JP4770909B2 - Method for manufacturing conductive pattern forming body - Google Patents

Description

  The present invention relates to a method for producing a conductive pattern forming body that can be used for various high-definition electric circuits such as printed circuit boards.

  Conventionally, when manufacturing a high-definition conductive pattern forming body, for example, a printed circuit board, generally, a photoresist such as a dry film is laminated on a copper-clad laminate formed by plating the entire surface of the substrate with copper. Then, pattern exposure is performed using a photomask or the like, and development is performed.

  However, in the method using such a photolithography method, it is necessary to go through various steps such as metal plating on the substrate, formation of a photoresist layer, exposure, development, etc., and the manufacturing method is complicated and costly. In some cases, problems may occur. Further, a large amount of waste liquid generated during development is harmful, and there is also an environmental problem such as a need to perform processing in order to discharge it to the environment.

  Further, there is a method of manufacturing a printed circuit board by a method using screen printing, but there is a problem in accuracy, and it cannot be applied to manufacture of a high-definition conductive pattern.

  In view of the above, there is a demand for a method for producing a conductive pattern that can form a high-definition pattern, can be formed by a simple process, and has no problem of waste liquid treatment.

The present invention includes a photocatalyst-containing layer side substrate preparation step of preparing a photocatalyst-containing layer side substrate having a photocatalyst-containing layer and a base material,
A pattern forming body substrate preparation step of preparing a pattern forming body substrate having a characteristic change layer in which the surface characteristics change by the action of the photocatalyst in the photocatalyst containing layer;
A characteristic change pattern forming step of forming a characteristic change pattern having a changed characteristic on the surface of the characteristic change layer by irradiating energy from a predetermined direction after the photocatalyst-containing layer and the characteristic change layer are arranged in contact with each other When,
A metal colloid solution coating step in which a metal colloid solution is deposited in a pattern by applying a metal colloid solution to the surface of the substrate for a pattern forming body on which the characteristic change pattern is formed;
And a conductive pattern forming step in which the metal colloid solution adhering to the characteristic change pattern in a pattern is solidified to form a conductive pattern.

  According to the present invention, a colloidal metal solution can be deposited in a pattern on a characteristic change pattern whose characteristics have changed, for example, using dip coating or an inkjet method. It can be a conductive pattern. Therefore, since a high-definition conductive pattern can be formed with high accuracy by a simple process, a high-definition conductive pattern can be formed at low cost. Further, for example, when the characteristic change layer is an insulating material, it is possible to obtain a highly accurate conductive pattern.

The present invention also provides:
A photocatalyst-containing layer side substrate having a photocatalyst-containing layer and a substrate containing a photocatalyst, and a substrate for a pattern forming body having a characteristic change layer whose characteristics change due to the action of the photocatalyst in the photocatalyst-containing layer, And a characteristic change pattern in which a characteristic change pattern having a changed characteristic is formed on the surface of the characteristic change layer by irradiating energy from a predetermined direction after the gap is arranged such that the characteristic change layer is 200 μm or less. Forming process;
A metal colloid solution coating step in which a metal colloid solution is deposited in a pattern by applying a metal colloid solution to the surface of the substrate for a pattern forming body on which the characteristic change pattern is formed;
And a conductive pattern forming step in which the metal colloid solution adhering to the characteristic change pattern in a pattern is solidified to form a conductive pattern.

  According to the present invention, the photocatalyst-containing layer and the characteristic change layer are arranged at a predetermined interval and irradiated with energy, thereby efficiently changing the characteristic of the characteristic change layer in the portion irradiated with energy to form a pattern. In particular, a post-treatment after energy irradiation is not required, and a conductive pattern forming body having a high-definition pattern with changed characteristics can be manufactured. Further, for example, when the characteristic change layer is an insulating material, it is possible to obtain a highly accurate conductive pattern.

  In the present invention, after the conductive pattern forming step, there is a non-image portion removing step for removing the non-image portion which is a portion where the characteristic change layer is exposed on the surface of the pattern forming substrate. You may do it. As a result, when the characteristic change layer is formed of a conductive material, the characteristic change layer is removed and the insulating base is exposed, whereby a conductive pattern forming body can be obtained. Because.

  In the present invention, the non-image area removing step is preferably a step of removing the characteristic change layer with an alkaline solution. This is because the characteristic change layer can be easily removed, which is preferable in terms of manufacturing efficiency and cost.

  In this invention, it is preferable that the said photocatalyst content layer side board | substrate consists of a base material and the photocatalyst content layer formed in the pattern form on the said base material. Thus, by forming the photocatalyst-containing layer in a pattern, it is possible to form patterns having different characteristics on the characteristic change layer without using a photomask. In addition, since the characteristics change only in contact with or facing the photocatalyst containing layer, the energy to be irradiated is not particularly limited to parallel energy, and the energy irradiation direction is not particularly limited. This is because there is an advantage that the type of energy source and the degree of freedom in arrangement are greatly increased.

  Further, in the present invention, it comprises a base material, a photocatalyst-containing layer formed on the base material, and a photocatalyst-containing layer side light-shielding portion formed in a pattern, and energy irradiation in the characteristic pattern forming step is performed. The photocatalyst-containing layer side substrate is preferably used.

  By having the photocatalyst-containing layer side light-shielding portion on the photocatalyst-containing layer side substrate in this way, it is not necessary to use a photomask or the like when irradiating energy, so that alignment with the photomask is unnecessary and the process is simplified. This is because it becomes possible.

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

  It can be said that the photocatalyst-containing layer-side light-shielding portion is preferably disposed in contact with or close to the property change layer in terms of accuracy of the property change pattern obtained. 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 contacting or facing the photocatalyst-containing layer and the property change layer in the property change pattern forming step. Is.

  Moreover, in this invention, it is preferable that the said photocatalyst content layer is a layer which consists of a photocatalyst. This is because, if the photocatalyst-containing layer is a layer composed only of a photocatalyst, it is possible to improve the efficiency of changing the characteristics of the characteristic change layer, and it is possible to efficiently produce a pattern forming body.

  In the present invention, the photocatalyst-containing layer is preferably a layer formed by depositing a photocatalyst on a substrate by a vacuum film-forming method. By forming the photocatalyst-containing layer by vacuum film formation in this way, it is possible to obtain a homogeneous photocatalyst-containing layer having a uniform film thickness with less surface irregularities, and a characteristic change pattern on the surface of the characteristic change layer. This is because the formation can be performed uniformly and with high efficiency.

  On the other hand, in the present invention, the photocatalyst-treated layer may be a layer having a photocatalyst and a binder. By using the binder in this manner, it becomes possible to form the photocatalyst-containing layer relatively easily, and as a result, the pattern formed body can be manufactured at a low cost.

In the present invention, the photocatalyst is titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide (Bi ₂ O). ₃ ), and one or more substances selected from iron oxide (Fe ₂ O ₃ ), preferably the photocatalyst is titanium oxide (TiO ₂ ) as described in claim 13. Preferably there is. This is because titanium dioxide has a high band gap energy and is effective as a photocatalyst, and is chemically stable, non-toxic and easily available.

  In the present invention, it is preferable that the pattern forming body substrate is prepared by forming the characteristic change layer on the substrate in the pattern forming body substrate preparing step. This is because when the strength of the characteristic change layer is weak and does not have self-supporting properties, it is preferable that the characteristic change layer is formed on the substrate.

  In the present invention, the property change layer is a wettability change layer in which the wettability changes so that the contact angle with the liquid decreases when irradiated with energy by the action of the photocatalyst in the photocatalyst-containing layer. It is preferable. Since the property change layer is a wettability change layer, it is possible to make the region irradiated with energy a lyophilic region and the region not irradiated with energy a liquid repellent region, and use this difference in wettability. This is because the metal colloid solution can be attached only to the lyophilic region, and a conductive pattern can be easily formed.

  In the present invention, it is preferable that 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 a portion irradiated. If the wettability of the liquid-repellent region that is not irradiated with energy on the wettability changing layer and the lyophilic region that is irradiated is not within the above-described range, metal This is because when the colloidal solution is applied to the entire surface, the metal colloidal solution may not be attached only to the lyophilic region.

  In the present invention, the wettability changing layer is preferably a layer containing organopolysiloxane. In the present invention, the properties required for the wettability changing layer are liquid repellency when energy is not irradiated, and by the action of the photocatalyst in the photocatalyst-containing layer that is in contact or facing when energy is irradiated. It is a characteristic that it becomes lyophilic. This is because it is preferable to use organopolysiloxane as a material for imparting such characteristics to the wettability changing layer.

  In the present invention, the organopolysiloxane is preferably an organopolysiloxane containing a fluoroalkyl group. This is because if it contains a fluoroalkyl group, the difference in wettability between the energy irradiated portion and the unirradiated portion can be increased.

In the present invention, the organopolysiloxane is Y _n SiX _(4-n) (where Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group, or an epoxy group, and X represents an alkoxyl group. Or n represents an integer from 0 to 3. It is preferably an organopolysiloxane that is a hydrolytic condensate or a cohydrolytic condensate of one or more of the silicon compounds represented by . This is because by using such an organopolysiloxane, it is possible to exhibit the characteristics against the change in wettability as described above.

  In the present invention, the pattern forming body substrate may be composed of a wettability changing layer having self-supporting properties. If the wettability changing layer has a self-supporting property, it is not necessary to use a substrate or the like. For example, if a commercially available resin plate is used, a pattern-formed body can be produced at low cost.

  In the present invention, the characteristic change layer is preferably a decomposition / removal layer that is decomposed and removed when irradiated with energy by the action of the photocatalyst in the photocatalyst-containing layer. Since the characteristic change layer is a decomposition removal layer, it is possible to form irregularities on the surface by the energy irradiation, and thus the metal colloid solution can be easily attached by, for example, an ink jet method. Because it becomes.

  In the present invention, the contact angle of the liquid with respect to the decomposition / removal layer is preferably different from the contact angle of the liquid with respect to the substrate exposed by the decomposition / removal layer. As a result, it becomes possible to make the substrate exposed by the energy irradiation a lyophilic region and a portion where the decomposition / removal layer not irradiated with the energy remains a liquid repellent region, and easily attach the metal colloid solution. This is because it becomes possible.

  In the present invention, the decomposition removal layer is preferably a self-assembled monomolecular film, a Langmuir Blodgett film, or an alternately adsorbed film. This is because, when the decomposition / removal layer is the film described above, a defect-free film having a relatively high strength can be easily formed.

  In the present invention, the contact angle of the decomposition removal layer with respect to the metal colloid solution is preferably 50 ° or more, and the contact angle of the substrate with respect to the metal colloid solution is preferably 40 ° or less. The wettability between the liquid-repellent region, which is a portion made of the remaining decomposition-removed layer that is not irradiated with energy on the decomposition-removed layer, and the lyophilic region, which is a portion where the substrate is exposed by energy irradiation, is described above. This is because if the metal colloid solution is applied to the entire surface, the metal colloid solution may not be attached only to the lyophilic region.

  In the present invention, when irradiating the surface of the property change layer with energy, the distance between the photocatalyst-containing layer and the property change layer surface is preferably in the range of 0.2 μm to 10 μm. This is because the characteristics of the surface of the characteristic change layer can be changed more effectively by irradiating the energy at intervals within the above-described range when irradiating the energy.

