energy, and the like. 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.

In the above description, the photocatalyst-containing layer side light-shielding part is formed between the base material and the photocatalyst-containing layer and on the surface of the photocatalyst-containing layer. It is also possible to adopt a mode in which the photocatalyst containing layer side light-shielding portion is formed on the surface on the side where the photocatalyst containing layer is not formed. In this aspect, 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 when changing the characteristic change pattern in a small lot.

(Primer Layer) Next, the primer layer used for the photocatalyst containing layer side substrate of the present invention will be described. In the present invention, 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 action and function of this 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 primer layer changes its characteristics 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 impurities existing not only in the photocatalyst-containing layer side light-shielding portion but also in 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.

FIG. 5 shows an example of the photocatalyst containing layer side substrate on which such a primer layer is formed. A primer layer 14 is formed on the surface of the substrate 1 on which the photocatalyst-containing layer side light-shielding portion 13 of the photocatalyst-containing layer side substrate 3 is formed, on the side where the photocatalyst-containing layer side light-shielding portion 13 is formed. The photocatalyst containing layer 2 is formed on the surface of 14.

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.

(2) Substrate Preparation Step for Pattern Formed Body Next, in the present invention, a substrate for a pattern formed body having a characteristic changing layer whose surface characteristics are changed by the action of the photocatalyst in the photocatalyst containing layer is prepared. The substrate for pattern-forming body preparation step is performed. The substrate for pattern-forming body prepared in this step is not particularly limited as long as it has at least a characteristic change layer whose surface characteristics are changed by the action of the photocatalyst in the photocatalyst containing layer, and the characteristic change layer is not particularly limited. When the above-mentioned property-changing layer does not have the self-supporting property, the property-changing layer may be formed on the substrate. Further, the pattern forming substrate may have a light shielding part or the like. Hereinafter, each structure of the pattern forming body substrate forming step will be described.

(Characteristic Change Layer) First, the characteristic change layer used in the substrate for a pattern forming body according to the present invention will be described. The property changing layer used in the substrate for a patterned body of the present invention is not particularly limited as long as it is a property changing layer whose surface properties are changed by the action of the photocatalyst in the photocatalyst-containing layer described above. In the invention, in particular, when the characteristic change layer is a wettability change layer in which the wettability is changed by the action of the photocatalyst to form a pattern due to the wettability, and the characteristic change layer is decomposed and removed by the action of the photocatalyst to form a pattern due to unevenness. The two cases of the decomposition and removal layer to be formed are preferable because they bring out the effectiveness of the present invention more from the relationship of the obtained characteristic change pattern and the like. Hereinafter, the wettability changing layer and the decomposition removing layer will be described.

A. Wettability change layer The wettability change layer in the present invention is not particularly limited as long as the wettability of the surface is changed by the action of the photocatalyst, but generally by the action of the photocatalyst accompanying the irradiation of energy, It is preferable that the wettability changing layer is a layer whose wettability changes so that the contact angle with the liquid on the surface of the wettability changing layer decreases.

By thus forming the wettability changing layer whose wettability changes so that the contact angle with the liquid is reduced by energy irradiation, as described above, for example, when a photomask is used or a photocatalyst-containing layer is used. When the layer-side light-shielding portion is used, or when the photocatalyst-containing layer is formed in a pattern, the wettability is easily changed to a pattern by irradiating energy, and the parent having a small contact angle with the liquid is used. It is possible to form a pattern of the liquid region.
Therefore, the conductive pattern forming body can be efficiently manufactured, which is advantageous in cost.

Here, the lyophilic region is a region having a small contact angle with a liquid and having a good wettability with a metal colloid solution described later. Further, the liquid repellent region is a region having a large contact angle with the liquid and having poor wettability with the metal colloid solution.

The wettability changing layer has a contact angle with the metal colloid solution of 50 ° or more, preferably 60, in the portion not irradiated with energy, that is, in the liquid repellent area.
It is preferably at least °, especially at least 70 °. This is because the part which is not irradiated with energy is the part which is required to have liquid repellency in the present invention. Therefore, when the contact angle with the liquid is small, the liquid repellency is not sufficient, and the metal colloid described later is used. This is because when the metal colloid solution is applied to the entire surface in the solution applying step, the metal colloid solution may remain in the region where the conductive pattern is not formed, which is not preferable.

Further, the wettability changing layer has a contact angle with the metal colloid solution of 40 ° or less, preferably 3 in the portion irradiated with energy, that is, the lyophilic region.
It is preferably 0 ° or less, and particularly preferably 20 ° or less. If the contact angle with the metal colloid solution in the part irradiated with energy, that is, the lyophilic region is high, the metal colloid solution may be repelled even in the lyophilic region when applying the metal colloid solution described later. The reason is that it may be difficult to pattern the metal colloid solution on the lyophilic region.

The contact angle with the liquid here is measured by using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) with a liquid having various surface tensions (micro). The droplet was dropped from the syringe 30 seconds later), and the result was obtained or a graph was obtained. In addition, in this measurement, as a liquid having various surface tensions, wetting index standard liquid manufactured by Junsei Chemical Co., Ltd. was used.

When the wettability changing layer as described above is used in the present invention, fluorine is contained in the wettability changing layer, and the fluorine content on the surface of the wettability changing layer is changed to the wettability changing layer. On the other hand, when the energy is irradiated, the wettability changing layer may be formed so as to be decreased by the action of the photocatalyst as compared with before the energy irradiation.

With the wettability changing layer having such characteristics, it is possible to easily form a pattern including a portion having a low fluorine content by pattern irradiation with energy. Here, since fluorine has an extremely low surface energy, the surface of a substance containing a large amount of fluorine has a smaller critical surface tension.
Therefore, the critical surface tension of the portion containing a small amount of fluorine becomes higher than the critical surface tension of the surface of the portion containing a large amount of fluorine. This means that the portion having a low fluorine content is a lyophilic region as compared with the portion having a high fluorine content. Therefore, forming a pattern composed of a portion having a smaller fluorine content than that of the surrounding surface forms a pattern of the lyophilic region in the lyophobic region.

Therefore, when such a wettability changing layer is used, a pattern of the lyophilic region can be easily formed in the lyophobic region by irradiating the pattern with energy. It is possible to easily form a conductive pattern by depositing a metal colloid solution only on the liquid region, and it is possible to form a highly precise conductive pattern at low cost.

As the content of fluorine contained in the wettability changing layer containing fluorine as described above, the fluorine content in the lyophilic region having a low fluorine content formed by irradiation with energy is When the fluorine content in the non-irradiated portion is 100, it is preferably 10 or less, preferably 5 or less, and particularly preferably 1 or less.

By setting the content within such a range, a large difference can be caused in the wettability between the energy-irradiated portion and the non-irradiated portion. Therefore, by forming a conductive pattern on such a wettability changing layer, it becomes possible to form a conductive pattern accurately only in the lyophilic region where the fluorine content is lowered, and it is possible to form the conductive pattern accurately. Because you can get a body. The rate of decrease is based on weight.

The fluorine content in the wettability changing layer can be measured by various commonly used methods, for example, X-ray photoelectron spectroscopy (X-ray Phot spectroscopy).
oelectron Spectroscopy, ESCA (Electron Spectroscop
y for Chemical Analysis). ), A fluorescent X-ray analysis method, a mass spectrometry method, or the like, as long as the amount of fluorine on the surface can be quantitatively measured.

The material used for such a wettability changing layer is the above-mentioned characteristic of the wettability changing layer, that is, the material whose wettability is changed by the photocatalyst in the photocatalyst containing layer which contacts or faces by energy irradiation, and There is no particular limitation as long as it has a main chain that is not easily degraded or decomposed by the action of the photocatalyst, and specific examples thereof include organopolysiloxane. In the present invention, it is preferable that the above-mentioned organopolysiloxane is a fluoroalkyl group-containing organopolysiloxane.

Examples of such an organopolysiloxane include (1) an organopolysiloxane which exhibits great strength by hydrolyzing and polycondensing chloro or alkoxysilane by a sol-gel reaction or the like, and (2) water repellency or Examples thereof include organopolysiloxanes such as organopolysiloxanes obtained by crosslinking reactive silicone having excellent oil repellency.

In the case of the above (1), the general formula: Y _n SiX _(4-n) (wherein Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group,
X represents an alkoxyl group, an acetyl group or halogen. n is an integer from 0 to 3. It is preferable that the organopolysiloxane is a hydrolysis-condensation product or a co-hydrolysis-condensation product of one or more silicon compounds represented by the formula (1). The number of carbon atoms of the group represented by Y is preferably within the range of 1 to 20, and the alkoxy group represented by X is a methoxy group, an ethoxy group, a propoxy group or a butoxy group. preferable.

