JP4459829B2 - Pattern forming body and manufacturing method thereof - Google Patents

Description

  The present invention relates to a pattern forming body having a pattern with different wettability on the surface, which can be used for fine patterning applications such as a color filter, a microlens, an organic EL light emitting layer, an electrode pattern, and a biochip, and a method for producing the same. is there.

  Conventionally, as a method of forming a high-definition pattern, pattern exposure is performed on a photoresist layer coated on a substrate, and after exposure, the photoresist is developed and further etched, or the photoresist has functionality. There is known a method of manufacturing a pattern forming body by photolithography, such as directly forming a target pattern by exposing a photoresist using a substance.

  The formation of high-definition patterns by photolithography is used for the formation of colored patterns for color filters used in liquid crystal display devices, the formation of microlenses, the manufacture of fine electrical circuit boards, the manufacture of chromium masks used for pattern exposure, etc. However, depending on these methods, it is necessary to use a photoresist and develop with a liquid developer after exposure or to perform etching. In addition, when a functional substance is used as a photoresist, there is a problem that it deteriorates due to an alkali solution or the like used during development.

  In addition, a high-definition pattern such as a color filter is also formed by printing or the like, but the pattern formed by printing has problems such as positional accuracy, and it is difficult to form a high-precision pattern. there were. In addition, the prior art regarding this invention has not been discovered.

  Therefore, it is desired to provide a pattern forming body that can form a high-definition pattern and can be efficiently manufactured, and a manufacturing method thereof.

  In the present invention, plasma is irradiated to a resin base material using a fluorine compound as an introduction gas, and fluorine is introduced, and energy is applied in a pattern to the base material into which fluorine has been introduced by the plasma irradiation step. And providing a wettability change pattern forming step of forming a wettability change pattern having a reduced contact angle with a liquid on the substrate.

  According to the present invention, fluorine can be easily introduced into the surface of a resin base material by plasma irradiation in the plasma irradiation step, and the base material can have liquid repellency. Furthermore, since the wettability change pattern forming step is performed after the plasma irradiation step, the fluorine introduced by the plasma irradiation step can be removed in a high-definition pattern, and the lyophilic solution from which the fluorine has been removed. Thus, a pattern-formed body having a conductive region and a liquid repellent region in which fluorine remains can be obtained. Moreover, in this invention, since the introduction | transduction of the fluorine to the said base material is performed by the said plasma irradiation, a fluorine shall be introduced only into the surface of the said base material. Therefore, it is possible to easily remove fluorine by energy irradiation in the wettability change pattern forming step, and there is an advantage that a pattern formed body can be manufactured efficiently.

  In the above invention, the wettability change pattern forming step is performed by introducing fluorine into the semiconductor photocatalyst containing layer containing the semiconductor photocatalyst and the semiconductor photocatalyst containing layer of the semiconductor photocatalyst containing layer side substrate having the substrate and the plasma irradiation step. It is preferable that it is a step of placing the substrate facing the substrate and irradiating energy. Thereby, in the said wettability change pattern formation process, it becomes possible to remove a fluorine also using the effect | action of the semiconductor photocatalyst accompanying energy irradiation, and a pattern formation body can be manufactured more efficiently.

  Moreover, this invention provides the pattern formation body which has a base material containing a fluorine in a pattern shape on the surface.

  According to the present invention, the region in which the substrate contains fluorine can be defined as a liquid repellent region, and the region in which the substrate does not contain fluorine can be defined as a lyophilic region. It can be set as the pattern formation body which can form a functional part with high definition.

  According to the present invention, it is possible to efficiently produce a pattern forming body in which a liquid repellent region and a lyophilic region are formed in a highly fine pattern.

  The present invention relates to a pattern forming body having a pattern with different wettability on a surface, which can be used for various applications including a color filter, and a method for producing the same. Each will be described in detail below.