  In the present invention, the energy irradiation is preferably performed while heating the photocatalyst-containing layer. This is because by heating the photocatalyst, the sensitivity of the photocatalyst is improved, and it is possible to efficiently change the characteristics on the characteristic change layer.

  In the present invention, the characteristic change layer is preferably a layer not containing a photocatalyst. In the present invention, since the characteristic change layer is a layer that does not contain a photocatalyst as described above, it is possible to avoid the problem that the characteristic change layer is affected over time.

  In the present invention, the metal colloid solution is preferably a silver colloid aqueous solution or a gold colloid aqueous solution.

  In the present invention, the application of the metal colloid solution in the metal colloid solution application step may be a dip coating method or a spin coating method.

In the present invention, the metal colloid solution may be applied in the metal colloid solution application step by a nozzle discharge method, and among them, an ink jet method is preferable as described in claim 31.
Further, in the present invention, it has a wettability changing layer whose wettability changes by the action of the photocatalyst, and a metal composition formed by solidifying a metal colloid solution in a pattern on the wettability changing layer. A conductive pattern forming body is provided. According to the present invention, by having the wettability changing layer, it becomes possible to easily form a metal composition, and when the wettability changing layer is insulative, excellent conductive pattern formation is achieved. It becomes possible to be a body.

  In the present invention, the wettability changing layer may be formed on a substrate. This is because when the strength of the wettability changing layer is weak and does not have self-supporting property, the characteristic changing layer is preferably formed on the substrate.

  In the present invention, it is preferable that 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 a portion irradiated. As a result, it becomes possible to make the portion irradiated with energy a lyophilic region and the portion not irradiated with energy to be a lyophobic region, so that it becomes possible to easily manufacture a conductive pattern forming body, This is because it is preferable in terms of manufacturing efficiency and cost.

  In the present invention, the wettability changing layer is preferably a layer containing an organopolysiloxane. In particular, as described in claim 36, the organopolysiloxane is a polysiloxane containing a fluoroalkyl group. Preferably there is. This is because such a wettability changing layer can obtain a significant change in wettability by energy irradiation.

In the present invention, the organopolysiloxane is Y _n SiX _(4-n) (where Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group, or an epoxy group, and X represents an alkoxyl group. Or n represents an integer from 0 to 3. It is preferably an organopolysiloxane that is a hydrolytic condensate or a cohydrolytic condensate of one or more of the silicon compounds represented by . This is because by forming a wettability changing layer using such an organopolysiloxane as a material, a conductive pattern forming body on which a wettability pattern having a large difference in wettability is formed can be obtained.

  The present invention also includes a substrate, a decomposition removal layer that is decomposed and removed on the substrate by the action of a photocatalyst, and a metal colloid solution that is solidified in a pattern on the substrate that is exposed after the decomposition removal layer is decomposed and removed. And a metal composition formed by the method described above.

  According to the present invention, by having the decomposition removal layer, it is possible to form a pattern having irregularities on the substrate, and it is possible to easily form a conductive pattern using the irregularities. Further, when the decomposition removal layer is insulative, an excellent conductive pattern forming body can be obtained.

  In the present invention, it is preferable that the contact angle of the liquid with respect to the decomposition / removal layer is different from the contact angle of the liquid with respect to the substrate exposed when the decomposition / removal layer is decomposed. As a result, not only the unevenness of the surface but also, for example, the substrate exposed by energy irradiation can be made lyophilic region, and the portion where the decomposition removal layer not irradiated with energy remains can be made lyophobic region. This is because a sex pattern can be formed.

  In the present invention, the decomposition / removal layer is preferably a self-assembled monomolecular film, a Langmuir Blodgett film, or an alternating adsorption film. This is because, when the decomposition removal layer is the film described above, a film having a relatively high strength and no defects can be easily formed.

  In the present invention, the contact angle of the decomposition removal layer with respect to the metal colloid solution is preferably 50 ° or more, and the contact angle of the substrate with respect to the metal colloid solution is preferably 40 ° or less. As a result, it is possible to make the portion where the substrate is exposed by energy irradiation become a lyophilic region and the portion where the decomposition removal layer not irradiated with energy remains as a lyophobic region. This is because the formed body can be manufactured, which is preferable in terms of manufacturing efficiency and cost.

  In addition, the present invention is formed by solidifying a base, a wettability changing layer formed in a pattern on the base and having wettability changed by the action of a photocatalyst, and the wettability changing layer. And a conductive pattern forming body characterized by comprising the above-described metal composition. By having the wettability changing layer on the substrate, it is possible to easily produce a conductive pattern formed body, and when the substrate is insulative, an excellent conductive pattern formed body is obtained. This is because it becomes possible.

  According to the present invention, a colloidal metal solution can be deposited in a pattern on a characteristic change pattern whose characteristics have changed, for example, using dip coating or an inkjet method. It can be a conductive pattern. Therefore, since a high-definition conductive pattern can be formed with high accuracy by a simple process, a high-definition conductive pattern can be formed at low cost. Further, for example, when the characteristic change layer is an insulating material, it is possible to obtain a highly accurate conductive pattern.

  The present invention relates to a method for producing a conductive pattern forming body and a conductive pattern forming body. Each will be described in detail below.

A. First, the manufacturing method of the conductive pattern formation body of this invention is demonstrated.
The method for producing a conductive pattern formed body of the present invention comprises:
A photocatalyst-containing layer side substrate preparation step of preparing a photocatalyst-containing layer side substrate having a photocatalyst-containing layer and a base material;
A pattern forming body substrate preparation step of preparing a pattern forming body substrate having a characteristic change layer in which the surface characteristics change by the action of the photocatalyst in the photocatalyst containing layer;
A characteristic change pattern forming step of forming a characteristic change pattern having a changed characteristic on the surface of the characteristic change layer by irradiating energy from a predetermined direction after the photocatalyst-containing layer and the characteristic change layer are arranged in contact with each other When,
A metal colloid solution coating step in which a metal colloid solution is deposited in a pattern by applying a metal colloid solution to the surface of the substrate for a pattern forming body on which the characteristic change pattern is formed;
A conductive pattern forming step of solidifying the colloidal metal solution adhering to the characteristic change pattern in a pattern to form a conductive pattern.

Moreover, the manufacturing method of the electroconductive pattern formation body of this invention,
A photocatalyst-containing layer side substrate having a photocatalyst-containing layer and a substrate containing a photocatalyst, and a substrate for a pattern forming body having a characteristic change layer whose characteristics change due to the action of the photocatalyst in the photocatalyst-containing layer, And a characteristic change pattern in which a characteristic change pattern having a changed characteristic is formed on the surface of the characteristic change layer by irradiating energy from a predetermined direction after the gap is arranged such that the characteristic change layer is 200 μm or less. Forming process;
A metal colloid solution coating step in which a metal colloid solution is deposited in a pattern by applying a metal colloid solution to the surface of the substrate for a pattern forming body on which the characteristic change pattern is formed;
And a conductive pattern forming step in which the metal colloid solution adhering to the characteristic change pattern in a pattern is solidified to form a conductive pattern.

  In the manufacturing method of the electroconductive pattern formation body of this invention, although it may have the said photocatalyst containing layer side board | substrate preparation process and the said substrate preparation process for pattern formation bodies, the photocatalyst content layer side board | substrate preparation process mentioned later If the same thing as the photocatalyst containing layer side board | substrate formed by (1) and the pattern formation body board | substrate formed at the pattern formation body board | substrate preparation process is used, it does not necessarily need to have the said process in particular.

  In the method for producing a conductive pattern forming body of the present invention, by arranging the photocatalyst-containing layer and the characteristic change layer at a predetermined position, by irradiating energy from a predetermined direction, by the action of the photocatalyst in the photocatalyst-containing layer, A characteristic change pattern in which the characteristic of the portion irradiated with energy is changed is formed. Since this pattern formation does not require post-processing such as development and washing after energy irradiation, patterns having different characteristics can be formed with fewer steps and at lower cost. Then, by applying a metal colloid solution to the characteristic change pattern on the characteristic change layer, the metal colloid solution can be attached in a pattern, and a conductive pattern can be easily formed by solidifying the metal colloid solution. be able to.

  Furthermore, in the present invention, the characteristics on the characteristic change layer are changed by the action of the photocatalyst in the photocatalyst containing layer, and then the photocatalyst containing layer side substrate is removed to make the pattern forming body side substrate a conductive pattern forming body. Therefore, the obtained electroconductive pattern forming body does not necessarily contain a photocatalyst. Therefore, it is possible to prevent a problem that the obtained conductive pattern formed body is affected by the action of the photocatalyst over time.

Such a method for producing a conductive pattern forming body of the present invention will be specifically described with reference to the drawings. FIG. 1 shows an example of a method for producing a conductive pattern forming body of the present invention.
In this example, first, a photocatalyst containing layer side substrate 3 in which a photocatalyst containing layer 2 is formed on a substrate 1 and a pattern forming body substrate 6 in which a characteristic change layer 5 is formed on a base 4 are provided. Prepare (see FIG. 1A, photocatalyst-containing layer side substrate preparation step and pattern formation substrate preparation step).
Next, as shown in FIG. 1 (b), after the photocatalyst containing layer side substrate 3 and the pattern forming body substrate 6 are arranged with the photocatalyst containing layer 2 and the characteristic change layer 5 in predetermined positions, A photomask 7 on which a required characteristic change pattern is drawn is used, and ultraviolet light 8 is irradiated through the photomask 7 from the photocatalyst containing layer side substrate 3 side. Thereby, as shown in FIG. 1C, a characteristic change pattern including the characteristic change region 9 and the characteristic non-change 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 completely adhered in FIG. 1, but in the present invention, in the case where they are physically contacted as described above, In addition, it may be arranged such that a gap that allows the photocatalyst in the photocatalyst containing layer 2 to act exists between the photocatalyst containing layer 2 and the characteristic change layer 5.
In the above example, the ultraviolet irradiation is performed through the photomask 7. However, as will be described later, the photocatalyst containing layer is formed in a pattern, or the photocatalyst containing layer side substrate has a light shielding portion (photocatalyst). In this case, energy irradiation is performed on the entire surface without using the photomask 7 or the like.
Then, the step of removing the photocatalyst-containing layer side substrate from the pattern forming body substrate 6 is performed (FIG. 1D), and the pattern forming body in which the characteristic change region 9 and the characteristic non-change region 10 are formed on the surface. The substrate 6 for use can be obtained.
Then, by applying a metal colloid solution on the pattern forming body substrate 6, the metal colloid solution is attached only on the characteristic change region (metal colloid solution coating step), and then cured to conduct the conductive property. The conductive pattern forming body 12 in which the conductive pattern 11 is formed on the characteristic change layer 5 can be obtained.

  Such a method for producing a 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 and a base material.
Thus, the photocatalyst containing layer side substrate manufactured in this step has at least a photocatalyst containing layer and a base material, and is usually a thin film photocatalyst containing layer formed on the base material by a predetermined method. Is formed. In addition, as the photocatalyst-containing layer side substrate, a substrate in which a photocatalyst-containing layer side light-shielding portion or primer layer formed in a pattern is formed can 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 change layer, and includes a photocatalyst and a binder. It may be a thing, and the thing formed into a film by the photocatalyst single-piece | unit may be used. The surface characteristics may be particularly lyophilic or lyophobic.