Organopolysiloxane containing a fluoroalkyl group can be preferably used.
Specific examples thereof include hydrolyzed condensates and co-hydrolyzed condensates of one or more of the following fluoroalkylsilanes, and those generally known as fluorine-based silane coupling agents can be used. .

CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₇ CH ₂ CH _{2 Si (OCH 3) 3; CF} 3 (CF 2) 9 CH 2 CH 2 Si (OCH 3) 3; (CF 3) 2 CF (CF 2) 4 CH 2 CH 2 Si (OC
_{H 3) 3; (CF 3} ) 2 CF (CF 2) 6 CH 2 CH 2 Si (OC
_{H 3) 3; (CF 3} ) 2 CF (CF 2) 8 CH 2 CH 2 Si (OC
_{H 3) 3; CF 3 (} C 6 H 4) C 2 H 4 Si (OCH 3) 3; CF 3 (CF 2) 3 (C 6 H 4) C 2 H 4 Si (OCH
₃ ) ₃ ; CF ₃ (CF ₂ ) ₅ (C ₆ H ₄ ) C ₂ H ₄ Si (OCH
₃ ) ₃ ; CF ₃ (CF ₂ ) ₇ (C ₆ H ₄ ) C ₂ H ₄ Si (OCH
₃ ) ₃ ; CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ SiCH ₃ (OC
_{H 3) 2; CF 3 (} CF 2) 5 CH 2 CH 2 SiCH 3 (OC
_{H 3) 2; CF 3 (} CF 2) 7 CH 2 CH 2 SiCH 3 (OC
H ₃ ) ₂ ; CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ SiCH ₃ (OC
_{H 3) 2; (CF 3} ) 2 CF (CF 2) 4 CH 2 CH 2 SiCH 3
(OCH ₃ ) ₂ ; (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ Si CH
₃ (OCH ₃ ) ₂ ; (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ Si CH
₃ (OCH ₃ ) ₂ ; CF ₃ (C ₆ H ₄ ) C ₂ H ₄ SiCH ₃ (OC
_{H 3) 2; CF 3 (} CF 2) 3 (C 6 H 4) C 2 H 4 SiCH
₃ (OCH ₃ ) ₂ ; CF ₃ (CF ₂ ) ₅ (C ₆ H ₄ ) C ₂ H ₄ SiCH
₃ (OCH ₃ ) ₂ ; CF ₃ (CF ₂ ) ₇ (C ₆ H ₄ ) C ₂ H ₄ SiCH
₃ (OCH ₃ ) ₂ ; CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ Si (OCH ₂ C
_{H 3) 3; CF 3 (} CF 2) 5 CH 2 CH 2 Si (OCH 2 C
H ₃ ) ₃ ; CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₂ C
_{H 3) 3; CF 3 (} CF 2) 9 CH 2 CH 2 Si (OCH 2 C
H _{3) 3;} and _{CF 3 (CF 2) 7 SO} 2 N (C 2 H 5) C 2 H 4 CH
₂ Si (OCH ₃ ) ₃ .

By using the above-mentioned fluorosiloxane-containing polysiloxane as a binder,
The liquid repellency of the energy non-irradiated part of the wettability changing layer is greatly improved, and when the metal colloid solution is applied over the entire surface, it becomes possible to prevent the adhesion of the metal colloid solution, and the lyophilic region which is the energy irradiated part. It is possible to attach the metal colloid solution only to the above.

As the reactive silicone of the above (2), compounds having a skeleton represented by the following general formula can be mentioned.

[0133]

[Chemical 1]

However, n is an integer of 2 or more, and R ¹ ,
R ² is a substituted or unsubstituted alkyl, alkenyl, aryl or cyanoalkyl group having 1 to 10 carbon atoms, and 40% or less by mole of the total is vinyl, phenyl or phenyl halide. Further, it is preferable that R ¹ and R ² have a methyl group because the surface energy becomes the smallest, and the molar ratio of the methyl group is preferably 60% or more. Further, the chain end or side chain has at least one reactive group such as a hydroxyl group in the molecular chain.

In addition to the above-mentioned organopolysiloxane, a stable organosilicone compound which does not undergo a crosslinking reaction such as dimethylpolysiloxane may be mixed.

In the present invention, various materials such as organopolysiloxane can be used in the wettability changing layer as described above. However, as described above, it is necessary to add fluorine to the wettability changing layer. It is effective for forming a wettability pattern. Therefore, deterioration due to the action of the photocatalyst
It can be said that it is preferable to add fluorine to a material that is difficult to decompose, specifically, to add fluorine to an organopolysiloxane material to form the wettability changing layer.

As described above, as the method of incorporating fluorine into the organopolysiloxane material, the fluorine compound is usually bonded to the main agent having a relatively high binding energy with a relatively weak binding energy, and the bonding is carried out with a relatively weak binding energy. Examples thereof include a method of mixing the obtained fluorine compound into the wettability changing layer. By introducing fluorine by such a method, when energy is irradiated, first, a fluorine bond site having a relatively small bond energy is decomposed, whereby fluorine can be removed from the wettability changing layer. Is.

As the first method, that is, the method of binding the fluorine compound to the binder having a high binding energy with a relatively weak binding energy, a fluoroalkyl group is introduced into the organopolysiloxane as a substituent. Etc. can be mentioned.

For example, as a method for obtaining an organopolysiloxane, as described in (1) above, chloro or alkoxysilane is hydrolyzed and polycondensed by a sol-gel reaction or the like to obtain an organopolysiloxane exhibiting great strength. be able to. Here, in this method, as described above, the above general formula: Y _n SiX _(4-n) (wherein Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group). ,
X represents an alkoxyl group, an acetyl group or halogen. n is an integer from 0 to 3. The organopolysiloxane is obtained by hydrolytically condensing or co-hydrolytically condensing one or more of the silicon compounds represented by the formula (1), which has a fluoroalkyl group as the substituent Y in the general formula. By synthesizing using a silicon compound, an organopolysiloxane having a fluoroalkyl group as a substituent can be obtained. When an organopolysiloxane having such a fluoroalkyl group as a substituent is used as a binder, the carbon bond of the fluoroalkyl group is changed by the action of the photocatalyst in the photocatalyst-containing layer which contacts or opposes when irradiated with energy. Since the portion is decomposed, the fluorine content of the portion where the surface of the wettability changing layer is irradiated with energy can be reduced.

The silicon compound having a fluoroalkyl group used in this case is not particularly limited as long as it has a fluoroalkyl group, but it has at least one fluoroalkyl group. Has a carbon number of 4 to 30, preferably 6 to 20,
Particularly preferably, a silicon compound having 6 to 16 is preferably used. Specific examples of such a silicon compound are as described above, but among them, the above silicon compound having a fluoroalkyl group having 6 to 8 carbon atoms, that is, a fluoroalkylsilane is preferable.

In the present invention, such a silicon compound having a fluoroalkyl group is used as a mixture with the above-mentioned silicon compound having no fluoroalkyl group, and a cohydrolyzed condensate thereof is used as the above organopolysiloxane. Alternatively, one or more silicon compounds having such a fluoroalkyl group may be used, and a hydrolysis-condensation product or a co-hydrolysis-condensation product thereof may be used as the organopolysiloxane.

In the organopolysiloxane having a fluoroalkyl group thus obtained, among the silicon compounds constituting the organopolysiloxane, the silicon compound having a fluoroalkyl group is 0.01 mol% or more, preferably It is preferably contained in an amount of 0.1 mol% or more.

By including the fluoroalkyl group in this amount, the liquid repellency on the wettability changing layer can be increased, and the difference in the wettability from the portion which is irradiated with energy to form the lyophilic region is large. Because you can do it.

According to the method (2), an organopolysiloxane is obtained by crosslinking a reactive silicone having excellent liquid repellency. In this case as well, R in the general formula described above is similarly obtained. ^{By making} either or both of ¹ and R ² a fluorine-containing substituent such as a fluoroalkyl group, fluorine can be contained in the wettability changing layer, and in the case of being irradiated with energy, Since the portion of the fluoroalkyl group having a smaller binding energy than the siloxane bond is decomposed, the content of fluorine on the surface of the wettability changing layer can be reduced by the energy irradiation.

On the other hand, in the latter case, that is, as a method of introducing a fluorine compound bound with an energy weaker than the binding energy of the binder, for example, in the case of introducing a low molecular weight fluorine compound, for example, a fluorine-based surfactant is used. And a method of introducing a high molecular weight fluorine compound include a method of mixing a fluorine resin having a high compatibility with the binder resin.

The wettability changing layer in the present invention may further contain a surfactant. Specifically, NIKKOL BL, BC, B manufactured by Nikko Chemicals Co., Ltd.
Hydrocarbons such as O and BB series, Z made by DuPont
ONYL FSN, FSO, Surflon S-141, 145, manufactured by Asahi Glass Co., Ltd., Megafac F-141, 144, manufactured by Dainippon Ink and Chemicals, Inc., Futgent F-200, F251, manufactured by Neos Co., Ltd., Daikin Industries ( Fluorine-based or silicone-based nonionic surfactants such as Unidyne DS-401, 402 manufactured by 3D Co., Ltd., Florard FC-170, 176 manufactured by 3M Co., Ltd., and cationic surfactants and anionic surfactants. It is also possible to use a surfactant or an amphoteric surfactant.