A. First, the manufacturing method of the pattern formation body of this invention is demonstrated. The method for producing a pattern forming body of the present invention includes a plasma irradiation step of irradiating a resin substrate with plasma using a fluorine compound as an introduction gas, and introducing fluorine, and the above-described base into which fluorine has been introduced by the plasma irradiation step. It is characterized by having a wettability change pattern forming step of irradiating the material with energy in a pattern and forming a wettability change pattern in which the contact angle with the liquid is reduced on the base material.

  For example, as shown in FIG. 1, the method for producing a pattern forming body of the present invention includes a plasma irradiation step (FIG. 1A) of irradiating a resin base material 1 with plasma 2 using a fluorine compound as an introduction gas, By irradiating energy 4 in a pattern using, for example, a photomask 3 or the like on the substrate 1 into which fluorine has been introduced (FIG. 1B), the fluorine introduced into the substrate 1 is removed in a pattern. And a wettability change pattern forming step of forming the wettability change pattern 5 having a reduced contact angle with the liquid (FIG. 1C).

  According to the present invention, in the plasma irradiation step, the resin base material is irradiated with the plasma, so that fluorine can be introduced to the surface of the base material, and the base material has liquid repellency. Can do it. In addition, after the plasma irradiation step, a wettability change pattern forming step is performed in which energy is irradiated in a pattern, so that fluorine introduced in the plasma irradiation step can be removed in a pattern, and fluorine is removed by energy irradiation. The formed region can be a lyophilic region, and a pattern forming body can be obtained in which energy is not irradiated and a region where fluorine remains is a lyophobic region.

  At this time, in the present invention, since the introduction of the fluorine is performed by plasma irradiation, the fluorine introduced into the substrate is present only on the surface of the substrate. Therefore, the molecular chain bonded to fluorine is easily cleaved by energy irradiation in the wettability change pattern forming step, and fluorine can be easily removed. Therefore, according to this invention, the said pattern formation body can be manufactured efficiently. Hereafter, it demonstrates in detail for every process in the manufacturing method of the pattern formation body of this invention.

1. Plasma Irradiation Process First, the plasma irradiation process of the present invention will be described. The plasma irradiation step of the present invention is a step of introducing fluorine into a resin base material by irradiating plasma using a fluorine compound as an introduction gas.

  The plasma irradiation method in this step is not particularly limited as long as it is a method capable of introducing fluorine into the surface of the base material using a fluorine compound as an introduction gas. Plasma irradiation is performed under reduced pressure. Alternatively, plasma irradiation may be performed under atmospheric pressure.

  Further, the plasma irradiation area or the like is not particularly limited. For example, the entire surface of the substrate may be irradiated with plasma. For example, only a part of the substrate may be irradiated with plasma. It may be.

Here, examples of the fluorine compound of the introduced gas used when the plasma is irradiated include carbon fluoride (CF ₄ ), fluorine nitride (NF ₃ ), sulfur fluoride (SF ₆ ), and C ₂ Cl ₃ F _3. , C ₂ F ₆ , C ₃ F _{6 and the} like. Moreover, the irradiation condition of the plasma to be irradiated is appropriately selected depending on the irradiation apparatus or the like.

  Here, in the present invention, the plasma irradiation is preferably plasma irradiation at atmospheric pressure. This is because an apparatus for decompression or the like is not necessary, which can be preferable in terms of cost, manufacturing efficiency, and the like. The irradiation conditions of such atmospheric pressure plasma can be as follows. For example, the power output can be the same as that used in a general atmospheric pressure plasma irradiation apparatus. At this time, the distance between the plasma electrode to be irradiated and the substrate is preferably about 0.2 mm to 20 mm, and more preferably about 1 mm to 5 mm. Furthermore, the flow rate of the fluorine compound used as the introduction gas is preferably about 1 L / min to 100 L / min, more preferably about 5 L / min to 50 L / min, and the substrate conveyance speed at this time is 0.1 m / min. It is preferably about 10 to 10 m / min, and more preferably about 0.5 to 5 m / min.