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

  By forming the photocatalyst-containing layer in a pattern in this manner, pattern irradiation using a photomask or the like is performed when the photocatalyst-containing layer is irradiated with energy as described in the characteristic change pattern forming step described later. By irradiating the entire surface, it is possible to form a characteristic change pattern including a characteristic change area and a characteristic unchanged area on the characteristic change layer.

  The patterning method of the photocatalyst processing layer is not particularly limited, but can be performed by, for example, a photolithography method.

  In addition, when energy irradiation is performed with the photocatalyst-containing layer and the characteristic change layer in close contact with each other, the characteristics of only the portion where the photocatalyst-containing layer is actually changed, so the energy irradiation direction is As long as the photocatalyst-containing layer and the property changing layer are irradiated or energy is irradiated to the facing portion, the photocatalyst-containing layer may be irradiated from any direction, and the irradiated energy is also particularly parallel light such as parallel light. It has the advantage that it is not limited to a thing.

  In such a photocatalyst-containing layer, the mechanism of action of a photocatalyst represented by titanium dioxide as described later is not necessarily clear, but a carrier generated by light irradiation reacts directly with a nearby compound, or It is considered that the active oxygen species generated in the presence of oxygen and water change the chemical structure of organic matter. In the present invention, this carrier is considered to act on the compound in the property change layer on the photocatalyst-containing layer.

Examples of the photocatalyst used in the present invention include titanium dioxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), which are known as photo semiconductors. Bismuth oxide (Bi ₂ O ₃ ) and iron oxide (Fe ₂ O ₃ ) can be mentioned, and one or a mixture of two or more selected from these can be used.

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

  Examples of such anatase type titanium dioxide include hydrochloric acid peptizer type anatase type titania sol (STS-02 manufactured by Ishihara Sangyo Co., Ltd. (average particle size 7 nm), ST-K01 manufactured by Ishihara Sangyo Co., Ltd.), nitric acid solution An anatase type titania sol (TA-15 manufactured by Nissan Chemical Co., Ltd. (average particle size 12 nm)) and the like can be mentioned.

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

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

  In the case of a photocatalyst-containing layer composed only of a photocatalyst, the efficiency with respect to the change in characteristics on the characteristic change layer is improved, which is advantageous in terms of cost such as shortening the processing time. On the other hand, in the case of a photocatalyst-containing layer comprising a photocatalyst and a binder, there is an advantage that the formation of the photocatalyst-containing layer is easy.

  Examples of a method for forming a photocatalyst-containing layer composed only of a photocatalyst include a method using a vacuum film forming method such as a sputtering method, a CVD method, or a vacuum deposition method. By forming the photocatalyst-containing layer by a vacuum film-forming method, it is possible to obtain a photocatalyst-containing layer that is a uniform film and contains only the photocatalyst, which can uniformly change the characteristics on the characteristic change layer. Since it is possible and consists only of a photocatalyst, it is possible to change the characteristics on the characteristic change layer more efficiently than in the case of using a binder.

  Examples of a method for forming a photocatalyst-containing layer consisting of only a photocatalyst include a method in which amorphous titania is formed on a substrate and then phase-changed to crystalline titania by firing when the photocatalyst is titanium dioxide. . As the amorphous titania used here, for example, hydrolysis, dehydration condensation, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetrabutoxytitanium, titanium inorganic salts such as titanium tetrachloride and titanium sulfate, An organic titanium compound such as tetramethoxytitanium can be obtained by hydrolysis and dehydration condensation in the presence of an acid. Next, it can be modified to anatase titania by baking at 400 ° C. to 500 ° C. and modified to rutile type titania by baking at 600 ° C. to 700 ° C.

  In the case of using a binder, it is preferable that the binder main skeleton has a high binding energy that is not decomposed by photoexcitation of the photocatalyst. For example, in the description of the wettability changing layer in the characteristic changing layer described later. Examples thereof include organopolysiloxanes described in detail.

  When organopolysiloxane is used as a binder in this way, the photocatalyst-containing layer is prepared by dispersing the photocatalyst and the binder organopolysiloxane in a solvent together with other additives as necessary. It can be formed by applying this coating solution on a substrate. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The coating can be performed by a known coating method such as spin coating, spray coating, dip coating, roll coating or bead coating. When an ultraviolet curable component is contained as the binder, the photocatalyst-containing layer can be formed by irradiating ultraviolet rays and performing a curing treatment.

An amorphous silica precursor can be used as the binder. This amorphous silica precursor is represented by the general formula SiX _4, X is a halogen, a methoxy group, an ethoxy group or a silicon compound an acetyl group or the like, and silanol or average molecular weight of 3,000 or less, their hydrolysates Polysiloxane is preferred.

  Specific examples include tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetrabutoxysilane, and tetramethoxysilane. In this case, the amorphous silica precursor and the photocatalyst particles are uniformly dispersed in a non-aqueous solvent, and hydrolyzed with moisture in the air on the substrate to form silanol, and then at room temperature. A photocatalyst-containing layer can be formed by dehydration-condensation polymerization. If dehydration condensation polymerization of silanol is carried out at 100 ° C. or higher, the degree of polymerization of silanol increases and the strength of the film surface can be improved. Moreover, these binders can be used individually or in mixture of 2 or more types.

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

  In addition to the photocatalyst and the binder, the photocatalyst containing layer can contain a surfactant. Specifically, hydrocarbons such as NIKKOL BL, BC, BO, BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Dainippon Megafac F-141, 144 manufactured by Ink Chemical Industry Co., Ltd., Footgent F-200, F251 manufactured by Neos Co., Ltd., Unidyne DS-401, 402 manufactured by Daikin Industries, Ltd., Fluorard FC-170 manufactured by 3M Co., Ltd. Fluorine-based or silicone-based nonionic surfactants such as 176, and cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.

  In addition to the above surfactants, the photocatalyst-containing layer includes polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate, Polyvinyl chloride, polyamide, polyimide, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, oligomers, polymers, etc. It can be included.

(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.

  Under the present circumstances, the material which comprises the base material used is suitably selected by the irradiation direction of the energy in the characteristic change pattern formation process mentioned later, whether the electroconductive pattern formation body obtained requires transparency, etc.

  That is, for example, when the conductive pattern forming body is an opaque substrate such as a paper base phenolic resin laminate, the energy irradiation direction is necessarily from the photocatalyst-containing layer side substrate side, as shown in FIG. As shown, it is necessary to arrange the photomask 7 on the photocatalyst containing layer side substrate 3 side and irradiate energy. As will be described later, the photocatalyst-containing layer side light-shielding portion is formed in a predetermined pattern on the photocatalyst-containing layer side substrate in advance, and the photocatalyst containing layer-side light-shielding portion is used to form the characteristic change pattern. It is necessary to irradiate energy from the containing layer side substrate side. In such a case, the base material needs to have transparency.

  On the other hand, when the conductive pattern forming body is, for example, a transparent resin film, it is possible to arrange a photomask on the pattern forming body substrate side and irradiate energy. As will be described later, when the pattern forming body-side light-shielding portion is formed in the pattern forming body substrate, it is necessary to irradiate energy from the pattern forming body substrate side. In such a case, the transparency of the substrate is not particularly required.

  The base material used in the present invention may be a flexible material such as a resin film, or may be a non-flexible material such as a glass substrate. This is appropriately selected according to the energy irradiation method in the characteristic change pattern forming step described later.

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

  Specific examples include glass, ceramic, metal, and plastic.

  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 an anchor layer include silane-based and titanium-based coupling agents.

(Photocatalyst containing layer side light shielding part)
As the photocatalyst containing layer side substrate used in the present invention, a substrate on which a photocatalyst containing layer side light shielding portion formed in a pattern is formed may be used. Thus, by using the photocatalyst containing layer side substrate having the photocatalyst containing layer side light-shielding portion, it is not necessary to use a photomask or perform drawing irradiation with laser light when irradiating energy. Therefore, since alignment between the photocatalyst-containing layer side substrate and the photomask is not necessary, it is possible to use a simple process, and an expensive apparatus necessary for drawing irradiation is also unnecessary, so that the cost is reduced. Has the advantage of being advantageous.

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

  For example, as shown in FIG. 3, a photocatalyst containing layer side light shielding portion 13 is formed on the base material 1, and a photocatalyst containing layer 2 is formed on the photocatalyst containing layer side light shielding portion 13, so that the photocatalyst containing layer side In this embodiment, the substrate 3 is used. For example, as shown in FIG. 4, the photocatalyst-containing layer side substrate 3 is formed by forming the photocatalyst-containing layer 2 on the base material 1 and forming the photocatalyst-containing layer side light-shielding portion 13 thereon. It is.

  In any of the embodiments, the photocatalyst-containing layer-side light-shielding portion is disposed in the vicinity of the contact portion or the facing portion between the photocatalyst-containing layer and the property change layer as compared with the case of using a photomask. Since the influence of energy scattering in the substrate or the like can be reduced, the energy pattern irradiation can be performed very accurately.

  Furthermore, 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. If the thickness of the photocatalyst containing layer side light-shielding part is made to coincide with the width of the gap, the photocatalyst containing layer side light shielding part is used to make the gap constant. It has the advantage that it can also be used as a spacer.

  That is, when the photocatalyst containing layer and the characteristic change layer are arranged in contact with or opposed to each other with a predetermined gap, the photocatalyst containing layer side light shielding portion and the characteristic change layer are arranged in close contact with each other. Thus, the predetermined gap can be made accurate, and by irradiating energy from the photocatalyst-containing layer side substrate in this state, a characteristic change pattern can be accurately formed on the characteristic change layer. It becomes.

The method for forming such a photocatalyst-containing layer side light-shielding part is not particularly limited, and is appropriately selected according to the characteristics of the formation surface of the photocatalyst-containing layer side light-shielding part, the shielding property against the required energy, and the like. 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 mm by a sputtering method, a vacuum deposition method, or the like, and patterning the thin film. As this patterning method, a normal patterning method such as sputtering can be used.

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

  In the above description, the two positions of the photocatalyst-containing layer side light-shielding portion are described between the base material and the photocatalyst-containing layer and on the surface of the photocatalyst-containing layer. It is also possible to adopt a mode in which the photocatalyst-containing layer side light-shielding portion is formed on the surface on which no is formed. In this aspect, for example, a case where the photomask is brought into close contact with the surface so as to be detachable can be considered, and it can be preferably used when the characteristic change pattern is changed 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, as described above, when the photocatalyst-containing layer side light-shielding portion is formed in a pattern on the substrate and the photocatalyst-containing layer is formed thereon to form a photocatalyst-containing layer side substrate, the photocatalyst-containing layer side substrate is formed. A primer layer may be formed between the layer side light shielding portion and the photocatalyst containing layer.