In addition to the above-mentioned surfactant, the wettability changing layer contains polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane and melamine. Oligomers such as resin, polycarbonate, polyvinyl chloride, polyamide, polyimide, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene , A polymer, etc. can be contained.

Such a wettability changing layer is formed by dispersing the above-mentioned components in a solvent together with other additives, if necessary, to prepare a coating solution, and coating the coating solution on a substrate. be able to. 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. In addition, when the composition contains an ultraviolet curable component, the wettability changing layer can be formed by irradiating an ultraviolet ray to perform a curing treatment.

The wettability changing layer used in the present invention may be a self-supporting material as long as it is made of a material whose surface wettability can be changed by the action of a photocatalyst. Further, it may be a material having no self-supporting property. Incidentally, having self-supporting property in the present invention means
It means that it can exist in a tangible state without other supporting materials.

When the wettability changing layer is a material having a self-supporting property, it is possible to use, for example, a commercially available resin film made of a material capable of forming the wettability changing layer,
It can be said that it is advantageous in terms of cost. As such a material, if a film formed from the above-mentioned material has self-supporting property, it is also possible to use it. For example, polyethylene, polycarbonate, polypropylene, polystyrene, polyester, polyvinyl fluoride , Acetal resin, nylon, ABS, PTFE, methacrylic resin, phenol resin, polyvinylidene fluoride, polyoxymethylene, polyvinyl alcohol, polyvinyl chloride, polyethylene terephthalate, silicone and the like.

In the present invention, the wettability changing layer having no self-supporting property is preferable. The wettability changing layer, which is formed of a material whose characteristics change drastically as described above, usually has few self-supporting materials, and when formed on a substrate, the strength and the like increase, and it is used as various pattern forming bodies. This is because it becomes possible.

The wettability changing layer used in the present invention is not particularly limited as long as the wettability is changed by the action of the photocatalyst as described above, but it is particularly a layer containing no photocatalyst. Preferably there is. If the photocatalyst is not contained in the wettability changing layer, it is possible to use the photocatalyst for a long period of time without problems when using it as a functional element afterwards, without worrying about the influence of the photocatalyst over time. That's why.

In the present invention, the wettability changing layer has a thickness of 0.
The thickness is preferably 001 μm to 1 μm, particularly preferably 0.01 to 0.1 μm.

By using the wettability changing layer of the above-mentioned components in the present invention, the action of the photocatalyst in the photocatalyst-containing layer which contacts or opposes the action such as oxidation and decomposition of the organic group which is a part of the above-mentioned components. By using it, the wettability of the energy-irradiated portion can be changed to be lyophilic, and a large difference in wettability with the unirradiated portion can be generated. Therefore, even when the metal colloid solution described below is applied over the entire surface, the metal colloid solution can be relatively easily attached only within the lyophilic region, which is the energy irradiation portion, and high-definition conductive pattern formation is possible. The body can be manufactured at low cost.

B. Decomposition removal layer Next, the decomposition removal layer will be described. The decomposition removal layer used in the present invention is not particularly limited as long as it is a layer in which the decomposition removal layer of the portion irradiated with energy is decomposed and removed by the action of the photocatalyst in the photocatalyst-containing layer when irradiated with energy. is not.

As described above, since the portion irradiated with energy is decomposed and removed by the action of the photocatalyst in the decomposition / removal layer, a pattern composed of a portion with and without a decomposition / removal layer without performing a developing step or a washing step, That is, a pattern having unevenness can be formed.

The decomposition / removal layer is oxidatively decomposed by the action of a photocatalyst due to energy irradiation and vaporized, so that it is removed without any special post-treatment such as a developing / washing step. A cleaning step or the like may be performed depending on the material of the removal layer.

The decomposition / removal layer used in the present invention is
In addition to forming irregularities, it is preferable that the decomposition / removal layer has a high contact angle with the liquid as compared with the substrate described later. As a result, the decomposition removal layer is decomposed and removed, and the region where the substrate is exposed can be made a lyophilic region, and the region where the decomposition removal layer remains can be made a liquid repellent region, and various patterns can be formed. This is possible.

Here, the lyophilic region is a region having a small contact angle with a liquid and having a good wettability with a metal colloid solution described later. Further, the liquid repellent region is a region having a large contact angle with the liquid and having poor wettability with the metal colloid solution.

The decomposition and removal layer preferably has a contact angle with the metal colloid solution of 50 ° or more, preferably 60 ° or more, and particularly preferably 70 ° or more. This is because the present invention is that the remaining decomposition / removal layer is a portion that requires liquid repellency, so when the contact angle with the liquid is small, the liquid repellency is not sufficient, and the metal colloid solution described below is used. This is because when the metal colloid solution is applied to the entire surface in the applying step, the metal colloid solution may remain in the region where the conductive pattern is not formed, which is not preferable.

Further, in the present invention, the contact angle of the substrate, which will be described later, with the metal colloid solution is preferably 40 ° or less, preferably 30 ° or less, and particularly preferably 20 ° or less.
In the present invention, since the substrate is a part that is required to be lyophilic, there is a possibility that the metal colloid solution may be repelled even in the lyophilic region when the metal colloid solution described later is applied. It may be difficult to pattern the metal colloid solution on the area. Here, the contact angle with the liquid is a value measured by the method described above.

In this case, the substrate to be described later may be surface-treated so that the surface becomes lyophilic. Examples of the surface treatment of the surface of the material to be lyophilic include a lyophilic surface treatment by plasma treatment using argon or water, and the lyophilic layer formed on the substrate, For example, a silica film formed by a sol-gel method of tetraethoxysilane can be used.

Specific examples of the film that can be used for the decomposition and removal layer described above include films made of a fluorine-based or hydrocarbon-based resin having liquid repellency. The fluorine-based or hydrocarbon-based resin is not particularly limited as long as it has liquid repellency, and these resins are dissolved in a solvent and, for example, a general method such as spin coating is used. It can be formed by a film method.

Further, in the present invention, by using a functional thin film, that is, a self-assembled monolayer film, a Langmuir-Brocket film, an alternate adsorption film, etc., it is possible to form a film without defects. Therefore, it can be said that it is more preferable to use such a film forming method.

Here, the self-assembled monolayer film, Langmuir-Brocket film, and alternate adsorption film used in the present invention will be specifically described.

(I) Self-Assembled Monolayer Although the inventors do not know the existence of a formal definition of a self-assembled monolayer, it is generally recognized as a self-assembled monolayer. For example, see the review article “Formation and Structu” by Abraham Ulman.
re of Self-Assembled Monolayers ”, Chemical Revie
w, 96, 1533-1554 (1996) are excellent. With reference to this review, it can be said that a self-assembled monolayer is a monolayer formed as a result of adsorption and binding (self-assembly) of appropriate molecules to an appropriate substrate surface. Examples of materials capable of forming a self-assembled film include surfactant molecules such as fatty acids, organic silicon molecules such as alkyltrichlorosilanes and alkylalkoxides, organic sulfur molecules such as alkanethiols, and alkylphosphates. Examples of organic phosphoric acid molecules include The general commonality of molecular structures is
It has a relatively long alkyl chain and has a functional group that interacts with the surface of the substrate at one end of the molecule. The portion of the alkyl chain is a source of intermolecular force when the molecules are packed two-dimensionally. However, the example shown here has the simplest structure and has a functional group such as an amino group or a carboxyl group at the other end of the molecule, an alkylene chain portion of which is an oxyethylene chain, or a fluorocarbon chain. , A self-assembled monolayer composed of various molecules such as those of a complex type chain has been reported.
There is also a composite type self-assembled monolayer composed of multiple molecular species. In addition, recently, a polymer such as a dendrimer having a plurality of functional groups (there may be one functional group) or a linear polymer (which may have a branched structure) has been used. The one formed on the surface of the substrate (the latter is generally called a polymer brush) may be considered to be a self-assembled monolayer. The present invention also includes these in self-assembled monolayers.

(Ii) Langmuir-Blodgett film The Langmuir-Blodgett film (Lan) used in the present invention.
The gmuir-Blodgett film) does not differ much from the above-mentioned self-assembled monolayer in terms of morphology once formed on a substrate. It can be said that the Langmuir-Blodgett film is characterized by its formation method and a high degree of two-dimensional molecular packing property (high orientation, high ordering property) resulting therefrom. That is, generally, the Langmuir-Blodgett film-forming molecules are first spread on the gas-liquid interface, and the spread film is condensed by the trough and converted into a highly packed condensed film. In fact,
This is transferred to an appropriate substrate and used. It is possible to form from a monomolecular film to a multilayer film of an arbitrary molecular layer by the method outlined here. Also, not only small molecules,
Polymers, colloidal particles and the like can also be used as the film material. For recent examples of applying various materials, see Tokuharu Miyashita et al. “Prospects for nanotechnology in the creation of soft nanodevices” Polymer 50, September issue 644-647 (2001)
In detail.