  In this process, the presence of fluorine introduced into the substrate is determined by the ratio of the elemental fluorine in the total elements detected from the surface of the substrate in the analysis using an X-ray photoelectron spectrometer (XPS: ESCALAB 220i-XL). This can be confirmed by measuring. At this time, the proportion of the fluorine is preferably 10% or more.

  Furthermore, in the present invention, the contact angle of the substrate with the liquid having a contact angle of 40 mN / m is 10 ° or more, and particularly the contact angle with the liquid having a surface tension of 30 mN / m is 10 ° or more. Fluorine is preferably introduced so that the contact angle with a liquid having a surface tension of 20 mN / m is 10 ° or more. This is because when the contact angle with the liquid is small, the liquid repellency is not sufficient, and in the wettability change pattern forming process described later, the wettability with the region that has been made lyophilic by removing fluorine or the like. This is because it is difficult to form various functional parts by utilizing the difference in wettability.

  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.

  Here, as the resin-made base material into which fluorine is introduced in this step, the surface on the side into which fluorine is introduced is made of resin, and the configuration can be used as long as fluorine can be introduced by the plasma irradiation. Is not particularly limited, and may be, for example, a resin film, a resin flat plate, or the like. For example, a resin substrate coated on an inorganic substrate may be used. In addition, the shape, transparency, flexibility, and the like of the substrate are appropriately selected according to the use of the pattern forming body.

  Specifically, as the resin used for the substrate, organopolysiloxane, 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 mentioned.

  Moreover, in this invention, the light-shielding part may be formed on the said base material as needed. In this case, in the wettability change pattern forming process to be described later, even if the entire surface is irradiated with energy from the side opposite to the surface where fluorine is introduced, the portion where the light shielding portion is formed is not irradiated with energy. The fluorine introduced onto the region where the light shielding portion is formed cannot be removed. Such a light shielding part is not particularly limited as long as it can shield the energy irradiated with the wettability change pattern described later, and is formed on the surface of the base material on the side where fluorine is introduced. It may be formed on the surface of the substrate opposite to the side where fluorine is introduced. In addition, when the said light shielding part is formed in the surface into which a fluorine is introduce | transduced, and a fluorine is also introduce | transduced on a light shielding part by this process, the thing made from resin will be used as the said light shielding part.

2. Next, the wettability change pattern forming process in the present invention will be described. In the wettability change pattern forming step in the present invention, the substrate into which fluorine has been introduced by the plasma irradiation step is irradiated with energy in a pattern, and the wettability change pattern having a reduced contact angle with the liquid is applied to the substrate. It is a process of forming.

  In this step, if the method can remove the fluorine introduced onto the substrate in the plasma irradiation step in a pattern by irradiating the substrate with energy in a pattern, the energy The irradiation method, energy type, and the like are not particularly limited.

  As a method of irradiating the substrate with energy in a pattern, for example, fluorine is introduced using a method of irradiating energy using a mask such as a photomask or a substrate having a light shielding portion as described above. And a method of irradiating energy from a surface opposite to the opposite surface. In addition, the energy used in this case is not particularly limited as long as it is an energy capable of removing fluorine. Specifically, the light is 500 nm or less, particularly in the range of 150 nm to 500 nm, particularly in the range of 170 nm to 480 nm. Are preferably used. Examples of the lamp used for the irradiation of energy include ultraviolet excimer lamps such as argon, krypton, and xenon, low pressure mercury lamps, high pressure mercury lamps, and ultra high pressure mercury lamps. In the present invention, it is also possible to use a method of drawing and irradiating in a pattern using a laser such as excimer or YAG. The energy irradiation amount is set to an amount necessary for removing fluorine introduced into the substrate by the action of the energy.

  In this step, the contact angle with the liquid irradiated with the energy irradiation region, that is, the liquid with the wettability change pattern is less than 9 °, preferably with the liquid with a surface tension of 50 mN / m. It is preferable that the energy is applied so that the angle is 10 ° or less, particularly the contact angle with a liquid having a surface tension of 60 mN / m is 10 ° or less. This is because when the contact angle with the liquid is large, the lyophilic property is not sufficient, and the functional part forming coating solution is applied on the wettability change pattern formed by this process. In this case, the functional part forming coating solution may be repelled, making it difficult to form the functional part with high definition. The contact angle with the liquid is a value measured by the method described above.