  The function and function of this primer layer are not always clear, but by forming a primer layer between the photocatalyst-containing layer side light-shielding part and the photocatalyst-containing layer, the primer layer is characterized by the characteristics of the layer that changes the characteristics of the photocatalyst. Impurities from the openings existing between the photocatalyst containing layer side light shielding part and the photocatalyst containing layer side light shielding part, which are factors that hinder the change, in particular, residues generated when patterning the photocatalyst containing layer side light shielding part, metal, metal It is considered that it has a function of preventing diffusion of impurities such as ions. Therefore, by forming the primer layer, the characteristic change process proceeds with high sensitivity, and as a result, a high-resolution pattern can be obtained.

In the present invention, the primer layer prevents impurities existing in not only the photocatalyst containing layer side light shielding part but also the opening formed between the photocatalyst containing layer side light shielding parts from affecting the action of the photocatalyst. The primer layer is preferably formed over the entire surface of the photocatalyst containing layer side light shielding portion including the opening.
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. The photocatalyst containing layer 2 is formed on the surface 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 is not in contact with the photocatalyst containing layer.

The material constituting the primer layer is not particularly limited, but an inorganic material that is not easily decomposed by the action of the photocatalyst is preferable. Specific examples include amorphous silica. When such amorphous silica is used, the precursor of the amorphous silica is represented by the general formula SiX ₄ and 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 thickness of the primer layer is preferably in the range of 0.001 μm to 1 μm, particularly preferably in the range of 0.001 μm to 0.1 μm.

(2) Pattern Forming Body Substrate Preparation Step Next, in the present invention, a pattern forming body for preparing a pattern forming body substrate having a characteristic change layer whose surface characteristics are changed by the action of the photocatalyst in the photocatalyst-containing layer. A substrate preparation step is performed. The substrate for a 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 change due to the action of the photocatalyst in the photocatalyst-containing layer. May have only a characteristic change layer, and if the characteristic change layer does not have self-supporting property, the characteristic change layer may be formed on a substrate. Moreover, you may have a light-shielding part etc. in the board | substrate for pattern formation bodies. Hereinafter, each structure of this pattern formation body substrate formation process is demonstrated.

(Characteristic change layer)
First, the characteristic change layer used for the substrate for pattern formation in this invention is demonstrated. The characteristic change layer used in the substrate for a pattern forming body of the present invention is not particularly limited as long as it is a characteristic change layer whose surface characteristics change due to the action of the photocatalyst in the above-described photocatalyst-containing layer. 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 and a pattern due to the wettability is formed, and the characteristic change layer is decomposed and removed by the action of the photocatalyst. The two cases of the decomposition and removal layer to be formed are preferable because the effectiveness of the present invention is further extracted from the relationship of the characteristic change pattern obtained. Hereinafter, the wettability changing layer and the decomposition removal layer will be described.

a. Wetting change layer The wettability changing 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 in general, by the action of the photocatalyst accompanying irradiation of energy, The wettability changing layer is preferably a layer whose wettability changes so that the contact angle with the liquid is reduced.

  Thus, by using a wettability changing layer in which the wettability changes so that the contact angle with the liquid is reduced by energy irradiation, as described above, for example, when using a photomask, or when the photocatalyst-containing layer side shields light. When the part is used, and when the photocatalyst-containing layer is formed in a pattern, etc., the wettability is easily changed into a pattern by irradiating energy, and the lyophilic region having a small contact angle with the liquid This pattern can be formed. Therefore, the conductive pattern formed body can be efficiently manufactured, which is advantageous in terms of cost.

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

  The wettability changing layer preferably has a contact angle with respect to the metal colloid solution of 50 ° or more, preferably 60 ° or more, particularly 70 ° or more in a portion not irradiated with energy, that is, a liquid repellent region. This is because the portion that is not irradiated with energy is a portion that requires liquid repellency in the present invention, so when the contact angle with the liquid is small, the liquid repellency is not sufficient, and the metal colloid described later This is because when the metal colloid solution is applied to the entire surface in the solution coating step, the metal colloid solution may remain in a region where the conductive pattern is not formed.

  In the wettability changing layer, the contact angle with the colloidal metal solution is 40 ° or less, preferably 30 ° or less, and particularly preferably 20 ° or less in the energy-irradiated portion, that is, the lyophilic region. If the contact angle with the colloidal metal solution in the energy-irradiated part, that is, the lyophilic region is high, the metal colloid solution may be repelled in the lyophilic region when the metal colloid solution described later is applied. This is because it may be difficult to pattern the metal colloid solution on the lyophilic region.

  In addition, the contact angle with the liquid here is measured using a contact angle measuring instrument (Kyowa Interface Science Co., Ltd. CA-Z type) with a liquid having various surface tensions (from the microsyringe to the liquid. 30 seconds after dropping), and the result was obtained or the result was graphed. In this measurement, as a liquid having various surface tensions, a wetting index standard solution manufactured by Pure Chemical Co., Ltd. was used.

  Further, 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 more energy than the wettability changing layer. The wettability changing layer may be formed so as to be lower than that before energy irradiation by the action of the photocatalyst.

  In the wettability changing layer having such characteristics, a pattern composed of a portion having a small fluorine content can be easily formed by pattern irradiation with energy. Here, fluorine has an extremely low surface energy. Therefore, 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 having a small fluorine content is larger than the critical surface tension of the surface of the portion having a large fluorine content. This means that the portion with a low fluorine content is a lyophilic region compared to the portion with a high fluorine content. Therefore, forming a pattern composed of a portion having a lower fluorine content than the surrounding surface forms a pattern of a lyophilic region in the liquid repellent 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 attaching a metal colloid solution only to a low-cost and high-definition conductive pattern.

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

  By setting it within such a range, it is possible to make a great difference in wettability between the energy irradiated portion and the unirradiated portion. Therefore, by forming a conductive pattern on such a wettability changing layer, it is possible to accurately form a conductive pattern only in a lyophilic region having a reduced fluorine content, and the conductive pattern can be formed with high accuracy. This is because the body can be obtained. This rate of decrease is based on weight.

  The fluorine content in such a wettability changing layer can be measured by various commonly used methods such as X-ray Photoelectron Spectroscopy, ESCA (Electron Spectroscopy for Chemical Analysis)), and any method capable of quantitatively measuring the amount of fluorine on the surface, such as X-ray fluorescence analysis and mass spectrometry.

  The material used for such a wettability changing layer is a material whose wettability changing layer has the above-described characteristics, that is, a material whose wettability is changed by a photocatalyst in a photocatalyst-containing layer that contacts or faces by energy irradiation, and the action of the photocatalyst The main chain is not particularly limited as long as it has a main chain that is difficult to deteriorate and decompose, and specific examples include organopolysiloxane. In the present invention, the organopolysiloxane is preferably an organopolysiloxane containing a fluoroalkyl group.

  Examples of such an organopolysiloxane include (1) an organopolysiloxane that exerts great strength by hydrolyzing and polycondensing chloro or alkoxysilane by sol-gel reaction or the like, and (2) water repellency and oil repellency. Mention may be made of organopolysiloxanes such as organopolysiloxanes crosslinked with excellent reactive silicones.

In the case of (1) above, the general formula:
Y _n SiX _(4-n)
(Here, 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 a halogen. N is an integer from 0 to 3. )
It is preferable that it is the organopolysiloxane which is a 1 type, or 2 or more types of hydrolysis condensate or cohydrolysis condensate of the silicon compound shown by these. Here, the number of carbon atoms of the group represented by Y is preferably in 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.

In particular, an organopolysiloxane containing a fluoroalkyl group can be preferably used, and specific examples thereof include one or two or more hydrolytic condensates and cohydrolytic condensates of the following fluoroalkylsilanes. In general, those 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 (OCH ₃ ) ₃ ;
_{(CF 3) 2 CF (CF} 2) 6 CH 2 CH 2 Si (OCH 3) 3;
_{(CF 3) 2 CF (CF} 2) 8 CH 2 CH 2 Si (OCH 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 (OCH 3) 2;
_{CF 3 (CF 2) 5 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 7 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 9 CH} 2 CH 2 SiCH 3 (OCH 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 (OCH 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 CH 3) 3;
_{CF 3 (CF 2) 5 CH} 2 CH 2 Si (OCH 2 CH 3) 3;
_{CF 3 (CF 2) 7 CH} 2 CH 2 Si (OCH 2 CH 3) 3;
_{CF 3 (CF 2) 9 CH} 2 CH 2 Si (OCH 2 CH 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 a polysiloxane containing a fluoroalkyl group as described above as a binder, the liquid repellency of the non-irradiated part of the wettability changing layer is greatly improved. The adhesion of the solution can be prevented, and the metal colloid solution can be adhered only to the lyophilic region that is the energy irradiation part.
Examples of the reactive silicone (2) include compounds having a skeleton represented by the following general formula.

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

  Moreover, you may mix the stable organosilicone compound which does not carry out a crosslinking reaction like dimethylpolysiloxane with said organopolysiloxane.

  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 possible to include fluorine in the wettability changing layer. It is effective for pattern formation. Therefore, it can be said that it is preferable that fluorine be contained in a material that is not easily deteriorated or decomposed by the action of the photocatalyst, specifically, that the organopolysiloxane material contains fluorine to form a wettability changing layer.

  As described above, as a method for containing fluorine in the organopolysiloxane material, a method in which a fluorine compound is bonded with a relatively weak bond energy to a main agent that usually has a high bond energy, or a fluorine bonded with a relatively weak bond energy. Examples include a method of mixing a compound into the wettability changing layer. By introducing fluorine by such a method, when energy is irradiated, a fluorine bonding site having a relatively low binding energy is first decomposed, and thus fluorine can be removed from the wettability changing layer. It is.

  Examples of the first method, that is, a method of bonding a fluorine compound with a relatively weak binding energy to a binder having a high binding energy include a method of introducing a fluoroalkyl group as a substituent into the organopolysiloxane. be able to.

For example, as described in (1) above, as a method for obtaining an organopolysiloxane, an organopolysiloxane exhibiting high strength can be obtained by hydrolyzing and polycondensing chloro or alkoxysilane or the like by a sol-gel reaction or the like. . Here, in this method, as described above, the above general formula:
Y _n SiX _(4-n)
(Here, 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 a halogen. N is an integer from 0 to 3. )
An organopolysiloxane is obtained by hydrolyzing or co-hydrolyzing and condensing one or two or more of the silicon compounds represented by formula (1). In this general formula, silicon having a fluoroalkyl group as the substituent Y is obtained. By synthesizing using a 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 caused by the action of the photocatalyst in the photocatalyst-containing layer that is in contact or facing when irradiated with energy. Since the portion is decomposed, the fluorine content in the portion irradiated with energy on the wettability changing layer surface can be reduced.

  The silicon compound having a fluoroalkyl group used at this time is not particularly limited as long as it has a fluoroalkyl group, but has at least one fluoroalkyl group, and the carbon number of the fluoroalkyl group A silicon compound in which is 4 to 30, preferably 6 to 20, particularly preferably 6 to 16, is preferably used. Specific examples of such a silicon compound are as described above, and among these, 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 may be used in combination with the above-mentioned silicon compound having no fluoroalkyl group, and these cohydrolyzed condensates may be used as the organopolysiloxane. In addition, one or two or more silicon compounds having such a fluoroalkyl group may be used, and these hydrolyzed condensates and cohydrolyzed condensates 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 the fluoroalkyl group is 0.01 mol% or more, preferably 0.1%. It is preferable that it is contained in mol% or more.