(Iii) Alternate Adsorption Film An alternate adsorption film (Layer-by-Layer Self-Assembled Film) is
Generally, it is a film formed by sequentially adsorbing / bonding a material having at least two functional groups having positive or negative charges on a substrate and stacking the materials. Materials having a large number of functional groups have more advantages such as increased strength and durability of the film, and therefore, ionic polymers (polymer electrolytes) are often used as materials recently. Particles having a surface charge such as proteins, metals and oxides, so-called "colloidal particles" are also frequently used as film-forming substances. More recently, membranes that positively utilize interactions weaker than ionic bonds such as hydrogen bonds, coordination bonds, and hydrophobic interactions have also been reported. For the case of the relatively recent alternating adsorption film,
Although it is slightly biased toward material systems that use electrostatic interaction as a driving force, a review by Paula T. Hammond “Recent Explorations
in Electrostatic Multilayer Thin Film Assembly ”Cu
rrent Opinion in Colloid & Interface Science, 4, 4
Details on 30-442 (2000). Taking the simplest process as an example, the alternating adsorption film is obtained by repeating a cycle of adsorption of a material having a positive (negative) charge-cleaning-adsorption of a material having a negative (positive) charge-cleaning a predetermined number of times. This is the film that is formed. No development-condensation-transfer operations are required as with Langmuir-Blodgett membranes. Also, as is clear from the difference in these manufacturing methods, the alternating adsorption film has a two-dimensional high orientation property like the Langmuir-Blodgett film.
There is generally no high order. However, the alternate adsorption film and its manufacturing method have advantages that conventional film forming methods do not have, such as easily forming a dense film with no defects, and forming a film uniformly on minute uneven surfaces, tube inner surfaces, spherical surfaces, etc. Have many.

The film thickness of the decomposition / removal layer is not particularly limited as long as it is decomposed / removed by the energy applied in the characteristic change pattern forming step described later. The specific film thickness varies greatly depending on the type of energy to be irradiated, the material of the decomposition and removal layer, etc., but generally 0.001 μm to
It is preferably within the range of 1 μm, particularly preferably within the range of 0.01 μm to 0.1 μm.

(Substrate) Next, the substrate will be described. In the present invention, a substrate is used, for example, when the above-mentioned characteristic changing layer has no self-supporting property or is a decomposition and removal layer. For example, as shown in FIG. A change layer 5 is provided.

Such a substrate is appropriately selected according to the intended use of the finally obtained conductive pattern forming body, and is generally used in the case of an ordinary printed wiring board or the like. Known materials, specifically, a paper-based resin laminated plate, a glass cloth / glass nonwoven fabric-based resin laminated plate, ceramic, metal or the like can be used. Further, in the flexible wiring board, it is possible to use a flexible resin film as the base.

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

In this case, since it is necessary to perform energy irradiation in the characteristic change pattern forming step, which will be described later, from the side of the pattern forming substrate, it is preferable that the above-mentioned characteristic changing layer and the substrate are formed of a transparent material. preferable.

When the characteristic changing layer is formed on the substrate, it is preferable that the substrate side light-shielding portion for the pattern forming body is formed in a pattern on the surface of the substrate and the characteristic changing layer is formed thereon. When the characteristic changing layer has a self-supporting property and is not formed on the substrate, it is preferable that the substrate side light-shielding portion for the pattern forming body is formed on the surface of the characteristic changing layer on the side where the characteristic changing pattern is not formed.

The method of forming such a light-shielding portion is the same as that of the above-mentioned photocatalyst containing layer side light-shielding portion, and therefore the description thereof is omitted here.

(3) Characteristic Change Pattern Forming Step In the present invention, next, the photocatalyst containing layer and the characteristic change layer are arranged at predetermined positions, and then energy is irradiated from a predetermined direction to obtain the above characteristics. A characteristic change pattern forming step of forming a pattern on the surface of the change layer is performed. Hereinafter, each configuration of the characteristic change pattern forming step will be described.

(Arrangement of Photocatalyst Containing Layer and Characteristic Change Layer)
In this step, first, the photocatalyst-containing layer and the characteristic change layer need to be brought into contact with each other at the time of energy irradiation or arranged at a predetermined interval so that the action of the photocatalyst may be exerted.

Here, the contact in the present invention means a state in which the action of the photocatalyst substantially extends to the surface of the characteristic change layer, and the state of being in actual physical contact. In addition, the concept also includes a state in which the photocatalyst containing layer and the characteristic change layer are arranged at a predetermined interval. This gap is preferably 200 μm or less.

In the present invention, the above-mentioned gap is in a range of 0.2 μm to 10 μm in view of the fact that the pattern accuracy is extremely good, the photocatalyst sensitivity is high, and therefore the efficiency of property change of the property change layer is good. , Preferably 1μ
It is preferably within the range of m to 5 μm. Such a range of the gap is particularly effective for a conductive pattern forming body having a small area where the gap can be controlled with high accuracy.

On the other hand, when the conductive pattern forming body having a large area of, for example, 300 mm × 300 mm is processed, the above-mentioned fine gaps are not contacted with each other and the photocatalyst containing layer side substrate and the pattern forming body are formed. It is extremely difficult to form it with the substrate for use. Therefore, when the conductive pattern forming body has a relatively large area, the gap is in the range of 10 to 100 μm, particularly 50 to 75 μm.
It is preferably within the range of m. By setting the gap within such a range, there is no problem of deterioration of pattern accuracy such as blurring of a pattern, and deterioration of sensitivity of a photocatalyst and deterioration of efficiency of characteristic change. This is because there is an effect that unevenness in characteristics of the layers does not occur.

When the conductive pattern forming body having a relatively large area is irradiated with energy as described above, the gap between the photocatalyst containing layer side substrate and the pattern forming body substrate in the energy irradiating device is set in the positioning device. 10 μm to 200
It is preferable to set in the range of μm, particularly in the range of 25 μm to 75 μm. By setting the set value within such a range, the pattern accuracy is not significantly lowered and the photocatalyst sensitivity is not significantly deteriorated, and the photocatalyst-containing layer side substrate and the pattern-forming substrate are not in contact with each other. This is because they can be arranged.

By thus disposing the photocatalyst-containing layer and the surface of the characteristic changing layer at a predetermined distance, oxygen, 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 is difficult to desorb the active oxygen species, and as a result, the characteristic change speed may be slowed, which is preferable. Absent. In addition, when it is arranged at a distance from the above range, the generated active oxygen species are hard to reach the characteristic change layer, and in this case as well, the rate of characteristic change may be slowed, which is not preferable.

In the present invention, such a contact or facing state may be maintained at least only during energy irradiation.

As a method of 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,
A uniform gap can be formed, and since the action of the photocatalyst does not extend to the surface of the characteristic change layer at the portion where the spacer contacts, the spacer should have a pattern similar to the characteristic pattern described above. Thereby, it becomes possible to form a predetermined characteristic change pattern on the characteristic change layer.

In the present invention, such a spacer may be formed as one member, but for the sake of simplification of the process and the like, as described in the section of the photocatalyst containing layer side substrate preparation step, the photocatalyst containing layer is prepared. It is preferably formed on the surface of the photocatalyst containing layer of the 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.

(Energy Irradiation to Contact or Opposing Portion) Next, energy irradiation is performed to the contacting or opposing portion while maintaining the above-mentioned contact or opposing state. 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.

Generally, the wavelength of light used for such energy irradiation is in the range of 400 nm or less, preferably 380 n.
It is set from a range of m or less. This is because the preferable photocatalyst used in the photocatalyst-containing layer is titanium dioxide as described above, and the light having the above-mentioned wavelength is preferable as the energy for activating the photocatalytic action by the titanium dioxide.

Examples of the light source that can be used for such energy irradiation 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 energy irradiation amount at the time of energy irradiation 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, by irradiating energy while heating the photocatalyst-containing layer, it is possible to increase the sensitivity and 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 energy irradiation direction is the method of forming a characteristic change pattern such as whether the photocatalyst-containing layer side light-shielding portion or the pattern-forming substrate-side light-shielding portion is formed, the photocatalyst-containing layer side substrate or pattern. It is determined by whether or not the formed body substrate is transparent.