  Here, in the present invention, particularly during the energy irradiation, as shown in FIG. 2, for example, the semiconductor photocatalyst-containing layer-side substrate 13 having the semiconductor photocatalyst-containing layer 11 and the substrate 12 containing the semiconductor photocatalyst is contained. It is preferable to arrange the layer 11 and the surface of the substrate 1 on the side where fluorine is introduced to face each other and irradiate energy 4 in a pattern using, for example, a photomask 3 or the like.

  Thereby, not only the effect | action by the irradiated energy but the said fluorine can be removed also by the effect | action of the semiconductor photocatalyst accompanying energy irradiation. Therefore, fluorine can be efficiently removed, and a pattern forming body can be produced efficiently. Hereinafter, the semiconductor photocatalyst-containing layer side substrate used in this step and its arrangement will be described in detail.

(Semiconductor photocatalyst containing layer side substrate)
The semiconductor photocatalyst containing layer side substrate used in this step is not particularly limited as long as it has a substrate and a semiconductor photocatalyst containing layer formed on the substrate.

a. First, the semiconductor photocatalyst containing layer used for the semiconductor photocatalyst containing layer side substrate will be described. The semiconductor photocatalyst-containing layer used in this step is not particularly limited as long as the semiconductor photocatalyst in the semiconductor photocatalyst-containing layer can remove fluorine introduced into the base material. And a binder, or a film formed of a single semiconductor photocatalyst. Further, the surface characteristics may be particularly lyophilic or lyophobic.

  The action mechanism of the semiconductor photocatalyst represented by titanium dioxide as described below in the semiconductor photocatalyst containing layer is not necessarily clear, but the carrier generated by light irradiation reacts directly with a nearby compound, or It is considered that the active oxygen species generated in the presence of oxygen and water change the chemical structure of organic matter. In the present invention, it is considered that this carrier acts on the bond between fluorine introduced into the base material arranged in the vicinity of the semiconductor photocatalyst-containing layer and the organic substance existing around the fluorine.

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

  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.

  Further, a visible light responsive type may be used as the titanium oxide. Visible light responsive titanium oxide is also excited by the energy of visible light. Examples of such a visible light responsive method include a method of nitriding titanium oxide.

When titanium oxide (TiO ₂ ) is subjected to nitriding treatment, a new energy level is formed inside the band gap of titanium oxide (TiO ₂ ), and the band gap is narrowed. As a result, the excitation wavelength of titanium oxide (TiO ₂ ) is usually 380 nm, but it can be excited even by visible light having a longer wavelength than the excitation wavelength. As a result, the wavelength in the visible light region of energy irradiation from various light sources can also contribute to the excitation of titanium oxide (TiO ₂ ), so that it is possible to further increase the sensitivity of titanium oxide. .

Here, the nitriding treatment of titanium oxide referred to in the present invention is a treatment for replacing part of the oxygen sites of the titanium oxide (TiO ₂ ) crystal with nitrogen atoms, or between the lattices of the titanium oxide (TiO ₂ ) crystal. A treatment of doping nitrogen atoms or a treatment of arranging nitrogen atoms at the grain boundaries of a polycrystalline aggregate of titanium oxide (TiO ₂ ) crystals.

The method of nitriding titanium oxide (TiO ₂ ) is not particularly limited. For example, crystalline titanium oxide fine particles are doped with nitrogen by heat treatment at 700 ° C. in an ammonia atmosphere, and the nitrogen is doped. Examples thereof include a method of forming a dispersion using fine particles and an inorganic binder, a solvent, or the like.