  By including the fluoroalkyl group to such a degree, the liquid repellency on the wettability changing layer can be increased, and the difference in wettability with the portion that has been made lyophilic by irradiation with energy can be increased. Because it can.

In the method shown in (2) above, organopolysiloxane is obtained by crosslinking reactive silicone having excellent liquid repellency. In this case as well, R ¹ and R in the above general formula are similarly used. ² or ² can be substituted with a fluorine-containing substituent such as a fluoroalkyl group, so that the wettability changing layer can contain fluorine, and when energy is irradiated, a siloxane bond Since the portion of the fluoroalkyl group having a lower binding energy is decomposed, the fluorine content on the wettability changing layer surface can be reduced by energy irradiation.

  On the other hand, as a method for introducing a fluorine compound bonded with energy lower than the binding energy of the binder, for example, when introducing a low molecular weight fluorine compound, for example, a fluorine-based surfactant is mixed. Examples of the method of introducing a high molecular weight fluorine compound include a method of mixing a fluorine resin having high compatibility with the binder resin.

  The wettability changing layer in the present invention may further contain a surfactant. Specifically, hydrocarbons such as NIKKOL BL, BC, BO, BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Dainippon Megafac F-141, 144 manufactured by Ink Chemical Industry Co., Ltd., Footgent F-200, F251 manufactured by Neos Co., Ltd., Unidyne DS-401, 402 manufactured by Daikin Industries, Ltd., Fluorard FC-170 manufactured by 3M Co., Ltd. Fluorine-based or silicone-based nonionic surfactants such as 176, and cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.

  In addition to the above surfactants, the wettability changing layer includes polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate. , Polyvinyl chloride, polyamide, polyimide, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, oligomers, polymers, etc. Can be contained.

  Such a wettability changing layer can be formed by preparing a coating solution by dispersing the above-described components in a solvent together with other additives as necessary, and coating the coating solution on a substrate. . As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The application can be performed by a known application method such as spin coating, spray coating, dip coating, roll coating, or bead coating. In the case where an ultraviolet curable component is contained, the wettability changing layer can be formed by performing a curing treatment by irradiating ultraviolet rays.

  Further, the wettability changing layer used in the present invention may be a self-supporting material as long as it is formed of a material whose surface wettability can be changed by the action of a photocatalyst. The material which does not have property may be sufficient. In addition, having self-supporting property as used in the field of this invention means that it can exist in a tangible state without another support material.

  When the wettability changing layer is a material having a self-supporting property, for example, a commercially available resin film made of a material that can become the wettability changing layer can be used, which can be said to be advantageous in terms of cost. As such a material, if the above-mentioned material formed into a film has a self-supporting property, it can be used. 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, a wettability changing layer having no self-supporting property is preferable. The wettability changing layer formed of a material whose characteristics change greatly as described above usually has few self-supporting materials. By forming it on a substrate, the strength and the like increase, and it is used as various pattern forming bodies. Because it becomes possible.

  In addition, the wettability changing layer used in the present invention is not particularly limited as long as the wettability changing layer is changed by the action of the photocatalyst as described above. preferable. If the photocatalyst is not included in the wettability changing layer in this way, there is no need to worry about the effect of the photocatalyst over time when used as a functional element, and it can be used without problems for a long time. That's why.

  In the present invention, the thickness of the wettability changing layer is preferably 0.001 μm to 1 μm, particularly preferably in the range of 0.01 to 0.1 μm, from the relationship of the wettability change rate by the photocatalyst. is there.

  By using the wettability changing layer of the component described above in the present invention, by the action of the photocatalyst in the photocatalyst-containing layer that is in contact with or facing, the action of oxidation, decomposition, etc. of the organic group that is a part of the component It is possible to change the wettability of the energy irradiated portion to make it lyophilic and to make a large difference in wettability with the non-energy irradiated portion. Therefore, even when a metal colloid solution to be described later is applied over the entire surface, it is possible to attach the metal colloid solution only within the lyophilic region, which is the energy irradiation part, to form a high-definition conductive pattern. The body can be manufactured at low cost.

b. Decomposition and removal layer Next, the decomposition and removal layer will be described. The decomposition / removal layer used in the present invention is particularly limited as long as 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, the decomposed / removed layer is decomposed and removed by the action of the photocatalyst, so that the pattern composed of the part with and without the decomposed / removed layer without performing the development process or the washing process, that is, the unevenness is formed. The pattern which has can be formed.

  This decomposition / removal layer is oxidatively decomposed and vaporized by the action of the photocatalyst by energy irradiation, and is therefore removed without any special post-treatment such as development / washing process. Depending on the material, a cleaning process or the like may be performed.

  In addition, the decomposition / removal layer used in the present invention not only forms irregularities, but the decomposition / removal layer preferably has a higher contact angle with the liquid as compared to a 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, thereby forming various patterns. This is because it becomes possible.

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

  Moreover, the decomposition removal layer has a contact angle with respect to the metal colloid solution of 50 ° or more, preferably 60 ° or more, particularly preferably 70 ° or more. This is because, in the present invention, the remaining decomposition and removal layer is a part where liquid repellency is required, so when the contact angle with the liquid is small, the liquid repellency is not sufficient, and the metal colloid solution described later This is because when the metal colloid solution is applied to the entire surface in the coating process, the metal colloid solution may remain in a region where the conductive pattern is not formed.

  In the present invention, the contact angle of the substrate described later with respect to the metal colloid solution is 40 ° or less, preferably 30 ° or less, and particularly preferably 20 ° or less. In the present invention, since the substrate is a part that requires lyophilicity, there is a possibility of repelling the metal colloidal solution even in the lyophilic region when the metal colloid solution described later is applied. This is because it may be difficult to pattern the metal colloid solution on the region. Here, the contact angle with the liquid is a value measured by the method described above.

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

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

  In the present invention, since a functional thin film, that is, a self-assembled monomolecular film, a Langmuir-Brocket film, and an alternating adsorption film can be used, it is possible to form a film without defects. It can be said that it is more preferable to use such a film forming method.

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

(I) Self-assembled monolayer The inventors do not know the existence of an official definition of a self-assembled monolayer, but explanation of what is generally recognized as a self-assembled monolayer As a sentence, for example, a review by Abraham Ulman “Formation and Structure of Self-Assembled Monolayers”, Chemical Review, 96, 1533-1554 (1996) is excellent. Referring to this review article, a self-assembled monolayer can be said to be a monolayer formed as a result of adsorbing and binding (self-organizing) appropriate molecules to the appropriate substrate surface. Examples of materials capable of forming a self-assembled film include surfactant molecules such as fatty acids, organosilicon molecules such as alkyltrichlorosilanes and alkylalkoxides, organic sulfur molecules such as alkanethiols, and alkyl phosphates. And organic phosphoric acid molecules. The common commonality of the molecular structure is that there is a functional group that has a relatively long alkyl chain and that interacts with the substrate surface at one molecular end. The portion of the alkyl chain is a source of intermolecular force when molecules are packed two-dimensionally. However, the example shown here has the simplest structure, having a functional group such as an amino group or a carboxyl group at the other end of the molecule, an alkylene chain part having an oxyethylene chain, or a fluorocarbon chain. Self-assembled monolayers composed of various molecules such as those of complex type chains have been reported. There is also a composite type self-assembled monolayer composed of a plurality of molecular species. In addition, recently, a polymer having a plurality of functional groups (which may have one functional group) or a linear polymer (which may have a branched structure) as represented by dendrimers has been developed. One formed on the surface of the substrate (the latter is collectively referred to as a polymer brush) may be considered as a self-assembled monolayer. In the present invention, these are also included in the self-assembled monolayer.

(Ii) Langmuir-Blodgett Film If the Langmuir-Blodgett film used in the present invention is formed on a substrate, the major difference from the self-assembled monomolecular film described above is Absent. It can be said that the Langmuir-Blodgett film is characterized by its formation method and the advanced two-dimensional molecular packing properties (high orientation and high order). That is, in general, Langmuir-Blodgett film-forming molecules are first developed on the gas-liquid interface, and the developed film is condensed by the trough to change into a highly packed condensed film. In practice, this is transferred to a suitable substrate for use. It is possible to form a monomolecular film to a multilayer film of an arbitrary molecular layer by the method outlined here. Further, not only low molecules but also polymers and colloidal particles can be used as the film material. Recent examples of the application of various materials are described in detail in the review by Tokuharu Miyashita et al. “Prospects for Nanotechnology for the Creation of Soft Nanodevices” Polymer Vol. 50, September, 644-647 (2001).

(Iii) Alternating adsorptive film Alternating adsorptive film (Layer-by-Layer Self-Assembled Film) is generally a material that has at least two functional groups having positive or negative charges on the substrate sequentially. It is a film formed by adsorbing and bonding and laminating. Since a material having a large number of functional groups has many advantages such as increased strength and durability of the membrane, recently, an ionic polymer (polymer electrolyte) is often used as a material. Further, particles having surface charges such as proteins, metals and oxides, so-called “colloid particles” are also frequently used as film-forming substances. More recently, membranes that actively utilize weaker interactions than ionic bonds such as hydrogen bonds, coordination bonds, and hydrophobic interactions have been reported. A relatively recent example of alternating adsorption films is slightly biased toward materials with electrostatic interaction as the driving force, but a review by Paula T. Hammond “Recent Explorations in Electrostatic Multilayer Thin Film Assembly” Current Opinion in Colloid & Interface Science, 4, 430-442 (2000). The alternate adsorption film can be described by taking the simplest process as an example, by repeating the adsorption-washing of a material having a positive (negative) charge-adsorption-washing of a material having a negative (positive) charge a predetermined number of times. It is a film to be formed. As with Langmuir-Blodgett membranes, no development-condensation-transfer operations are required. Further, as apparent from the difference in these production methods, the alternate adsorption film generally does not have a two-dimensional high orientation / high order like the Langmuir-Blodgett film. However, the alternate adsorption film and its manufacturing method have advantages over conventional film formation methods, such as the ability to easily form a dense film without defects and the ability to form even fine irregular surfaces, tube inner surfaces, and spherical surfaces. Have many.

  In addition, the thickness of the decomposition removal layer is not particularly limited as long as it is a thickness that can be decomposed and removed by the energy irradiated 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 removal layer, and the like, but is generally within the range of 0.001 μm to 1 μm, particularly 0.01 μm to 0.001. It is preferable to be within the range of 1 μm.

(Substrate)
Next, the substrate will be described. In the present invention, for example, the substrate is used when the above-described property changing layer is not self-supporting or when it is a decomposition removal layer. As an example, as shown in FIG. A change layer 5 is provided.

  Such a substrate is appropriately selected according to the use of the finally obtained conductive pattern forming body, and is generally used in the case of a normal printed wiring board, for example. A material, specifically, a resin laminate of a paper base, a resin laminate of a glass cloth / glass nonwoven base, ceramic, metal, or the like can be used. Moreover, in a flexible wiring board, it is also possible to use the resin-made film which has flexibility as a base | substrate.