That is, when the photocatalyst containing layer side light-shielding portion is formed, it is necessary to irradiate energy from the photocatalyst containing layer side substrate side, and in this case, the photocatalyst containing layer side substrate is irradiated with energy. On the other hand, it needs 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 energy irradiation direction 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 irradiate energy from the pattern forming body substrate side, and in this case, the pattern forming body substrate is irradiated. Need to be transparent to the energy it consumes. 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 energy irradiation direction may be from the photocatalyst containing layer side substrate side or the pattern forming body substrate side.

Further, the energy irradiation direction in the case where the photocatalyst containing layer is formed in a pattern is such that the energy is irradiated to the portion where the photocatalyst containing layer and the characteristic change layer are in contact with each other or face each other as described above. It may be irradiated from any direction.

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

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.

(Removal of Photocatalyst-Containing Layer Side Substrate) When the energy irradiation as described above is completed, the photocatalyst-containing layer side substrate is brought into contact with the characteristic change layer or separated from the position arranged with a gap. As shown in FIG. 1D, a characteristic change pattern including a characteristic change region 9 and a characteristic unchanged region 10 is formed on the characteristic change layer 5.

(4) Metal Colloid Solution Coating Step In the present invention, next, the metal colloid solution is applied to the surface of the pattern forming substrate on which the above-mentioned characteristic change pattern is formed to form a pattern of the metal colloid solution. A metal colloid solution coating step for attaching the is carried out.

The method of applying the metal colloid solution is not particularly limited as long as it can be applied to the surface of the characteristic change layer. Specifically, the characteristic change such as the dip coating method or the spin coating method can be used. It may be a method of coating the entire surface of the layer, or a method of coating the above metal colloid solution in a desired pattern like a nozzle discharge method. Further, among the nozzle ejection methods, the inkjet method is preferable.

The viscosity of the metal colloid solution used in the present invention is 1 to 100 cps, preferably 5 to 50 cps.
Especially, it is preferable that it is in the range of 10 to 20 cps,
The concentration is 1 to 70 wt%, preferably 10 to 50 w
It is preferably in the range of t%, particularly 20 to 30% by weight. When the viscosity and the concentration are lower than the above ranges, it depends on the use, but it is not preferable because it may be difficult to put into practical use because the film thickness of the obtained metal pattern is too thin. On the other hand, if the viscosity and the concentration are higher than the above ranges, patterning may not be possible when such a metal colloid solution is applied to the entire surface, which is not preferable.

Further, the surface tension of the metal colloid solution is preferably 20 mN / m or more, preferably 50 mN / m or more, and particularly 70 mN / m or more. When the surface tension is lower than the above range, for example, it may not be possible to obtain a large contact angle in the liquid repellent region, and as a result, the metal colloid solution may remain in the liquid repellent region, which is preferable. Absent. The upper limit of the surface tension of the metal colloid solution is not particularly limited, but it can be said that it is preferably 80 mN / m or less.

As described above, the metal colloid solution used in the present invention is preferably a solution having a large surface tension. This is because it is necessary to remove the metal colloid solution applied to the lyophobic area other than the lyophilic area when it is applied to the entire surface as described above, or to collect in the lyophilic area.
For this purpose, it is preferable that the contact angle of the metal colloid solution in the liquid repellent region is large. From such a viewpoint, in the present invention, it is preferable to use a metal colloid aqueous solution using water as a medium.

The type of metal used in the metal colloid solution used in the present invention is preferably silver or gold. This is because they have good conductivity and corrosion resistance.

Therefore, in the present invention, it is preferable to use a gold colloid aqueous solution or a silver colloid aqueous solution.

(5) Conductive Pattern Forming Step In the present invention, finally, a conductive pattern forming step of solidifying the metal colloidal solution adhering to the above pattern to form a conductive pattern is carried out, and finally the pattern is formed. The substrate for a forming body is used as a conductive pattern forming body.

Heating is the most general method of solidification used here, and heating is carried out in the range of 100 ° C. to 700 ° C., preferably 250 ° C. to 500 ° C., and the heating time is 10 minutes to In the range of 60 minutes, preferably 20
It is within the range of 40 minutes.

(6) Non-image area removing step In the method of manufacturing a conductive pattern forming body of the present invention,
In addition to the steps described above, a non-image area removing step of removing the characteristic change layer other than the conductive pattern forming section formed in the conductive pattern forming step may be included. When the above-mentioned characteristic change layer is conductive, it is difficult to form a conductive pattern forming body even if it has a conductive pattern on the pattern forming body. By removing the characteristic change layer in the area (1), the base is exposed to form a conductive pattern forming body. At this time, the substrate needs to be an insulating material among the above.

In the non-image area removing step of the present invention, for example, the pattern forming body substrate (FIG. 6 (a)) formed by the conductive pattern forming step is exposed on the surface other than the conductive pattern 11 region. This is a step of removing the non-image area 7 made of the characteristic change layer (FIG. 6B), and the method is not particularly limited as long as the non-image area 7 can be removed. .

Specific examples of the method for removing the non-image areas include a method of spraying an alkaline solution or a strong acid such as hydrofluoric acid and concentrated sulfuric acid, and a method of dipping.

(7) Others In the present invention, the conductive pattern forming body may be further electroplated to increase the thickness of the conductive pattern. By doing so, it is possible to reduce the resistance of the conductive pattern and at the same time improve the adhesion strength of the conductive pattern to the characteristic change layer, and to obtain a high-quality, high-definition wiring board. Because you can

Further, in the present invention, an insulating protective layer may be further formed after the conductive pattern is formed. By doing so, it is possible to prevent problems such as peeling of the conductive pattern. When this insulating protective layer is used as a characteristic change layer, it can be used as a multilayer printed wiring board by further forming a conductive pattern on it.

B. Pattern Formed Body Next, the pattern formed body of the present invention will be described. The pattern formed body of the present invention has three embodiments. Less than,
Each pattern forming body will be described.

1. First Embodiment First, a first embodiment of the pattern forming body of the present invention will be described. The first embodiment of the pattern-formed body of the present invention is
A wettability changing layer whose wettability changes by the action of a photocatalyst,
A metal composition formed by solidifying a metal colloid solution in a pattern on the wettability changing layer. Since the pattern forming body of the present embodiment has the wettability changing layer, it is possible to easily form the lyophilic region and the lyophobic region in a pattern by energy irradiation. By attaching the metal colloid solution to the area, the conductive pattern forming body can be easily manufactured.

Further, in this embodiment, since the conductive pattern is formed on the wettability changing layer, the electric resistance of the wettability changing layer is 1 × 10 ⁸ Ω · cm to 1 × 10 5.
¹⁸ Ω · cm, especially 1 × 10 ¹² Ω · cm to 1 × 10
It is preferably in the range of ¹⁸ Ω · cm. This makes it possible to obtain an excellent pattern-formed body.

The pattern forming body of the present embodiment is not particularly limited in its structure and the like as long as it has the wettability changing layer and the metal composition formed in a pattern on the wettability changing layer. For example, as shown in FIG. 7A, the wettability changing layer 5 which is one of the characteristic changing layers is formed on the substrate 4, and the metal composition 11 is formed on the wettability changing layer 5. May be formed in a pattern. Further, for example, as shown in FIG. 7B, when the wettability changing layer 5 has self-supporting property, the metal composition 11 is formed on the wettability changing layer 5. It may be formed in a pattern.

As the wettability changing layer and the substrate used in this embodiment, those described in "Pattern forming body substrate preparing step" in "A. Method for producing pattern forming body" described above can be used. Therefore, the description thereof is omitted here. Further, the metal composition used in the present embodiment is obtained by solidifying a metal colloid solution in a pattern, and includes the “metal colloid solution applying step” and the “conductivity” in the above-mentioned “A. Method for producing pattern-formed body”. Since the material and the manufacturing method are the same as those described in the "pattern forming step", description thereof will be omitted here.

2. Second Embodiment Next, a second embodiment of the conductive pattern forming body of the present invention will be described. A second embodiment of the conductive pattern forming body of the present invention is a substrate, a decomposition and removal layer decomposed and removed by the action of a photocatalyst on the substrate, and a pattern on the substrate exposed by decomposition and removal of the decomposition and removal layer. And a metal composition formed by solidifying a metal colloid solution.

The conductive pattern of this embodiment is not particularly limited in structure and the like. For example, as shown in FIG. 8, the base 4 and the decomposition and removal which is the characteristic change layer formed on the base 4 are removed. The layer 5 and the metal composition 11 formed on the base 4 exposed by the decomposition and removal of the decomposition and removal layer 5 are provided.

Since the conductive pattern forming body of this embodiment has the above-mentioned decomposition and removal layer, it becomes possible to easily form a pattern-like unevenness on the surface by irradiating with energy, and this unevenness is utilized. Thus, it becomes possible to manufacture a conductive pattern forming body. Further, in the decomposition / removal layer of this embodiment, it is preferable that the contact angle of the metal colloid solution with respect to the decomposition / removal layer and the contact angle of the metal colloid solution with respect to the substrate are different from each other. This makes it possible to manufacture the conductive pattern forming body by utilizing not only the unevenness of the surface but also the difference in wettability.