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

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

  In the case of a semiconductor photocatalyst-containing layer consisting only of a semiconductor photocatalyst, the efficiency of removing fluorine introduced into the substrate is improved, which is advantageous in terms of cost such as shortening of the processing time. On the other hand, in the case of a semiconductor photocatalyst containing layer comprising a semiconductor photocatalyst and a binder, there is an advantage that the formation of the semiconductor photocatalyst containing layer is easy.

  Examples of a method for forming a semiconductor photocatalyst-containing layer composed only of a semiconductor 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 semiconductor photocatalyst-containing layer by a vacuum film forming method, it is possible to obtain a semiconductor photocatalyst-containing layer that is a uniform film and contains only the semiconductor photocatalyst, and is more efficient than fluorine using a binder. Can be removed.

  As another example of the method for forming a semiconductor photocatalyst-containing layer consisting only of a semiconductor photocatalyst, for example, when the semiconductor photocatalyst is titanium dioxide, amorphous titania is formed on the substrate, and then the crystalline titania is phased by firing. The method of changing is mentioned. 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.

  Moreover, when using a binder, what has the high bond energy that the main frame | skeleton of a binder is not decomposed | disassembled by the photoexcitation of said semiconductor photocatalyst is preferable, for example, organopolysiloxane etc. can be mentioned.

  When organopolysiloxane is used as a binder as described above, the semiconductor photocatalyst-containing layer disperses the semiconductor photocatalyst and the binder organopolysiloxane in a solvent together with other additives as necessary, and applies the coating solution. It can be formed by preparing and 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 application can be performed by a known application method such as spin coating, spray coating, dip coating, roll coating, or bead coating. When an ultraviolet curable component is contained as a binder, the semiconductor 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 semiconductor photocatalyst particles are uniformly dispersed in a non-aqueous solvent and hydrolyzed with moisture in the air on the substrate to form silanol. A semiconductor photocatalyst-containing layer can be formed by dehydration condensation polymerization at room temperature. 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 semiconductor photocatalyst in the semiconductor 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 semiconductor photocatalyst containing layer is preferably in the range of 0.05 to 10 μm.

  In addition to the above-mentioned semiconductor photocatalyst and binder, a surfactant, an additive, and the like can be used for the semiconductor photocatalyst-containing layer. For example, those described in JP-A-2001-074928 can be used. .

  Here, in the present invention, for example, as shown in FIG. 2, the semiconductor photocatalyst containing layer 11 may be formed on the entire surface of the base 12, and for example, as shown in FIG. The photocatalyst containing layer 11 may be formed in a pattern. Such a patterning method for the semiconductor photocatalyst-containing layer is not particularly limited, and can be performed by, for example, a photolithography method.

  In the present invention, for example, as shown in FIG. 4, a semiconductor photocatalyst-containing layer side light-shielding portion 14 may be formed on the semiconductor photocatalyst-containing layer 11, and for example, as shown in FIG. The semiconductor photocatalyst containing layer side light shielding part 14 may be formed on the semiconductor photocatalyst containing layer side light shielding part 14 so as to cover the semiconductor photocatalyst containing layer side light shielding part 14. By forming such a semiconductor photocatalyst-containing layer side light-shielding part, it is not necessary to use a photomask or the like during the energy irradiation. Here, the semiconductor photocatalyst-containing layer side light shielding part is not particularly limited as long as it shields the energy irradiated in the wettability change pattern forming step, and is generally used as a light shielding part. The same can be said.

b. Substrate Next, the substrate used for the semiconductor photocatalyst-containing layer side substrate will be described. In the present invention, the semiconductor photocatalyst-containing layer side substrate has at least a substrate 12 and a semiconductor photocatalyst-containing layer 11 formed on the substrate 12 as shown in FIG.

  The substrate used in the present invention is not particularly limited as long as it can form the semiconductor photocatalyst-containing layer, and may be, for example, a resin film having flexibility. What does not have, for example, a glass substrate etc. may be sufficient.

  An anchor layer may be formed on the substrate in order to improve the adhesion between the substrate surface and the semiconductor photocatalyst-containing layer and to prevent the substrate from being deteriorated by the action of the semiconductor photocatalyst. Examples of such an anchor layer include silane-based and titanium-based coupling agents, silica films prepared by a reactive sputtering method, a CVD method, and the like.