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

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

  Further, when the characteristic change layer is formed on the substrate, it is preferable to form a pattern-forming substrate-side light-shielding portion on the surface of the substrate in a pattern, and to form the characteristic change layer thereon. If the substrate has self-supporting property and is not formed on the substrate, it is preferable that the pattern-forming substrate-side light-shielding portion is formed on the surface of the property-changing layer where the property-changing pattern is not formed.

  Since the method for forming such a light shielding part is the same as that of the above-described photocatalyst containing layer side light shielding part, description thereof is omitted here.

(3) Characteristic change pattern forming step In the present invention, after the photocatalyst-containing layer and the characteristic change layer are arranged at predetermined positions, the surface of the characteristic change layer is irradiated by irradiating energy from a predetermined direction. A characteristic change pattern forming step for forming a pattern is performed. Hereinafter, each configuration of the characteristic change pattern forming step will be described.

(Arrangement of photocatalyst containing layer and characteristic changing layer)
In this step, first, it is necessary to arrange the photocatalyst-containing layer and the characteristic change layer in contact with each other during energy irradiation or to be arranged at a predetermined interval so that the photocatalyst functions.

  Here, the contact in the present invention refers to a state where the action of the photocatalyst substantially extends to the surface of the property change layer, and in addition to a state in which the photocatalyst is actually in physical contact, a predetermined The concept also includes a state in which the photocatalyst-containing layer and the characteristic change layer are arranged with an interval of. This gap is preferably 200 μm or less.

  In the present invention, the gap has a very good pattern accuracy, a high photocatalyst sensitivity, and therefore a good property change efficiency of the property change layer, particularly in the range of 0.2 μm to 10 μm, preferably It is preferable to be within a range of 1 μm to 5 μm. Such a range of the gap is particularly effective for a conductive pattern forming body having a small area in which the gap can be controlled with high accuracy.

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

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

  Thus, by disposing the photocatalyst-containing layer and the property change layer surface at a predetermined interval, oxygen, water, and active oxygen species generated by the photocatalytic action are easily desorbed. That is, when the interval between the photocatalyst containing layer and the characteristic change layer is narrower than the above range, it is difficult to desorb the active oxygen species, and as a result, there is a possibility that the characteristic change rate may be slowed. Absent. In addition, it is not preferable that the active oxygen species generated are difficult to reach the characteristic change layer, and in this case as well, the speed of the characteristic change may be reduced.

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

  An example of a method for uniformly forming such an extremely narrow gap and arranging the photocatalyst-containing layer and the characteristic change layer is a method using a spacer. By using the spacer in this way, a uniform gap can be formed, and the portion in contact with the spacer is not affected by the photocatalyst action on the surface of the property change layer. By having a pattern similar to the pattern, a predetermined characteristic change pattern can be formed on the characteristic change layer.

  In the present invention, such a spacer may be formed as a single member, but for simplification of the process, etc., as described in the column of the photocatalyst-containing layer side substrate preparation step, the photocatalyst-containing layer side substrate It is preferable to form on the surface of the photocatalyst containing layer. In the description of the photocatalyst-containing layer side substrate preparation step, the photocatalyst-containing layer side light-shielding portion has been described. However, in the present invention, such a spacer has a surface that prevents the photocatalyst from acting on the surface of the property change layer. In particular, it may be formed of a material that does not have a function of shielding the irradiated energy.

(Energy irradiation to the contact or opposite part)
Next, in a state where the contact or facing state as described above is maintained, energy irradiation is performed on the contact or facing portion. The energy irradiation (exposure) in the present invention is a concept including irradiation of any energy ray capable of changing the characteristics of the surface of the characteristic change layer by the photocatalyst-containing layer, and is limited to irradiation with visible light. It is not something.

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

  Examples of light sources that can be used for such energy irradiation include mercury lamps, metal halide lamps, xenon lamps, excimer lamps, and various other light sources.

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

  Further, the energy irradiation amount at the time of energy irradiation is an irradiation amount necessary for the characteristic change layer surface to change the characteristics of the characteristic change layer surface by the action of the photocatalyst in the photocatalyst containing layer.

  At this time, it is preferable in that the sensitivity can be increased by irradiating the photocatalyst-containing layer with energy while heating and the characteristic can be changed efficiently. Specifically, it is preferable to heat within a range of 30 ° C to 80 ° C.

  The energy irradiation direction in the present invention is a method for forming a characteristic change pattern such as whether or not a photocatalyst-containing layer-side light-shielding portion or a pattern-forming substrate-side light-shielding portion is formed, a photocatalyst-containing layer-side substrate or a pattern-forming member It is determined by whether or not the substrate is transparent.

  That is, when the photocatalyst containing layer side light shielding portion is formed, it is necessary to irradiate energy from the photocatalyst containing layer side substrate side, and in this case, the photocatalyst containing layer side substrate is transparent to the energy irradiated. Need to be. In this case, when the photocatalyst-containing layer side light-shielding part is formed on the photocatalyst-containing layer and this photocatalyst-containing layer side light-shielding part is used so as to function as a spacer as described above, the energy irradiation direction May be from the photocatalyst containing layer side substrate side or from the pattern forming body 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. In this case, the pattern forming body substrate is irradiated with energy. It must be transparent to it. In this case as well, when the pattern forming body substrate-side light-shielding portion is formed on the characteristic change layer, and this pattern-forming body substrate-side light shielding portion is used so as to have the function as the spacer as described above, The energy irradiation direction may be from the photocatalyst containing layer side substrate side or from the pattern forming body substrate side.

  In addition, the energy irradiation direction when the photocatalyst-containing layer is formed in a pattern is any direction as long as energy is irradiated to the portion where the photocatalyst-containing layer and the property change layer are in contact with or opposed to each other as described above. May be irradiated.

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

  In the case of using a photomask, energy is irradiated from the side where the photomask is arranged. In this case, the substrate on which the photomask is arranged, that is, either the photocatalyst containing layer side substrate or the pattern forming body substrate needs to be transparent.

(Removal of photocatalyst containing layer side substrate)
When the energy irradiation as described above is completed, the photocatalyst containing layer side substrate is moved away from the position where it is in contact with or spaced from the characteristic change layer, and as a result, as shown in FIG. And a characteristic change pattern including the characteristic unchanged region 10 is formed on the characteristic change layer 5.

(4) Metal colloid solution coating step In the present invention, the metal colloid solution is then applied to the surface of the substrate for the pattern forming body on which the characteristic change pattern is formed, thereby attaching the metal colloid solution in a pattern. A metal colloid solution coating process is performed.

  The method for applying the metal colloid solution is not particularly limited as long as it is a method that can be applied to the surface of the property change layer, and specifically, the entire surface of the property change layer such as a dip coating method or a spin coating method. The method of apply | coating may be sufficient and the method of apply | coating the said metal colloid solution to the target pattern shape like the nozzle discharge method may be sufficient. Of the nozzle ejection methods, the inkjet method is preferred.

  The viscosity of the metal colloid solution used in the present invention is preferably in the range of 1 to 100 cps, preferably 5 to 50 cps, particularly 10 to 20 cps, and its concentration is 1 to 70 wt%, preferably 10 to 50 wt%. %, Particularly preferably in the range of 20-30 wt%. When the viscosity and concentration are lower than the above ranges, although depending on the application, the film thickness of the obtained metal pattern is too thin, so that it may be difficult to put to practical use, which is not preferable. On the other hand, when the viscosity and concentration are higher than the above ranges, it is not preferable because patterning may not be possible when such a metal colloid solution is applied over the entire surface.

  Furthermore, the surface tension in the metal colloid solution is preferably 20 mN / m or more, preferably 50 mN / m or more, particularly preferably 70 mN / m or more. When the surface tension is lower than the above range, for example, it may be impossible to increase the contact angle in the liquid repellent region, and as a result, the metal colloid solution may remain in the liquid repellent region. Absent. In addition, although it does not specifically limit regarding the upper limit of the surface tension of this metal colloid solution, it can be said that it is preferable that it is 80 mN / m or less.

  Thus, the metal colloid solution used in the present invention is preferably a solution having a large surface tension. This is because the metal colloid solution applied to the lyophobic region other than the lyophilic region needs to be removed or collected in the lyophilic region when applied to the entire surface as described above. This is because a larger contact angle of the metal colloid solution in the liquid repellent region is preferable. From such a viewpoint, in the present invention, it is preferable to use an aqueous metal colloid solution using water as a medium.

  Moreover, as a kind of metal used for the metal colloid solution used in this invention, it is preferable that they are silver or gold | metal | money. This is because it has 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 formation step In the present invention, finally, a conductive pattern formation step is performed in which the metal colloid solution adhering to the pattern is solidified to form a conductive pattern. The substrate is made into a conductive pattern forming body.

  As the solidification method used here, heating is the most common, and heating is performed within a range of 100 ° C to 700 ° C, preferably within a range of 250 ° C to 500 ° C. The heating time is 10 minutes to 60 minutes. Within the range, preferably within the range of 20 to 40 minutes.

(6) Non-image part removal process In the manufacturing method of the conductive pattern formation body of this invention, in addition to the said process, characteristic change layers other than the conductive pattern formation part formed at the conductive pattern formation process mentioned above There may be a non-image area removing step for removing the image. When the characteristic change layer described above is conductive, it is difficult to obtain a conductive pattern formed body even if it has a conductive pattern on the pattern formed body. By removing the characteristic change layer in this region, the substrate is exposed to form a conductive pattern forming body. At this time, the substrate needs to be an insulating material, as described above.

  The non-image area removing step of the present invention includes, for example, a characteristic change layer exposed on the surface other than the conductive pattern 11 region of the pattern forming substrate (FIG. 6A) formed by the conductive pattern forming step. The method is not particularly limited as long as the non-image portion 7 can be removed, as long as it is possible to remove the non-image portion 7 (FIG. 6B).

  Specific methods for removing the non-image area include a method of applying an alkaline solution or a strong acid such as hydrofluoric acid or concentrated sulfuric acid by spraying, a method of immersing, and the like.

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

  Furthermore, in the present invention, an insulating protective layer may be further formed after the conductive pattern is formed. This is because it is possible to prevent problems such as peeling off of the conductive pattern. Further, when this insulating protective layer is a characteristic change layer, it can be used as a multilayer printed wiring board by further forming a conductive pattern thereon.

B. Next, the pattern forming body of the present invention will be described. The pattern forming body of the present invention has three embodiments. Hereinafter, each pattern formation body is demonstrated.

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 forming body of the present invention is a metal formed by solidifying a wettability changing layer whose wettability is changed by the action of a photocatalyst, and a pattern of the metal colloid solution on the wettability changing layer. It is characterized by having a composition. The pattern formed body of this embodiment can form the lyophilic region and the lyophobic region in a pattern by energy irradiation easily by having the wettability changing layer. By attaching the metal colloid solution to the region, it becomes possible to easily manufacture the conductive pattern forming body.

In this embodiment, since the conductive pattern is formed on the wettability changing layer, the electrical resistance of the wettability changing layer is 1 × 10 ⁸ Ω · cm to 1 × 10 ¹⁸ Ω · cm, Especially, it is preferable to be in the range of 1 × 10 ¹² Ω · cm to 1 × 10 ¹⁸ Ω · cm. As a result, an excellent pattern forming body can be obtained.