Further, in this case, since the conductive pattern is formed on the substrate, the electrical resistance of the substrate is 1 × 10 ⁸ Ω.
・ Cm to 1 × 10 ¹⁸ Ω · cm, especially 1 × 10 ¹² Ω
- It is preferable cm~1 in the range of × ^{10 18} Ω · cm.

Further, since the decomposition / removal layer exists around the conductive pattern, the electric resistance of the decomposition / removal layer is from 1 × 10 ⁸ Ω · cm to 1 × 10 ¹⁸ Ω · cm, and particularly 1
It is preferably in the range of × 10 ¹² Ω · cm to 1 × 10 ¹⁸ Ω · cm. This is because it is possible to obtain an excellent pattern-formed body.

The decomposition-removal layer and the substrate used in this embodiment are the same as those described above in "A. Method for producing pattern-formed body".
Since it is possible to use the one described in the “Pattern forming body substrate preparing step” in the above, the description thereof is omitted here. Further, the metal composition used in this embodiment is
The metal colloid solution is solidified in a pattern, and the material and the manufacturing method described in “Metal colloid solution coating step” and “Conductive pattern forming step” in the above-mentioned “A. The description is omitted here because it is the same.

3. Third Embodiment Next, a third embodiment of the conductive pattern forming body of the present invention will be described. A third embodiment of the conductive pattern forming body of the present invention comprises a substrate, a wettability changing layer whose wettability is changed by the action of a photocatalyst formed in a pattern on the substrate, and a wettability changing layer on the wettability changing layer. And a metal composition formed by solidifying a metal colloid.

The conductive pattern forming body of the present invention is not particularly limited in structure and the like. For example, as shown in FIG. 9, the substrate 4 and the wetting layer which is a characteristic change layer in a pattern on the substrate 4 are formed. The sex change layer 5 is formed, and the metal composition 11 is formed on the wettability change layer 5.

Since the conductive pattern forming body of the present embodiment has the wettability changing layer, it is possible to easily manufacture the conductive pattern forming body by utilizing the difference in wettability. . In addition, since the wettability changing layer is formed in a pattern on the substrate and the conductive pattern is formed on the wettability changing layer, the substrate is exposed on the surface except the conductive pattern. There is. Thereby, even if the wettability changing layer is conductive, it becomes possible to form a conductive pattern forming body. In this case, the electric resistance of the substrate is 1 × 10 ⁸ Ω · cm to 1 × 10 ¹⁸ Ω · c.
m, especially 1 × 10 ¹² Ω · cm to 1 × 10 ¹⁸ Ω · c
It is preferably within the range of m. This makes it possible to obtain an excellent conductive pattern forming body.

The decomposition / removal layer and the substrate used in this embodiment are the above-mentioned "A. Method for producing pattern-formed body".
Since it is possible to use the one described in the “Pattern forming body substrate preparing step” in the above, the description thereof is omitted here. Further, the metal composition used in this embodiment is
The metal colloid solution is solidified in a pattern, and the material and the manufacturing method described in “Metal colloid solution coating step” and “Conductive pattern forming step” in the above-mentioned “A. The description is omitted here because it is the same.

The present embodiment is not limited to the above embodiment. The above-described embodiment is an exemplification, and it has substantially the same configuration as the technical idea described in the claims of the present embodiment, and has any similar effects. It is included in the technical scope of the present embodiment.

[0229]

EXAMPLES Hereinafter, the present embodiment will be described in more detail through examples.

[Example 1] A titanium oxide coating agent TKC301 for photocatalyst manufactured by Teika Co., Ltd. was coated on a quartz glass substrate on which a black matrix made of chromium having a thickness of 0.4 µm was formed in a line and space of 50 µm.
It was dried at 350 ° C. for 3 hours to prepare a photocatalyst-containing layer side substrate.

Next, MF-160E (trade name, manufactured by Tochem Products Co., Ltd.) containing fluoroalkylsilane as a main component
A glass substrate was coated with a solution prepared by adding 3 g of 0.1N hydrochloric acid solution to 0.4 g and stirring at room temperature for 1 hour, and dried at 150 ° C. for 10 minutes to prepare a substrate for a pattern forming body.

[0232] The photocatalyst containing layer side substrate was brought into close contact with this,
Exposure from the substrate on the photocatalyst containing layer side with an ultra-high pressure mercury lamp (36
5 nm 1000 mJ / cm ² ) to form a lyophilic region on the surface of the pattern forming substrate.

The contact angle with the aqueous silver colloid solution (concentration: 20 wt%) in the liquid repellent region was 75 °, and the contact angle in the lyophilic region was 10 °.

By dipping the substrate for a pattern forming body in an aqueous silver colloid solution (concentration: 20 wt%) and pulling it up at 10 mm / sec., The aqueous silver colloid solution was adhered in a pattern only on the lyophilic region. . The pattern of this silver colloid aqueous solution was heated at 300 ° C. for 20 minutes to obtain a conductive pattern forming body in which silver was patterned on the substrate.

[Example 2] A titanium oxide coating agent TKC301 for photocatalyst manufactured by Teika Co., Ltd. was coated on a quartz glass substrate on which a black matrix made of chromium having a thickness of 0.4 µm was formed in a line and space of 50 µm.
It was dried at 350 ° C. for 3 hours to prepare a photocatalyst-containing layer side substrate.

Next, MF-160E (trade name, manufactured by Tochem Products Co., Ltd.) containing fluoroalkylsilane as a main component
A glass substrate was coated with a solution prepared by adding 3 g of 0.1N hydrochloric acid solution to 0.4 g and stirring at room temperature for 1 hour, and dried at 150 ° C. for 10 minutes to prepare a substrate for a pattern forming body.

[0237] The photocatalyst containing layer side substrate was brought into close contact with this,
Exposure from the substrate on the photocatalyst containing layer side with an ultra-high pressure mercury lamp (36
5 nm 600 mJ / cm ² ) to form a lyophilic region on the surface of the pattern forming substrate.

The contact angle with respect to the aqueous silver colloid solution (concentration: 20 wt%) in the lyophobic region was 75 °, and the contact angle in the lyophilic region was 30 °.

By dipping the substrate for a pattern-forming body in an aqueous silver colloid solution (concentration: 20 wt%) and pulling it up at 10 mm / sec., The aqueous silver colloid solution was adhered in a pattern only on the lyophilic region. . The pattern of this silver colloid aqueous solution was heated at 300 ° C. for 20 minutes to obtain a conductive pattern forming body in which silver was patterned on the substrate.

Example 3 A photocatalyst-containing layer side substrate and a pattern forming substrate were prepared in the same manner as in Example 1 and exposed in a pattern in the same manner, whereby the substrate surface for the pattern forming substrate was exposed. A liquid region was formed.

The contact angle to the silver colloid aqueous solution (concentration 50 wt%) in the unexposed area, that is, the liquid repellent area was 83 °.
And the contact angle in the exposed portion, that is, the lyophilic region was 12 °.

An aqueous solution of silver colloid (concentration: 50 wt.
%) And pulled up at 10 mm / sec., The silver colloid aqueous solution was adhered in a pattern only on the lyophilic region. The pattern of this silver colloid solution is 300
By heating at 0 ° C. for 20 minutes, a conductive pattern forming body in which silver was patterned on the substrate was obtained.

[Comparative Example 1] A titanium oxide coating agent TKC301 for photocatalyst manufactured by Teika Co., Ltd. was coated on a quartz glass substrate on which a black matrix made of chromium having a thickness of 0.4 µm was formed in a line and space of 50 µm.
It was dried at 350 ° C. for 3 hours to prepare a photocatalyst-containing layer side substrate.

Next, MF-160E (trade name, manufactured by Tochem Products Co., Ltd.) containing fluoroalkylsilane as a main component
A glass substrate was coated with a solution prepared by adding 3 g of 0.1N hydrochloric acid solution to 0.4 g and stirring at room temperature for 1 hour, and dried at 150 ° C. for 10 minutes to prepare a substrate for a pattern forming body.

[0245] The photocatalyst containing layer side substrate was brought into close contact with this,
Exposure from the substrate on the photocatalyst containing layer side with an ultra-high pressure mercury lamp (36
5 nm 300 mJ / cm ² ) to form a lyophilic region on the surface of the pattern forming substrate.

The contact angle with respect to the aqueous silver colloid solution (concentration: 20 wt%) in the lyophobic region was 75 °, and the contact angle in the lyophilic region was 45 °.

An aqueous solution of silver colloid (concentration: 20 wt.
%) And pulled up at 10 mm / sec., But the silver colloid aqueous solution was repelled over the entire surface including the lyophilic region,
It was not possible to obtain a conductive pattern forming body.