(Arrangement of semiconductor photocatalyst containing layer side substrate)
Next, the arrangement of the semiconductor photocatalyst-containing layer side substrate will be described. In this step, the semiconductor photocatalyst-containing layer side substrate is disposed so that the base material into which fluorine has been introduced in the plasma irradiation step and the semiconductor photocatalyst-containing layer face each other, and is irradiated with energy. Under the present circumstances, it arrange | positions so that the surface in which the fluorine was introduce | transduced among the said base materials may face the said semiconductor photocatalyst content layer.

  Here, the above arrangement means a state in which the action of the semiconductor photocatalyst substantially extends to the base material, and the semiconductor photocatalyst-containing layer and the base material are in close contact with each other. In addition to the state, the semiconductor photocatalyst-containing layer and the base material are arranged at a predetermined interval. This gap is preferably 200 μm or less.

  In the present invention, the gap is particularly preferably in the range of 0.2 μm to 10 μm, preferably in the range of 1 μm to 5 μm. Such a gap range is particularly effective for a substrate having a small area where the gap can be controlled with high accuracy.

  On the other hand, when processing a large area substrate such as 300 mm × 300 mm or more, it is extremely difficult to form a fine gap as described above between the semiconductor photocatalyst containing layer side substrate and the substrate. It is. Therefore, when the substrate 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, it is possible to further remove fluorine without causing problems such as a decrease in pattern accuracy and a problem that the sensitivity of the semiconductor photocatalyst deteriorates and the efficiency of removing fluorine deteriorates. This is because there is an effect that unevenness does not occur.

  Thus, when energy irradiation is performed on a base material having a relatively large area, the setting of the gap in the positioning device between the semiconductor photocatalyst containing layer side substrate and the base material in the energy irradiation device is set within a range of 10 μm to 200 μm, particularly It is preferable to set within a range of 25 μm to 75 μm. This is because by setting the set value within such a range, it is possible to arrange the semiconductor photocatalyst without significantly degrading the sensitivity.

  Thus, by disposing the semiconductor photocatalyst-containing layer and the substrate surface at a predetermined interval, oxygen, water, and active oxygen species generated by the semiconductor photocatalytic action are easily desorbed. That is, when the interval between the semiconductor photocatalyst-containing layer and the substrate is narrower than the above range, it is difficult to desorb the active oxygen species, and as a result, the rate of removing fluorine may be reduced. It is not preferable. In addition, it is not preferable that the active oxygen species generated are difficult to reach the substrate when arranged at a distance from the above range, and in this case as well, the rate of removing fluorine may be reduced.

  An example of a method for uniformly forming such an extremely narrow gap and arranging the semiconductor photocatalyst-containing layer and the substrate is a method using a spacer. This is because a uniform gap can be formed by using the spacer in this way. In addition, by using such a spacer, the active oxygen species generated by the action of the semiconductor photocatalyst reaches the substrate surface at a high concentration without diffusing, so that fluorine can be efficiently removed.

  In the case where a semiconductor photocatalyst-containing layer side substrate formed on a flexible substrate such as a resin film having flexibility is used as the semiconductor photocatalyst-containing layer, it is difficult to provide the gap as described above. From the standpoint of production efficiency and the like, it is preferable that the semiconductor photocatalyst-containing layer and the substrate are disposed so as to contact each other.

  In the present invention, such an arrangement state of the semiconductor photocatalyst-containing layer side substrate only needs to be maintained at least during the energy irradiation. In this step, the type of energy used when the semiconductor photocatalyst-containing layer side substrate is used, the irradiation method thereof, and the like can be the same as those described above.

  In particular, it is preferable that the semiconductor photocatalyst-containing layer is irradiated with energy while being heated, so that sensitivity can be increased, and fluorine can be efficiently removed. Specifically, it is preferable to heat within a range of 30 ° C to 80 ° C.