  If the pattern forming body of this embodiment has the wettability changing layer and the metal composition formed in a pattern on the wettability changing layer, the structure and the like are particularly limited. Instead, for example, as shown in FIG. 7A, a wettability changing layer 5 which is one of the characteristic changing layers is formed on the substrate 4, and the metal composition 11 is patterned on the wettability changing layer 5. For example, as shown in FIG. 7B, when the wettability changing layer 5 has a self-supporting property, the metal composition 11 is formed in a pattern on the wettability changing layer 5. It may be formed.

  Since the wettability changing layer and the substrate used in this embodiment can be those described in the “pattern forming body substrate preparation step” in the “A. Pattern forming body manufacturing method” described above, The description here is omitted. In addition, the metal composition used in this embodiment is obtained by solidifying a metal colloid solution in a pattern, and the “metal colloid solution coating step” and “conductivity” in the above-mentioned “A. Method for producing a pattern forming body”. Since it is the same as that of the material and manufacturing method which were demonstrated by the characteristic pattern formation process ", description here is abbreviate | omitted.

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 includes a substrate, a decomposition removal layer that is decomposed and removed on the substrate by the action of a photocatalyst, and a pattern on the substrate that is exposed after the decomposition removal layer is decomposed and removed. And a metal composition formed by solidifying a metal colloid solution.

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

  Since the conductive pattern forming body of this embodiment has the above-described decomposition and removal layer, it is possible to easily form irregularities in a pattern on the surface by performing energy irradiation. This makes it possible to manufacture a pattern forming body. Moreover, 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 in the decomposition removal layer of this embodiment. This is because it is possible to manufacture a conductive pattern forming body using not only the surface irregularities but also the difference in wettability.

In this case, since the conductive pattern is formed on the substrate, the substrate has an electric resistance of 1 × 10 ⁸ Ω · cm to 1 × 10 ¹⁸ Ω · cm, and in particular 1 × 10 ¹² Ω · cm to 1 ×. It is preferably within the range of 10 ¹⁸ Ω · cm.
Furthermore, since there is a decomposition removal layer around the conductive pattern, the electric resistance of the decomposition removal layer is 1 × 10 ⁸ Ω · cm to 1 × 10 ¹⁸ Ω · cm, especially 1 × 10 ¹² Ω · cm. It is preferable to be within a range of ˜1 × 10 ¹⁸ Ω · cm. This is because an excellent pattern forming body can be obtained.

  As the decomposition removal layer and the substrate used in the present embodiment, those described in “Pattern forming body substrate preparation step” in “A. Pattern forming body manufacturing method” described above can be used. The description in is omitted. In addition, the metal composition used in this embodiment is obtained by solidifying a metal colloid solution in a pattern, and the “metal colloid solution coating step” and “conductivity” in the above-mentioned “A. Method for producing a pattern forming body”. Since it is the same as that of the material and manufacturing method which were demonstrated by the characteristic pattern formation process ", description here is abbreviate | omitted.

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 includes a substrate, a wettability changing layer whose wettability is changed by the action of a photocatalyst formed on the substrate, and a wettability changing layer on the wettability changing layer. And a metal composition formed by solidifying a metal colloid.

  The structure or the like of the conductive pattern formed body of the present invention is not particularly limited. For example, as illustrated in FIG. 9, the base 4 and the wettability changing layer which is a characteristic changing layer in a pattern on the base 4. 5 is formed, and the metal composition 11 is formed on the wettability changing layer 5.

Since the conductive pattern formed body of this embodiment has the wettability changing layer, the conductive pattern formed body can be easily manufactured using the difference in wettability. Further, 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 for the conductive pattern. Yes. Thereby, even when the wettability changing layer is conductive, a conductive pattern forming body can be obtained. In this case, the electric resistance of the substrate is preferably in the range of 1 × 10 ⁸ Ω · cm to 1 × 10 ¹⁸ Ω · cm, particularly 1 × 10 ¹² Ω · cm to 1 × 10 ¹⁸ Ω · cm. This is because an excellent conductive pattern formed body can be obtained.

  As the decomposition removal layer and the substrate used in the present embodiment, those described in “Pattern forming body substrate preparation step” in “A. Pattern forming body manufacturing method” described above can be used. The description in is omitted. In addition, the metal composition used in this embodiment is obtained by solidifying a metal colloid solution in a pattern, and the “metal colloid solution coating step” and “conductivity” in the above-mentioned “A. Method for producing a pattern forming body”. Since it is the same as that of the material and manufacturing method which were demonstrated by the characteristic pattern formation process ", description here is abbreviate | omitted.

  In addition, this embodiment is not limited to the said embodiment. The above embodiment is an exemplification, and any structure that has substantially the same configuration as the technical idea described in the claims of the present embodiment and has the same effect can be used. It is included in the technical scope of this embodiment.

  Hereinafter, this embodiment will be described in more detail through examples.

[Example 1]
On a quartz glass substrate on which a 0.4 μm thick chromium black matrix with a 50 μm line and space is formed, a titanium oxide coating agent TKC301 for photocatalyst manufactured by Teika Co., Ltd. is coated and dried at 350 ° C. for 3 hours. A photocatalyst-containing layer side substrate was prepared.

  Next, a solution obtained by adding 3 g of 0.1N hydrochloric acid water to 0.4 g of MF-160E (trade name, manufactured by Tochem Products Co., Ltd.), the main component of which is fluoroalkylsilane, and stirring for 1 hour at room temperature is placed on a glass substrate. The substrate was coated and dried at 150 ° C. for 10 minutes to prepare a pattern forming substrate.

The photocatalyst-containing layer side substrate was brought into close contact with this, and exposed from the photocatalyst-containing layer side substrate with an ultra-high pressure mercury lamp (365 nm, 1000 mJ / cm ² ) to form a lyophilic region on the surface of the pattern forming substrate.

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

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

[Example 2]
On a quartz glass substrate on which a 0.4 μm thick chromium black matrix with a 50 μm line and space is formed, a titanium oxide coating agent TKC301 for photocatalyst manufactured by Teika Co., Ltd. is coated and dried at 350 ° C. for 3 hours. A photocatalyst-containing layer side substrate was prepared.

  Next, a solution obtained by adding 3 g of 0.1N hydrochloric acid water to 0.4 g of MF-160E (trade name, manufactured by Tochem Products Co., Ltd.), the main component of which is fluoroalkylsilane, and stirring for 1 hour at room temperature is placed on a glass substrate. The substrate was coated and dried at 150 ° C. for 10 minutes to prepare a pattern forming substrate.

The photocatalyst-containing layer side substrate was brought into close contact with this, and exposed from the photocatalyst-containing layer side substrate with an ultrahigh pressure mercury lamp (365 nm 600 mJ / cm ² ) to form a lyophilic region on the surface of the pattern forming substrate.

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

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

[Example 3]
In the same manner as in Example 1, a photocatalyst-containing layer side substrate and a pattern forming body substrate were prepared, and the pattern forming body was exposed in the same manner to form a lyophilic region on the surface of the pattern forming body.

  The contact angle with respect to the silver colloid aqueous solution (concentration 50 wt%) in the unexposed area, that is, the lyophobic area was 83 °, and the contact angle in the exposed area, that is, the lyophilic area was 12 °.

  By immersing the substrate in an aqueous silver colloid solution (concentration 50 wt%) and pulling it up at 10 mm / sec, the aqueous silver colloid solution adhered in a pattern only on the lyophilic region. By heating this silver colloid aqueous solution pattern at 300 ° C. for 20 minutes, a conductive pattern formed body in which silver was patterned on the substrate was obtained.

[Comparative Example 1]
On a quartz glass substrate on which a 0.4 μm thick chromium black matrix with a 50 μm line and space is formed, a titanium oxide coating agent TKC301 for photocatalyst manufactured by Teika Co., Ltd. is coated and dried at 350 ° C. for 3 hours. A photocatalyst-containing layer side substrate was prepared.

  Next, a solution obtained by adding 3 g of 0.1N hydrochloric acid water to 0.4 g of MF-160E (trade name, manufactured by Tochem Products Co., Ltd.), the main component of which is fluoroalkylsilane, and stirring for 1 hour at room temperature is placed on a glass substrate. The substrate was coated and dried at 150 ° C. for 10 minutes to prepare a pattern forming substrate.

The photocatalyst-containing layer side substrate was brought into close contact with this, and exposed from the photocatalyst-containing layer side substrate with an ultrahigh pressure mercury lamp (365 nm, 300 mJ / cm ² ) to form a lyophilic region on the surface of the pattern forming substrate.

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

  The above substrate was immersed in a silver colloid aqueous solution (concentration 20 wt%) and pulled up at 10 mm / sec., But the silver colloid aqueous solution was repelled on the entire surface including the lyophilic region, and a conductive pattern formed body could be obtained. There wasn't.

[Comparative Example 2]
On a quartz glass substrate on which a 0.4 μm thick chromium black matrix with a 50 μm line and space is formed, a titanium oxide coating agent TKC301 for photocatalyst manufactured by Teika Co., Ltd. is coated and dried at 350 ° C. for 3 hours. A photocatalyst-containing layer side substrate was prepared.

Next, 3 g of trimethoxymethylsilane (trade name TSL8113, manufactured by Toshiba Silicone Co., Ltd.) and 3 g of 0.1N hydrochloric acid water are mixed with 30 g of isopropyl alcohol and stirred at 100 ° C. for 20 minutes to coat the solution on a glass substrate. The substrate for pattern formation was prepared by drying at 150 ° C. for 10 minutes and having a wettability changing layer not containing fluorine.
The photocatalyst-containing layer side substrate was brought into close contact with this, and exposed from the photocatalyst-containing layer side substrate with an ultrahigh pressure mercury lamp (365 nm 600 mJ / cm ² ) to form a lyophilic region on the surface of the pattern forming substrate.

The contact angle with the silver colloid aqueous solution (concentration 20 wt%) in the liquid repellent region was 44 °, and the contact angle in the lyophilic region was 10 °.
The above substrate was immersed in an aqueous silver colloid solution (concentration 20 wt%) and pulled up at 10 mm / sec., But the entire surface including the liquid-repellent region was coated with the aqueous silver colloid solution to obtain a conductive pattern formed body. I could not.

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

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

Next, 2 g of Iupilon Z400 (manufactured by Mitsubishi Gas Chemical), whose main component is polycarbonate, was dissolved in 30 g of dichloromethane and 70 g of 1,1,2-trichloroethane to obtain a composition for a decomposition layer removal layer. The composition for decomposition / removal layer is applied onto a glass substrate by a spin coater and dried at 100 ° C. for 60 minutes to form a transparent decomposition / removal layer (thickness: 0.01 μm). A substrate was obtained.
The photocatalyst-containing layer side substrate and the decomposition removal layer are aligned, face each other with a gap of 100 μm, and exposed from the photomask side with an ultrahigh pressure mercury lamp (wavelength 365 nm) at an illuminance of 40 mW / cm ² for 600 seconds. Then, the decomposition / removal layer was decomposed and removed, and a decomposition / removal pattern composed of the exposed glass substrate was formed in a pattern.