[Comparative Example 2] A silica glass substrate having a thickness of 0.4 µm and a black matrix made of chromium formed in a line and space of 50 µm was coated with TKC301, a titanium oxide coating agent for photocatalyst manufactured by Teika Co., Ltd.,
It was dried at 350 ° C. for 3 hours to prepare a photocatalyst-containing layer side substrate.

Next, 30 g of isopropyl alcohol was mixed with 3 g of trimethoxymethylsilane (manufactured by Toshiba Silicone Co., Ltd., trade name TSL8113) and 3 g of 0.1N hydrochloric acid water, and the mixture was mixed at 100 ° C.
Stir for 20 minutes, coat the solution on a glass substrate,
It was dried at 150 ° C. for 10 minutes to prepare a substrate for a pattern forming body having a fluorine-free wettability changing layer.

The photocatalyst-containing layer side substrate was brought into close contact with this,
Exposure from the substrate on the photocatalyst containing layer side with an ultra-high pressure mercury lamp (36
5 nm 600 mJ / cm ² ) to form a lyophilic region on the surface of the pattern forming substrate.

The contact angle with the aqueous silver colloid solution (concentration: 20 wt%) in the lyophobic region was 44 °, and the contact angle in the lyophilic region was 10 °.

A silver colloid solution (concentration: 20 wt.
%) And pulled up at 10 mm / sec. However, the entire surface including the liquid repellent region was coated with the aqueous silver colloid solution, and the conductive pattern forming body could not be obtained.

[Example 4] 5 g of trimethoxymethylsilane (GE Toshiba Silicone Co., Ltd., TSL8113)
And 0.5 N hydrochloric acid were mixed with 2.5 g, and the mixture was stirred for 8 hours. This was diluted 10 times with isopropyl alcohol to obtain a primer layer composition.

The above composition for a primer layer was applied onto a photomask substrate by a spin coater, and the composition was applied at 150 ° C. for 1 hour.
A transparent primer layer (thickness 0.2 μm) was formed by performing a drying treatment for 0 minutes. Next, 30 g of isopropyl alcohol, 3 g of trimethoxymethylsilane (TSL8113 manufactured by GE Toshiba Silicone Co., Ltd.) and 20 g of ST-K03 (manufactured by Ishihara Sangyo Co., Ltd.), which is a photocatalytic inorganic coating agent, were mixed, and the mixture was heated at 100 ° C. Stir for 20 minutes. This was diluted 3 times with isopropyl alcohol to obtain a photocatalyst-containing layer composition. The photocatalyst-containing layer composition is applied onto a photomask substrate on which a primer layer is formed by a spin coater, and dried at 150 ° C. for 10 minutes to obtain a transparent photocatalyst-containing layer (thickness 0.15 μm). Was formed.

Next, 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 1,1,2-trichloroethane to obtain a composition for the decomposition layer removing layer. The composition for decomposition and removal layer is applied onto a glass substrate by a spin coater, and 1
By performing a drying treatment at 00 ° C. for 60 minutes, a transparent decomposition and removal layer (thickness 0.01 μm) was formed to obtain a substrate for a pattern forming body.

The photocatalyst-containing layer side substrate and the decomposition and removal layer are aligned, face each other with a gap of 100 μm, and the photomask side is exposed to an ultrahigh pressure mercury lamp (wavelength 365 nm) at an illuminance of 40 mW / cm ² for 600. After exposure for 2 seconds, the decomposition and removal layer was decomposed and removed, and a decomposition and removal pattern made of the exposed glass substrate was formed in a pattern.

At this time, the contact angle between the unexposed portion and the decomposition removal pattern and the silver colloid solution (concentration 20%) was measured using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) (micro After 30 seconds from dropping the droplet from the syringe), the results were 65 ° and 6 °, respectively.

Next, a silver colloid solution (concentration: 20%) was attached to the decomposition / removal pattern using an ink jet device, and this was treated at 300 ° C. for 60 minutes and cured to form a conductive pattern.

Finally, the substrate on which the conductive pattern was formed was dipped in an alkaline aqueous solution containing PH13 as a main component for 2 minutes, and then rinsed with water for 5 minutes to remove non-image areas. A conductive pattern forming body was obtained.

Example 5 Trimethoxymethylsilane (G
E Toshiba Silicone Co., Ltd., TSL8113) 5g and 0.5N hydrochloric acid 2.5g 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 applied on a photomask substrate by a spin coater,
A transparent primer layer (thickness: 0.2 μm) was formed by performing a drying treatment at 150 ° C. for 10 minutes. next,
30 g of isopropyl alcohol and trimethoxymethylsilane (GE Toshiba Silicone Co., Ltd., TSL8113)
3 g and ST-K03 which is a photocatalytic inorganic coating agent
20g (manufactured by Ishihara Sangyo Co., Ltd.) is mixed and the mixture is mixed at 100 ° C for 2
Stir for 0 minutes. This was diluted 3 times with isopropyl alcohol to obtain a photocatalyst-containing layer composition.

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

Next, a cationic polymer, polydiallyldimethylammonium chloride (PDDA, average molecular weight)
100,000-200,000, Aldrich), polystyrenesulfonic acid sodium salt (PSS, average molecular weight 70,000, Aldrich), which is an anionic polymer, were alternately adsorbed on a glass substrate to a thickness of about 2 nm to form a pattern formation substrate. .

The photocatalyst-containing layer side substrate and the decomposition and removal layer are aligned to face each other with a gap of 50 μm, and the photomask side is exposed to an ultrahigh pressure mercury lamp (wavelength 3).
(65 nm) for 120 seconds at an illuminance of 40 mW / cm ² to decompose and remove the decomposition-removing layer to form a decomposition-removing pattern made of the exposed glass substrate.

At this time, the contact angle between the unexposed portion and the decomposition and removal pattern and the silver colloid solution (concentration 20%) was measured using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) (micro As a result of dropping the droplet from the syringe for 30 seconds), the results were 62 ° and 6 °, respectively.

Next, a silver colloid solution (concentration: 20%) was attached to the above decomposition and removal pattern using an ink jet device, and this was subjected to treatment at 300 ° C. for 60 minutes and cured to obtain a conductive pattern forming body. It was

[0266]

According to the present invention, it is possible to deposit a metal colloid solution in a pattern on a characteristic change pattern having changed characteristics by, for example, dip coating or an inkjet method, and solidify the solution. If so, a highly precise conductive pattern can be formed. Therefore, since a highly precise conductive pattern can be formed with high precision by a simple process, a highly precise conductive pattern can be formed at low cost. In addition, for example, when the characteristic change layer is made of an insulating material, it is possible to form a highly accurate conductive pattern.

[Brief description of drawings]

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

FIG. 2 is a schematic cross-sectional view showing an example of a photocatalyst containing layer side substrate used in the present embodiment.

FIG. 3 is a schematic cross-sectional view showing another example of the photocatalyst containing layer side substrate used in the present embodiment.

FIG. 4 is a schematic cross-sectional view showing another example of the photocatalyst containing layer side substrate used in the present embodiment.

FIG. 5 is a schematic cross-sectional view showing another example of the photocatalyst-containing layer side substrate used in the present embodiment.

FIG. 6 is a process drawing showing an example of a non-image area removing process of the method for manufacturing a conductive pattern forming body of the present invention.

FIG. 7 is a schematic cross-sectional view showing an example of a conductive pattern forming body of the present invention.

FIG. 8 is a schematic cross-sectional view showing another example of the conductive pattern forming body of the present invention.

FIG. 9 is a schematic cross-sectional view showing another example of the conductive pattern forming body of 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 7 ... Non-drawing part 9… Characteristic change area 10 ... Characteristic unchanged area 12 ... Conductive pattern forming body 13 ... Light-shielding part on photocatalyst containing layer side 14 ... Primer layer

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA02 AA19 AB15 AB17 AC01                       AD01 BH03 CB33 FA12                 2H096 AA26 AA27 BA01 BA20 FA05                       FA10                 4E351 AA01 AA07 AA14 BB01 CC08                       CC10 CC27 DD05 DD06 DD51                       GG20                 5E343 AA02 AA12 AA22 AA37 BB23                       BB25 BB80 DD80 EE37 ER35                       GG08

Claims (42)