3. Other In the method for producing a pattern formed body of the present invention, in addition to the plasma irradiation step and the wettability change pattern forming step, for example, a light shielding portion forming step for forming a light shielding portion on a substrate is appropriately performed as necessary. You may have the process of.

  The use of the pattern formed body produced according to the present invention is not particularly limited. For example, the conductive pattern in which the metal wiring is formed using the difference in wettability or the difference in wettability is used. It can be used for the manufacture of functional elements having various functional parts, such as microlenses formed with a lens. It is preferably used for manufacturing a color filter to be formed. This is because a color filter can be obtained efficiently in the process. In this case, a transparent substrate transparent in the visible light region is used as the substrate.

B. Next, the pattern forming body of the present invention will be described. The pattern forming body of the present invention is characterized by having a substrate containing fluorine in a pattern on the surface. For example, as shown in FIG. 6, fluorine is introduced into the surface of the substrate 1 in a pattern. It is characterized by having a region 5 formed.

  According to the present invention, since the region containing fluorine is formed in a pattern, the region having fluorine on the surface is the liquid-repellent region, and the region not having fluorine on the surface is the lyophilic region. It can be used as a sex region. Therefore, it is possible to obtain a pattern forming body that can easily form a functional part on the pattern forming body using the difference in wettability.

  Here, in the present invention, the fluorine is preferably contained in a region within 50 nm from the surface of the substrate. The measurement of the presence or absence of fluorine is confirmed by measuring the ratio of fluorine element in all elements detected from the surface of the semiconductor photocatalyst containing layer in the analysis by X-ray photoelectron spectrometer (XPS: ESCALAB 220i-XL) can do. At this time, the proportion of the fluorine is preferably 10% or more.

  At this time, the pattern having fluorine is not particularly limited, and is appropriately selected according to the use of the pattern forming body. In the present invention, the contact angle with the liquid in the region containing fluorine is 10 ° or more, the contact angle with a liquid having a surface tension of 30 mN / m is 10 ° or more, and the contact angle with a liquid having a surface tension of 30 mN / m, In particular, the contact angle with a liquid having a surface tension of 20 mN / m is preferably 10 ° or more. This is because when the contact angle with the liquid in the region is small, the liquid repellency is not sufficient, and various functional parts are formed on the pattern forming body using the difference in wettability due to the presence or absence of fluorine. This may be difficult.

  Further, in the region where the substrate surface does not contain fluorine, the contact angle with the liquid is less than 9 ° with respect to the liquid with 40 mN / m, preferably the contact angle with the liquid with a surface tension of 50 mN / m is 10 It is preferable that the contact angle with a liquid having a surface tension of 60 mN / m or less is 10 ° or less. When the contact angle with the liquid in the above region is high, a function for forming the functional part when forming various functional parts on the pattern forming body using the difference in wettability due to the presence or absence of fluorine This is because the functional part forming coating liquid may be repelled and the functional part forming coating liquid may not be sufficiently wetted and spread, which may make it difficult to form the functional part. The contact angle with the liquid is a value measured by the method described above.

  Here, since the base material used for the pattern formation body of this invention and the manufacturing method of a pattern formation body can be made to be the same as the method demonstrated in the section of the "A. manufacturing method of a pattern formation body" mentioned above. Detailed explanation here is omitted.

  In addition, the pattern formation body in this invention will not be specifically limited if it has the base material which has the said fluorine in a pattern shape, For example, it has other members, such as a light-shielding part, as needed. It may be.

  In addition, the pattern forming body of the present invention has various functions such as a conductive pattern in which metal wiring is formed using the difference in wettability and a microlens in which a lens is formed using the difference in wettability. In the present invention, it is particularly preferably used for the production of a color filter that forms a colored layer by utilizing the difference in wettability. . This is because a color filter can be obtained efficiently in the process. In this case, a transparent substrate that is transparent in the visible light region is used as the substrate.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

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

<Preparation of resin substrate>
Polyvinyl alcohol (Nippon Synthetic Chemical Co., Ltd. Gohsenol AH-26) was dissolved in ion-exchanged water to prepare a resin composition having a solid content of 1%. This was applied on a glass substrate and dried at 100 ° C. for 30 minutes to form a resin layer having a thickness of 1 μm to obtain a resin substrate. The contact angle of the resin layer surface with water was 10 °.

<Plasma irradiation process>
The resin layer surface of the resin substrate was irradiated with atmospheric pressure plasma under the following conditions. As a result, the contact angle of water on the surface of the resin layer was 93 °. Further, as a result of the surface analysis of the resin layer surface by XPS (ESCALAB 220i-XL), a large amount of organic fluorine-based components (CF ₃ -CF ₂ -CF _2- , CF ₂ -CF _2- , CF ₂ -CH ₂₎ -) Was detected.
(Plasma irradiation conditions)
Introducing gas: CF ₄ ... 15 (l / min.)
・ Distance between electrode and substrate: 2mm
・ Power supply output: 200V-5A

<Preparation of semiconductor photocatalyst containing layer side substrate>
A semiconductor photocatalyst inorganic coating agent (ST-K01 manufactured by Ishihara Sangyo Co., Ltd.) was diluted with isopropyl alcohol to prepare a composition for a 1% semiconductor photocatalyst-containing layer.
A semiconductor having a transparent semiconductor photocatalyst-containing layer (thickness 0.2 μm) by applying the above composition onto a photomask substrate (100 μm line and space) with a spin coater and performing a drying treatment at 150 ° C. for 10 minutes. A photocatalyst-containing layer side substrate was formed.

<Wettability change pattern formation process>
The resin layer of the resin substrate and the semiconductor photocatalyst containing layer on the semiconductor photocatalyst containing layer side substrate are held facing each other so as to have a gap of 50 μm, and an ultra high pressure mercury lamp (365 nm 40 mW / cm ² ) is used. Ultraviolet rays were irradiated from the photocatalyst containing layer side substrate side for 300 seconds. As a result, the contact angle between the exposed portion of the resin layer and the liquid decreased, and a hydrophilic portion and a hydrophobic portion were formed on the surface of the resin layer with a line and space of 100 μm.

It is process drawing which shows an example of the manufacturing method of the pattern formation body of this invention. It is a schematic sectional drawing which shows an example of the wettability change pattern formation process of the pattern formation body of this invention. It is a schematic sectional drawing which shows an example of the semiconductor photocatalyst content layer side board | substrate used for the manufacturing method of the pattern formation body of this invention. It is a schematic sectional drawing which shows the other example of the semiconductor photocatalyst containing layer side board | substrate used for the manufacturing method of the pattern formation body of this invention. It is a schematic sectional drawing which shows the other example of the semiconductor photocatalyst containing layer side board | substrate used for the manufacturing method of the pattern formation body of this invention. It is a schematic sectional drawing which shows an example of the pattern formation body of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Plasma 4 ... Energy 5 ... Wettability change pattern 11 ... Semiconductor photocatalyst containing layer 12 ... Base | substrate 13 ... Semiconductor photocatalyst containing layer side board | substrate

Claims (2)

A plasma irradiation step of irradiating a resin base material with plasma using a fluorine compound as an introduction gas, and introducing fluorine;
A wettability change pattern forming step of irradiating the substrate into which fluorine has been introduced in the plasma irradiation step with a pattern, and forming a wettability change pattern with a reduced contact angle with the liquid on the substrate. And
The method for producing a pattern forming body, wherein the plasma irradiation is plasma irradiation under atmospheric pressure .   The wettability change pattern forming step includes a semiconductor photocatalyst-containing layer containing a semiconductor photocatalyst and a semiconductor photocatalyst-containing layer-side substrate of the semiconductor photocatalyst-containing layer side substrate, and the base material into which fluorine has been introduced by the plasma irradiation step; The method for producing a pattern forming body according to claim 1, wherein the pattern forming body is disposed by facing each other and irradiating energy.

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