  At this time, the contact angle between the unexposed part 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.). As a result of dropping 30 seconds later, the result was 65 ° and 6 °, respectively.

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

  Finally, the substrate on which the conductive pattern is formed is dipped in an alkaline aqueous solution mainly composed of potassium hydroxide of PH13 for 2 minutes, and then rinsed with water for 5 minutes to remove the non-image area, and the conductive pattern. A formed body was obtained.

[Example 5]
5 g of trimethoxymethylsilane (manufactured by GE Toshiba Silicone Co., Ltd., TSL8113) and 2.5 g of 0.5 N hydrochloric acid were mixed and stirred for 8 hours. This was diluted 10 times with isopropyl alcohol to obtain a primer layer composition. The primer layer composition was applied onto a photomask substrate by a spin coater and dried at 150 ° C. for 10 minutes to form a transparent primer layer (thickness 0.2 μm). Next, 30 g of isopropyl alcohol, 3 g of trimethoxymethylsilane (manufactured by GE Toshiba Silicone Co., Ltd., TSL8113) and 20 g of ST-K03 (manufactured by Ishihara Sangyo Co., Ltd.), which is a photocatalytic inorganic coating agent, are mixed at 100 ° C. Stir for 20 minutes. This was diluted 3 times with isopropyl alcohol to obtain a composition for a photocatalyst-containing layer.

  A transparent photocatalyst-containing layer (thickness: 0.15 μm) is obtained by applying the composition for a photocatalyst-containing layer onto a photomask substrate on which a primer layer has been formed using a spin coater and performing a drying treatment at 150 ° C. for 10 minutes. Formed.

  Next, polydiallyldimethylammonium chloride (PDDA, average molecular weight 100,000-200,000, Aldrich), a cationic polymer, polystyrene sulfonate sodium salt (PSS, average molecular weight 70,000, Aldrich), an anionic polymer, is used as a glass substrate. A pattern forming substrate was formed by alternately adsorbing on the substrate to a thickness of about 2 nm.

The photocatalyst-containing layer side substrate and the decomposition removal layer are aligned and face each other with a gap of 50 μm, and exposed from the photomask side with an ultrahigh pressure mercury lamp (wavelength 365 nm) at an illuminance of 40 mW / cm ² for 120 seconds. Then, the decomposition / removal pattern composed of the glass substrate exposed by decomposing and removing the decomposition / removal layer was formed in a pattern.
At this time, the contact angle between the unexposed part 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.). As a result of dropping a droplet 30 seconds later, they were 62 ° and 6 °, respectively.

  Next, using an ink jet apparatus, a silver colloid solution (concentration 20%) was attached to the decomposition removal pattern, and this was treated by curing at 300 ° C. for 60 minutes to obtain a conductive pattern forming body.

It is process drawing which shows an example of the manufacturing method of the electroconductive pattern formation body of this invention. It is a schematic sectional drawing which shows an example of the photocatalyst containing layer side board | substrate used for this embodiment. It is a schematic sectional drawing which shows the other example of the photocatalyst containing layer side board | substrate used for this embodiment. It is a schematic sectional drawing which shows the other example of the photocatalyst containing layer side board | substrate used for this embodiment. It is a schematic sectional drawing which shows the other example of the photocatalyst containing layer side board | substrate used for this embodiment. It is process drawing which shows an example of the non-image part removal process of the manufacturing method of the conductive pattern formation body of this invention. It is a schematic sectional drawing which shows an example of the electroconductive pattern formation body of this invention. It is a schematic sectional drawing which shows the other example of the electroconductive pattern formation body of this invention. It is a schematic sectional drawing which shows the other example of the electroconductive pattern formation body of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Photocatalyst containing layer 3 ... Photocatalyst containing layer side board | substrate 4 ... Base | substrate 5 ... Characteristic change layer 6 ... Pattern forming body substrate 7 ... Non-image area 9 ... Characteristic change area 10 ... Characteristic unchanged area 12 ... Conductive pattern forming body 13 ... Photocatalyst containing layer side light shielding part 14 ... Primer layer

Claims (27)

A photocatalyst containing layer side substrate preparation step of preparing a photocatalyst containing layer side substrate comprising a base material and a photocatalyst containing layer formed in a pattern on the base material;
A pattern forming body substrate preparation step of preparing a pattern forming body substrate having a characteristic change layer in which the surface characteristics change by the action of the photocatalyst in the photocatalyst containing layer;
A characteristic change pattern forming step of forming a characteristic change pattern having a changed characteristic on the surface of the characteristic change layer by irradiating energy from a predetermined direction after the photocatalyst-containing layer and the characteristic change layer are arranged to contact each other When,
A metal colloid solution coating step of depositing the metal colloid solution in a pattern by applying the metal colloid solution to the surface of the substrate for the pattern forming body on which the characteristic change pattern is formed;
A method for producing a conductive pattern forming body comprising a conductive pattern forming step of solidifying a metal colloid solution adhering to the characteristic change pattern in a pattern to form a conductive pattern,
The photocatalyst containing layer side substrate prepared in the photocatalyst containing layer side substrate preparing step includes a base material, a photocatalyst containing layer formed on the base material, and a photocatalyst containing layer side light shielding portion formed in a pattern. Consists of
The irradiation of energy in the characteristic change pattern forming step is performed from the photocatalyst containing layer side substrate,
In the photocatalyst containing layer side substrate, the photocatalyst containing layer side light shielding portion is formed in a pattern on the substrate, and the photocatalyst containing layer is further formed thereon. Manufacturing method. A pattern forming body having a photocatalyst containing layer side substrate comprising a base material, a photocatalyst containing layer formed in a pattern on the base material, and a property changing layer whose properties are changed by the action of the photocatalyst in the photocatalyst containing layer The substrate is disposed with a gap so that the photocatalyst-containing layer and the property change layer are 200 μm or less, and then the energy is irradiated from a predetermined direction, whereby the property changes on the surface of the property change layer. A characteristic change pattern forming step for forming a characteristic change pattern;
A metal colloid solution coating step of depositing the metal colloid solution in a pattern by applying the metal colloid solution to the surface of the substrate for the pattern forming body on which the characteristic change pattern is formed;
A method for producing a conductive pattern forming body comprising a conductive pattern forming step of solidifying a metal colloid solution adhering to the characteristic change pattern in a pattern to form a conductive pattern,
The photocatalyst containing layer side substrate used in the characteristic change pattern forming step is composed of a base material, a photocatalyst containing layer formed on the base material, and a photocatalyst containing layer side light shielding portion formed in a pattern,
The irradiation of energy in the characteristic change pattern forming step is performed from the photocatalyst containing layer side substrate,
In the photocatalyst containing layer side substrate, the photocatalyst containing layer side light shielding portion is formed in a pattern on the substrate, and the photocatalyst containing layer is further formed thereon. Manufacturing method. After the conductive pattern forming step,
The non-image area removing step of removing the non-image area, which is a portion of the characteristic change layer exposed on the surface of the pattern forming substrate, according to claim 1 or 2. A method for producing a conductive pattern forming body. The said non-image part removal process is a process of removing the said characteristic change layer with an alkaline solution, The manufacturing method of the conductive pattern formation body of Claim 3 characterized by the above-mentioned. The said photocatalyst content layer is a layer which consists of photocatalysts, The manufacturing method of the electroconductive pattern formation body in any one of Claim 1 to 4 characterized by the above-mentioned. The method for producing a conductive pattern forming body according to claim 5, wherein the photocatalyst-containing layer is a layer formed by depositing a photocatalyst on a substrate by a vacuum film-forming method. The said photocatalyst containing layer is a layer which has a photocatalyst and a binder, The manufacturing method of the electroconductive pattern formation body in any one of Claim 1- Claim 4 characterized by the above-mentioned. The photocatalyst is composed of titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide (Bi ₂ O ₃ ), and oxide. The production of the conductive pattern forming body according to any one of claims 1 to 7, wherein the material is one or more substances selected from iron (Fe ₂ O ₃ ). Method. The method for producing a conductive pattern forming body according to claim 8, wherein the photocatalyst is titanium oxide (TiO ₂ ). 2. The conductive pattern forming body according to claim 1, wherein in the pattern forming body substrate preparing step, the pattern forming body substrate is prepared by forming the characteristic change layer on a substrate. Method. The characteristic change layer is a wettability change layer whose wettability changes so that a contact angle with a liquid is lowered when irradiated with energy by the action of a photocatalyst in the photocatalyst-containing layer. The manufacturing method of the electroconductive pattern formation body as described in any one of Claim 1-10. 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 a portion irradiated. A method for producing a conductive pattern forming body. The method for producing a conductive pattern forming body according to claim 11, wherein the wettability changing layer is a layer containing an organopolysiloxane. The method for producing a conductive pattern forming body according to claim 13, wherein the organopolysiloxane is a polysiloxane containing a fluoroalkyl group. The organopolysiloxane is Y _n SiX _(4-n) (where Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, and X represents an alkoxyl group or a halogen. 14. n is an integer from 0 to 3.) It is an organopolysiloxane which is one or more of the hydrolytic condensates or cohydrolytic condensates of the silicon compound represented by (13). Or the manufacturing method of the electroconductive pattern formation body of Claim 14. The method for producing a conductive pattern forming body according to any one of claims 11 to 15, wherein the substrate for the pattern forming body includes a wettability changing layer having self-supporting property. The claim according to any one of claims 1 to 10, wherein the characteristic change layer is a decomposition removal layer that is decomposed and removed when irradiated with energy by the action of a photocatalyst in the photocatalyst-containing layer. The manufacturing method of the electroconductive pattern formation body of description. 18. The conductive pattern forming body according to claim 17, 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 the decomposition / removal layer. Manufacturing method. The production of the conductive pattern forming body according to claim 17 or 18, wherein the decomposition / removal layer is a self-assembled monolayer, a Langmuir Blodgett film, or an alternating adsorption film. Method. 20. The contact angle of the decomposition removal layer with respect to the metal colloid solution is 50 [deg.] Or more, and the contact angle of the substrate with respect to the metal colloid solution is 40 [deg.] Or less. The manufacturing method of the electroconductive pattern formation body of Claim. The distance between the photocatalyst containing layer and the surface of the property change layer is set in a range of 0.2 μm to 10 μm when energy is applied to the surface of the property change layer. The method for producing a conductive pattern forming body according to any one of claims 20 to 20. The method for producing a conductive pattern forming body according to any one of claims 1 to 21, wherein the energy irradiation is performed while heating the photocatalyst-containing layer. The method for producing a conductive pattern forming body according to any one of claims 1 to 22, wherein the characteristic change layer is a layer not containing a photocatalyst. The method for producing a conductive pattern forming body according to any one of claims 1 to 23, wherein the metal colloid solution is a silver colloid aqueous solution or a gold colloid aqueous solution. The conductive pattern forming body according to any one of claims 1 to 24, wherein the application of the metal colloid solution in the metal colloid solution application step is a dip coating method or a spin coating method. Manufacturing method. The method for producing a conductive pattern forming body according to any one of claims 1 to 24, wherein the application of the metal colloid solution in the metal colloid solution application step is a nozzle discharge method. The method for producing a conductive pattern forming body according to claim 26, wherein the nozzle discharge method is an ink jet method.

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