[Claims] 1. A photocatalyst-containing layer side substrate preparing step of preparing a photocatalyst-containing layer side substrate having a photocatalyst-containing layer containing a photocatalyst and a base material, and the surface characteristics are changed by the action of the photocatalyst in the photocatalyst containing layer. A pattern forming body substrate preparing step of preparing a substrate for a pattern forming body having a characteristic changing layer, and arranging the photocatalyst containing layer and the characteristic changing layer in contact with each other, and then irradiating energy from a predetermined direction. A characteristic change pattern forming step of forming a characteristic change pattern having changed characteristics on the characteristic change layer surface; and a pattern by applying a metal colloid solution to the surface of the pattern forming body substrate on which the characteristic change pattern is formed, Metal colloid solution coating step of depositing a metal colloid solution in a pattern, and gold deposited in a pattern on the characteristic change pattern. Method for producing a conductive pattern formed body characterized by having a conductive pattern formation step of the conductive pattern solidifying the colloidal solution. 2. A photocatalyst-containing layer side substrate having a photocatalyst-containing layer containing a photocatalyst and a base material, and a substrate for a pattern forming body having a property changing layer whose properties are changed by the action of the photocatalyst in the photocatalyst containing layer. After arranging the photocatalyst-containing layer and the characteristic change layer with a gap so as to have a thickness of 200 μm or less, by irradiating energy from a predetermined direction, a characteristic change pattern having changed characteristics is formed on the surface of the characteristic change layer. A characteristic change pattern forming step to form, the substrate surface for pattern forming body on which the characteristic change pattern is formed, by applying a metal colloid solution, a metal colloid solution applying step of attaching the metal colloid solution in a pattern, A conductive pattern for solidifying a metal colloid solution adhered to the characteristic change pattern in a pattern to form a conductive pattern. Method for producing a conductive pattern formed body characterized by having a down forming process. 3. A non-image area removing step of removing a non-image area, which is a portion of the characteristic change layer exposed on the surface of the pattern forming substrate, after the conductive pattern forming step. The method for producing a conductive pattern forming body according to claim 1, wherein the conductive pattern forming body is manufactured. 4. The method of manufacturing a conductive pattern forming body according to claim 3, wherein the non-image area removing step is a step of removing the characteristic change layer with an alkaline solution. 5. The photocatalyst containing layer side substrate comprises a base material and a photocatalyst containing layer formed in a pattern on the base material, according to any one of claims 1 to 4. The method for producing a conductive pattern forming body according to claim 10. 6. The photocatalyst containing layer side substrate prepared in the photocatalyst containing layer side substrate preparing step comprises a base material, a photocatalyst containing layer formed on the base material, and a photocatalyst containing layer formed in a pattern. The layer-side light-shielding portion, and the irradiation of energy in the characteristic change pattern forming step is performed from the photocatalyst-containing layer-side substrate, according to any one of claims 1 to 4. A method for manufacturing a conductive pattern forming body. 7. 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 a conductive pattern forming body according to claim 6. 8. 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 producing a conductive pattern forming body according to claim 6. 9. The method for producing a conductive pattern forming body according to claim 1, wherein the photocatalyst-containing layer is a layer made of a photocatalyst. 10. The method for producing a conductive pattern forming body according to claim 9, wherein the photocatalyst-containing layer is a layer formed by forming a photocatalyst on a base material by a vacuum film forming method. 11. The method for producing a conductive pattern forming body according to claim 1, wherein the photocatalyst-containing layer is a layer having a photocatalyst and a binder. . 12. 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 producing a conductive pattern forming body according to any one of claims 1 to 11. 13. The photocatalyst is titanium oxide (TiO ₂ ).
The method for manufacturing a conductive pattern forming body according to claim 12, wherein 14. The substrate for a pattern-formed body is prepared by forming the characteristic change layer on a substrate in the substrate-for-pattern-formed-body preparation step. The method for producing a conductive pattern forming body according to claim 1. 15. The characteristic changing layer is irradiated with energy by the action of the photocatalyst in the photocatalyst containing layer,
The wettability changing layer, which changes wettability so that a contact angle with a liquid is reduced.
4. The method for manufacturing a conductive pattern forming body according to claim 4. 16. The contact angle with respect to the metal colloid solution on the wettability changing layer is 50 ° or more in a portion not irradiated with energy and 40 ° or less in an irradiated portion. Item 16. A method for producing a conductive pattern forming body according to Item 15. 17. The wettability changing layer is a layer containing an organopolysiloxane.
5 or the method for producing a conductive pattern forming body according to claim 16. 18. The method for producing a conductive pattern forming body according to claim 17, wherein the organopolysiloxane is a polysiloxane containing a fluoroalkyl group. 19. The organopolysiloxane is Y _n
SiX _(4-n) (wherein Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group or a halogen, and n is an integer from 0 to 3. 19. The electroconductive material according to claim 17, which is an organopolysiloxane which is a hydrolytic condensate or a co-hydrolytic condensate of one or more silicon compounds represented by the formula (1). Of manufacturing a patterned product. 20. The conductive pattern formation according to claim 15, wherein the substrate for pattern formation body comprises a wettability changing layer having a self-supporting property. Body manufacturing method. 21. The decomposition-removing layer, which is decomposed and removed when being irradiated with energy by the action of the photocatalyst in the photocatalyst-containing layer, as the characteristic change layer. The method for producing a conductive pattern forming body according to claim 1. 22. The contact angle of the liquid with respect to the decomposition and removal layer and the contact angle of the liquid with respect to the substrate that is exposed by decomposition and removal of the decomposition and removal layer are different from each other. A method for manufacturing a conductive pattern forming body. 23. The conductive material according to claim 21, wherein the decomposition and removal layer is one of a self-assembled monolayer film, a Langmuir-Blodgett film, and an alternate adsorption film. A method for manufacturing a pattern forming body. 24. The contact angle of the decomposition removal layer with respect to the metal colloid solution is 50 ° or more, and the contact angle of the substrate with the metal colloid solution is 40 ° or less. The method for producing a conductive pattern forming body according to any one of claims 1 to 7. 25. When the surface of the characteristic changing layer is irradiated with energy, the distance between the photocatalyst containing layer and the surface of the characteristic changing layer is within a range of 0.2 μm to 10 μm. The method for manufacturing a conductive pattern forming body according to any one of claims 1 to 24. 26. The method of manufacturing a conductive pattern forming body according to claim 1, wherein the energy irradiation is performed while heating the photocatalyst-containing layer. 27. The method of manufacturing a conductive pattern forming body according to claim 1, wherein the characteristic change layer is a layer containing no photocatalyst. 28. The method for producing a conductive pattern forming body according to claim 1, wherein the metal colloid solution is a silver colloid aqueous solution or a gold colloid aqueous solution. . 29. The method according to any one of claims 1 to 28, wherein the coating of the metal colloid solution in the metal colloid solution coating step is a dip coating method or a spin coating method. A method for manufacturing a conductive pattern forming body. 30. The conductive pattern formation according to claim 1, wherein the coating of the metal colloid solution in the metal colloid solution coating step is a nozzle discharge method. Body manufacturing method. 31. The method of manufacturing a conductive pattern forming body according to claim 30, wherein the nozzle discharging method is an inkjet method. 32. A wettability changing layer whose wettability is changed by the action of a photocatalyst, and a metal composition formed by solidifying a metal colloid solution in a pattern on the wettability changing layer. And a conductive pattern forming body. 33. The conductive pattern forming body according to claim 32, wherein the wettability changing layer is formed on a substrate. 34. The contact angle with respect to the metal colloid solution on the wettability changing layer is 50 ° or more in a portion not irradiated with energy, and 40 ° or less in an irradiated portion. Item 32. The conductive pattern formed body according to Item 32 or Item 33. 35. The wettability changing layer is a layer containing an organopolysiloxane.
The conductive pattern forming body according to any one of claims 2 to 34. 36. The conductive pattern forming body according to claim 35, wherein the organopolysiloxane is a polysiloxane containing a fluoroalkyl group. 37. The organopolysiloxane is Y _n
SiX _(4-n) (wherein Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group or a halogen, and n is an integer from 0 to 3. 37. The electroconductivity according to claim 35 or 36, which is an organopolysiloxane which is a hydrolysis-condensation product or a co-hydrolysis-condensation product of one or more kinds of silicon compounds represented by the formula (1). Pattern forming body. 38. A substrate, a decomposition and removal layer decomposed and removed by the action of a photocatalyst on the substrate, and a pattern of metal colloidal solution is solidified on the substrate exposed by decomposition and removal of the decomposition and removal layer. And a formed metal composition. 39. The conductive material according to claim 38, wherein a contact angle of the liquid with respect to the decomposition / removal layer is different from a contact angle of the liquid with respect to the substrate exposed by decomposition of the decomposition / removal layer. Pattern forming body. 40. The conductive material according to claim 38 or 39, wherein the decomposition and removal layer is one of a self-assembled monolayer film, a Langmuir-Blodgett film, and an alternate adsorption film. Patterned body. 41. The contact angle of the decomposition and removal layer with respect to the metal colloid solution is 50 ° or more, and the contact angle of the substrate with the metal colloid solution is 40 ° or less. The conductive pattern forming body according to claim 1. 42. A substrate, a wettability changing layer formed in a pattern on the substrate and having a wettability changing by the action of a photocatalyst, and a metal colloid solidified on the wettability changing layer. An electrically conductive pattern forming body, comprising: