JP2005191180A - Photo mask and method for manufacturing pattern formed body using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photo mask by which a pattern formed body for various uses can be easily formed under comparatively high exposure sensitivity. <P>SOLUTION: When the photo mask is manufactured by forming a light shielding film pattern on one side of a light transmitting substrate and demarcating a light transmitting part by the light shielding film pattern, a fluorine-containing photocatalyst active layer containing a photocatalyst and a fluorine-based compound is formed in a manner that it can be overlapped on the light transmitting part on the plane view. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photomask and a method of manufacturing a pattern forming body using the photomask, and more particularly to a photomask using a photocatalyst and a method of manufacturing a pattern forming body using the photomask.

  Here, the “pattern formed body” in the present specification refers to a material layer having a pattern (latent image) of a desired shape formed by locally changing the surface properties and a member provided with the material layer. It is a generic name.

  Nowadays, various patterning methods have been developed to mass-produce the same designs, images, characters, figures, elements, circuit patterns and the like.

  For example, in a heat mode recording method known as one of methods for producing an original plate for lithographic printing, the surface of a heat mode recording material is selectively irradiated with a laser beam, and a desired pattern ( Latent image). Although the surface of the heat mode recording material has ink repellency, a region having high receptivity to ink can be formed by irradiation with laser light. Therefore, by scanning the surface of the heat mode recording material with a laser beam and drawing a desired pattern, an original plate having a pattern (latent image) having a desired shape composed of a region having high receptivity to ink can be obtained. .

  Although the heat mode recording method has the advantage that the original plate is relatively easy to prepare, the adjustment of the intensity of the laser beam, the treatment of the residue that may occur in the region irradiated with the laser beam, or However, there is still room for improvement in terms of the printability of the obtained printing original plate.

  In a photolithography method known as a method for patterning a thin film with high definition, a photomask having a light-shielding film patterned in a predetermined shape is used as an original plate. For example, when the object to be patterned by the photolithography method is a photoresist film, the photoresist film is subjected to selective exposure using a photomask and then developed, so that a photo patterned into a desired shape is obtained. A resist film can be obtained. When the object to be patterned by photolithography is an inorganic film or an organic film other than a photoresist film, a photoresist layer is first formed on the film to be patterned, and a photomask is formed on the photoresist layer. A photoresist layer patterned into a desired shape is obtained by performing development treatment after selective exposure using the film. Thereafter, the patterned photoresist layer is used as an etching mask to etch the film to be patterned, and then the etching mask is peeled off, whereby a film patterned into a desired shape can be obtained.

  The photolithographic method is used in the manufacturing process of various members such as a color filter array, a microlens array, a light shielding film pattern used for a photomask, and the object to be patterned is either an organic film or an inorganic film. However, waste liquid is always generated in the development process, and it is difficult to process the waste liquid. Furthermore, when the object to be patterned is an inorganic film or an organic film other than a photoresist film, waste liquid is generated in the etching process and the etching mask peeling process, and it is difficult to process these waste liquids.

  In recent years, a patterning method using a photocatalyst has been developed as a method for easily forming a pattern (latent image) having a desired shape on the surface of an organic film. Hereinafter, this method will be described by collectively referring to an organic film as a target for forming a latent image as a “patterned layer”.

  For example, Patent Document 1 discloses that a pattern formation layer contains a photocatalyst, and this pattern formation layer (photocatalyst-containing layer) is selectively irradiated with laser light, or a pattern is formed using a photomask. A method of forming a pattern (latent image) on the surface of the pattern forming layer by selectively exposing the layer or a method of patterning the pattern forming layer into a desired shape is described. Patent Document 1 describes that the pattern formation layer may contain fluorine (fluoroalkyl group).

Patent Document 2 discloses a photocatalyst-containing layer having a pattern-forming body substrate on which a pattern formation layer (characteristic change layer or wettability change layer) having a light-shielding portion is formed, and a layer containing a photocatalyst (photocatalyst-containing layer). The side substrate is arranged so that the pattern forming layer and the photocatalyst-containing layer are in contact with each other, and in this state, exposure is performed from the pattern forming substrate side, whereby a pattern (latent image) is formed on the surface of the pattern forming layer. Or a method of patterning a pattern forming layer into a desired shape. Patent Document 2 describes that a desired pattern can be effectively obtained by including fluorine in the pattern forming layer.
JP-A-11-344804 (Claims) JP 2003-195029 A (Claims and 0086 to 0133, especially 0116)

  However, since the photocatalyst is contained in the pattern forming layer in the method described in Patent Document 1, the photocatalyst is inevitably included in the pattern formed body produced by this method. If the pattern forming body contains a photocatalyst, the photocatalyst may have an adverse effect depending on its use. In this respect, there is still room for improvement in the method described in Patent Document 1.

  Also, the methods described in both Patent Documents 1 and 2 have relatively low exposure sensitivity, and there is still room for improvement in this respect. Exposure sensitivity can be improved by adding fluorine to the pattern forming layer. However, when the pattern forming body is continuously produced, variation in exposure sensitivity becomes relatively large, and the control tends to be complicated. One reason for the variation in exposure sensitivity is considered to be that fluorine radicals generated from the pattern formation layer adhere to the surface of the photocatalyst-containing layer and contribute to the reaction during patterning of the next pattern formation layer.

  The present invention has been made to solve the above-described problems, and a first object of the present invention is to provide a photomask that can easily form a pattern forming body for various uses with a relatively high exposure sensitivity. Is to provide.

  A second object of the present invention is to provide a method for producing a pattern forming body that can easily form pattern forming bodies for various uses with a relatively high exposure sensitivity.

  The photomask of the present invention that achieves the first object described above is a photomask in which a light-shielding film pattern is formed on one surface of a light-transmitting substrate, and a light-transmitting portion is defined by the light-shielding film pattern, A fluorine-containing photocatalytic active layer containing a photocatalyst and a fluorine-based compound is formed so as to overlap the light transmitting portion in plan view (hereinafter, this photomask is referred to as “photomask I”) There is.)

  Since the photomask I of the present invention has a fluorine-containing photocatalytic active layer, the surface of the pattern forming layer can be selectively exposed by using the photomask I without including a photocatalyst in the pattern forming layer. It is possible to form a desired pattern (latent image). Further, at the time of exposure using the photomask I, fluorine radicals can be generated from the fluorine-containing photocatalytic active layer by the action of the photocatalyst, so that the exposure sensitivity can be increased as compared with the case where no fluorine radical is generated. Furthermore, although the reason is not clear, the variation in exposure sensitivity can be suppressed even when the pattern forming body is continuously produced. For these reasons, according to the photomask I of the present invention, it becomes easy to form pattern-formed bodies for various uses with relatively high exposure sensitivity.

  In the photomask I of the present invention, the light shielding film pattern and the fluorine-containing photocatalytic active layer are formed on the same surface of the light-transmitting substrate, and the fluorine-containing photocatalytic active layer covers the light shielding film pattern. It is preferable that this photomask be referred to as “photomask II” hereinafter.

  The manufacturing method of the pattern forming body of the present invention that achieves the second object described above includes a preparation step of preparing a pattern forming layer capable of changing the wettability of the surface by light irradiation, and a step of forming the pattern forming layer. A selective exposure step of selectively exposing to form a pattern consisting of a region having changed wettability on the surface of the pattern forming layer, wherein the selective exposure step is as described above. The photomask I or the photomask II of the present invention is disposed so that the fluorine-containing photocatalytic active layer faces the pattern formation layer, and the surface of the pattern formation layer is selectively exposed. .

  According to the method for producing a pattern forming body of the present invention, a pattern formation layer is selectively exposed using the above-described photomask I or photomask II of the present invention to form a pattern on the surface thereof. It becomes easy to form a pattern forming body for use under a relatively high exposure sensitivity.

  In the method for producing a patterned body of the present invention, (1) in the preparation step, a layer whose surface properties change from hydrophobic to hydrophilic by light irradiation is prepared as the pattern forming layer, (2) The pattern forming layer is a liquid crystal alignment film; (3) further includes a functional part forming step of forming a functional part on the pattern formed in the selective exposure step; and (4) the function. Preferably, a color filter array is formed as the functional part in the functional part forming step, or (5) a microlens array is formed as the functional part in the functional part forming step.

  According to the photomask of the present invention, it becomes easy to form pattern forming bodies for various uses with a relatively high exposure sensitivity, so that mass production of desired pattern forming bodies is facilitated.

  Also, according to the method for producing a pattern formed body of the present invention, it becomes easy to form a pattern formed body for various uses with a relatively high exposure sensitivity, so that mass production of a desired pattern formed body is facilitated. .

  Hereinafter, a method for manufacturing a photomask and a pattern forming body according to the present invention will be sequentially described with reference to the drawings as appropriate.

<Photomask (first form)>
FIG. 1A is a schematic view showing an example of a basic cross-sectional structure of the photomask of the present invention. In the illustrated photomask 10, a light shielding film pattern 3 is formed on one surface of a light transmissive substrate 1, and a light transmissive portion 5 is defined by the light shielding film pattern 3. Further, the fluorine-containing photocatalytic active layer 7 is formed so as to cover the light shielding film pattern 3 and to overlap each light transmission portion 5 in plan view. Hereinafter, the light transmissive substrate 1, the light shielding film pattern 3, and the fluorine-containing photocatalytic active layer 7 will be described in detail.

(1) Light transmissive substrate;
The light-transmitting substrate 1 is preferably excellent in the transmittance of electromagnetic waves (light) used for exposure, light resistance against the electromagnetic waves, and the like. A rigid material such as a glass plate, a high silicate glass plate, or a silicon carbide film, or a flexible material such as a transparent resin film or an optical resin plate can be used.

(2) light shielding film pattern;
The light-shielding film pattern 3 shields electromagnetic waves (light) used for exposure and demarcates a light transmission portion 5 of a predetermined pattern in the photomask 10. The light-shielding film pattern 3 is desired on the surface by selective exposure using the photomask 10. The pattern is formed on the light-transmitting substrate 1 corresponding to the portion corresponding to the non-exposed portion in the pattern forming layer to be formed. A region where transmitted light is not shielded by the light shielding film pattern 3 is a light transmitting portion 5.

  The light-shielding film pattern 3 includes, for example, an inorganic light-shielding material such as metallic chromium, an inorganic light-absorbing material such as tungsten, or a light-shielding particle such as carbon fine particles, metal oxide, and inorganic pigment in an organic binder. It can be formed of a composite material, and its overall shape is appropriately selected according to the pattern (latent image) to be formed on the surface of the patterning layer.

  When the light shielding film pattern 3 is to be formed using the above inorganic light shielding material or inorganic light absorbing material, for example, a thin film having a thickness of about 100 to 200 nm is formed by sputtering or vacuum deposition using these materials. The light shielding film pattern 3 is formed by patterning the thin film into a desired shape by a photolithography method.

  Moreover, when it is going to form the light shielding film pattern 3 using said composite material, resin, such as a polyimide, an acrylic resin, an epoxy resin, polyacrylamide, polyvinyl alcohol, is used as an organic binder, for example, 1 type or 2 types or more A coating composition is prepared using the coating composition, and the coating composition is applied to a desired shape by a printing method to form a light-shielding film pattern 3. Alternatively, a coating composition is prepared using a photosensitive resin, an O / W (oil in water) emulsion type resin composition (for example, an emulsion of reactive silicone), gelatin, casein, cellulose, etc. as an organic binder. The coating composition is applied in a desired shape by a printing method to form a light shielding film pattern 3. The light-shielding film pattern 3 can also be obtained by patterning a coating film formed from the above coating composition into a desired shape by a photolithography method.

(3) a fluorine-containing photocatalytic active layer;
The fluorine-containing photocatalytic active layer 7 is a layer containing a photocatalyst and a fluorine-based compound. When the patterning layer is selectively exposed using the photomask 10, the exposure of the surface of the pattern forming layer is performed. It plays a role of changing the property (wetting property) of the formed region.

As said photocatalyst, 1 type of photo-semiconductor particle or the mixture of multiple types of photo-semiconductor particle can be used. Specific examples of the optical semiconductor include titanium dioxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), and bismuth oxide (Bi ₂ O _3). ), Iron oxide (Fe ₂ O ₃ ), and the like.

  Among these optical semiconductors, titanium dioxide is preferably used from the viewpoints of being chemically stable, non-toxic and easily available. Titanium dioxide includes anatase type and rutile type, and any type of titanium dioxide can be used, but it is preferable to use anatase type titanium dioxide. Examples of the composition containing anatase type titanium dioxide particles include hydrochloric acid peptized type anatase type titania sol (STS-02 (average particle size: 7 nm) manufactured by Ishihara Sangyo Co., Ltd.) and ST manufactured by Ishihara Sangyo Co., Ltd. -K01), anatase titania sol of nitrate peptization type (TA-15 (average particle size 12 nm) manufactured by Nissan Chemical Co., Ltd.) and the like. These compositions can be used as a material for the fluorine-containing photocatalyst-containing layer 7.

  A photocatalytic reaction can be caused by photoexcitation of the photocatalyst. Since this photocatalytic reaction occurs effectively when the particle diameter of the photo semiconductor particles used as the photocatalyst is small to some extent, the average particle diameter is preferably 5 to 20 nm. The wavelength of the excitation light that photoexcites the photocatalyst varies depending on the magnitude of the band gap energy of the optical semiconductor used as the photocatalyst. Even if the photocatalysts have the same composition, the photocatalyst exhibiting the quantum size effect has a larger band gap energy than the photocatalyst not exhibiting the quantum size effect, so that the wavelength of the excitation light is shifted to the short wavelength side. For example, the anatase-type titanium dioxide exhibiting a quantum size effect has an excitation wavelength of 380 nm or less.

  The fluorine-based compound constituting the fluorine-containing photocatalytic active layer together with the photocatalyst described above generates fluorine radicals by a photocatalytic reaction. The fluorine-based compound is not particularly limited as long as it is a compound that generates a fluorine radical by a photocatalytic reaction, but is preferably a fluorine-based silicone, and particularly a fluorine-based silicone in which a fluoroalkyl group is bonded to a silicon atom of silicone. It is preferable that Among the fluorine-based compounds, a fluorine-based compound in which a fluoroalkyl group having about 6 to 18 carbon atoms is bonded to a silicon silicon atom is easily mixed with a photocatalyst and applied to the light-transmitting substrate 1. Is particularly preferred.

  Specific examples of suitable fluorinated compounds include the following hydrocondensation condensates of fluoroalkylsilanes and cohydrolyzed condensates of two or more mixtures of fluoroalkylsilanes shown below. What is known as an agent is mentioned.

[Fluoroalkylsilane]
_{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 SiCH 3 (OCH 3) 2, (CF 3) 2 CF (CF 2) 8 CH ₂ CH ₂ SiCH 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.

  The fluorine-containing photocatalytic active layer 7 can appropriately contain optional components such as a binder and a surfactant in addition to the above-described photocatalyst and fluorine-based compound.

The binder preferably has a high binding energy such that the main skeleton is not decomposed by the excitation light of the photocatalyst. For example, an organopolysiloxane described in detail in the description of the pattern forming layer described later can be used. . An amorphous silica precursor can also be used as a binder. Examples of the amorphous silica precursor include a silicon compound represented by the general formula SiX ₄ (wherein X is a halogen atom, a methoxy group, an ethoxy group, an acetyl group, or the like), and a silanol that is a hydrolyzate of the silicon compound. Or, polysiloxane having an average molecular weight of 3000 or less is preferable.

  Furthermore, polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene terpolymer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate, polyvinyl chloride, polyamide, polyimide, polypropylene, polybutylene, polystyrene, Monomers, oligomers or prepolymers for polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, styrene butadiene rubber, chloroprene rubber, etc. can be used as the binder. is there.

  On the other hand, as the surfactant, any of a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant can be used. Specific examples of the non-on surfactant include (i) hydrocarbon surfactants such as NIKKOL BL, BC, BO, and BB series manufactured by Nikko Chemicals, and (ii) ZONYL FSN manufactured by DuPont. , FSO, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Mega-Fac F-141, 144 manufactured by Dainippon Ink & Chemicals, Ltd., Footgent F-200, F251 manufactured by Neos Co., Ltd., Daikin Industries Fluorine surfactants such as Unidyne DS-401 and 402 manufactured by Co., Ltd., Fluorard FC-170 and 176 manufactured by 3M Co., and (iii) Silicone nonionic surfactants may be mentioned.

  The total amount of essential components (photocatalyst and fluorine-based compound) in the fluorine-containing photocatalytic active layer 7 is preferably about 0.1% by mass or more and 100% by mass or less, and preferably about 1% by mass or more and 100% by mass or less. More preferably. Moreover, it is preferable that the ratio of the photocatalyst to the total amount of essential components shall be about 20-40 mass%.

  The fluorine-containing photocatalytic active layer 7 is prepared by dissolving and dispersing the above-described components in a solvent to prepare a coating liquid, and this coating liquid is formed on a predetermined surface of the light-transmitting substrate 1, that is, the light-shielding film pattern 3 is formed. It can be obtained by curing the coating film after coating on the surface to form a coating film. The film thickness of the fluorine-containing photocatalytic active layer 7 can be appropriately selected within a range in which the light shielding film pattern 3 can be covered.

  In addition, a primer layer can also be formed in order to improve the adhesiveness between the light-transmitting substrate 1 and the fluorine-containing photocatalytic active layer as necessary. As a material for the primer layer, for example, a silane-based or titanium-based coupling agent can be used.

  The photomask 10 having the above-described configuration is used by being disposed so that the fluorine-containing photocatalytic active layer 7 faces the pattern formation layer. By irradiating the pattern forming layer with light having an excitation wavelength of the photocatalyst or light having a wavelength region including light of this excitation wavelength via the photomask 10, a photocatalytic reaction occurs due to the photocatalyst present in each light transmitting portion 5. The property (wetting property) of the exposed region of the surface of the pattern forming layer changes.

  The mechanism of action of the photocatalyst and the fluorine-based compound at this time is not necessarily clear, but as described later, fluorine radicals are generated from the fluorine-based compound by the action of the photoexcited photocatalyst, and oxygen or water in the air is used. Decomposition is promoted to produce active oxygen and active hydroxyl groups, which change the chemical structure of the patterned layer, resulting in a change in the properties (wetting properties) of the exposed region of the surface of the patterned layer. It is thought to do.

  Since the photomask 10 has the fluorine-containing photocatalytic active layer 7, even if the photocatalyst is not contained in the pattern formation layer, the surface of the pattern formation layer is hydrophilic by selective exposure using the photomask 10. It is possible to form a desired pattern (latent image) composed of a sex region. Further, at the time of exposure using the photomask 10, fluorine radicals can be generated from the fluorine-containing photocatalytic active layer 7 by the action of the photocatalyst, so that the exposure sensitivity can be increased as compared with the case where no fluorine radical is generated. Furthermore, although the reason is not clear, the variation in exposure sensitivity can be suppressed even when the pattern forming body is continuously produced. According to the photomask 10, it becomes easy to form pattern formation bodies for various uses with relatively high exposure sensitivity. Details of the method of manufacturing the pattern forming body will be described later.

  In addition, when a pattern formation body is continuously produced using the same photomask 10, the fluorine atoms in the fluorine-containing photocatalytic active layer 7 are consumed, and the exposure sensitivity gradually decreases. From the viewpoint of keeping the exposure sensitivity within a certain range, it is preferable to re-apply a coating liquid as a material for the fluorine-containing photocatalytic active layer 7 to re-form the fluorine-containing photocatalytic active layer 7 having a desired thickness. .

<Photomask (second form)>
FIG. 1B is a schematic view showing another example of the basic cross-sectional structure of the photomask of the present invention. In the illustrated photomask 20, a light shielding film pattern 13 is formed on one surface of the light transmissive substrate 11, and a light transmissive portion 15 is defined by the light shielding film pattern 13. In addition, one fluorine-containing photocatalytic active layer 17 is formed in each light transmitting portion 15 on the same surface as the surface on which the light shielding film pattern 13 is formed. The light transmitting portion 15 and the fluorine-containing photocatalytic active layer 17 corresponding to the light transmitting portion 15 overlap in plan view.

  The configuration of the photomask 20 is different from the configuration of the photomask 10 of the first embodiment in that the light shielding film pattern 13 is not covered with the fluorine-containing photocatalytic active layer 17. Other configurations are the same as the configuration of the photomask 10, and the technical effects produced by the photomask 20 are the same as the technical effects produced by the photomask 10.

<Photomask (third form)>
FIG. 1C is a schematic view showing still another example of the basic cross-sectional structure of the photomask of the present invention. In the illustrated photomask 30, a light shielding film pattern 23 is formed on one surface of a light transmissive substrate 21, and a light transmissive portion 25 is defined by the light shielding film pattern 23. Moreover, the fluorine-containing photocatalytic active layer 27 is formed on the entire surface opposite to the surface on which the light shielding film pattern 23 is formed. Each light transmission part 25 and the fluorine-containing photocatalytic active layer 27 overlap in plan view.

  The configuration of the photomask 30 is that the surface on which the light shielding film pattern 23 is formed and the surface on which the fluorine-containing photocatalytic active layer 27 is formed are different from each other on the light transmissive substrate 21. Different from the configuration of the mask 10. Other configurations are the same as the configuration of the photomask 10, and the technical effects produced by the photomask 30 are the same as the technical effects produced by the photomask 10.

<Method for producing pattern formed body>
As described above, the method for producing a patterned product of the present invention comprises a preparation step of preparing a pattern formation layer capable of changing the wettability of the surface by light irradiation, and selectively exposing the pattern formation layer. And a selective exposure step of forming a pattern composed of a region having changed wettability on the surface of the pattern forming layer, and the photomask of the present invention described above is used in the selective exposure step. In addition, if necessary, it further includes a functional part forming step of forming a functional part on the pattern formed on the surface of the pattern forming layer in the selective exposure step. Hereafter, each process is demonstrated, referring drawings suitably.

(1) Preparation process;
The pattern forming layer prepared in the preparation step may be any layer that can change the wettability of the surface by light irradiation, but the surface property can be changed from hydrophobic to hydrophilic by light irradiation. It is preferable that it contains a compound having a siloxane bond.

As a material of the pattern forming layer whose surface can be changed from hydrophobic to hydrophilic by light irradiation, a general formula Y _n SiX _(4-n) (wherein Y is an alkyl group, vinyl group, amino group) , A phenyl group, or an epoxy group, and X represents an alkoxyl group, an acetyl group, or a halogen atom (wherein n is an integer of 0 to 3)). An organopolysiloxane or an organopolysiloxane that is a cohydrolyzed condensate of two or more silicon compounds represented by the above general formula is preferred, and in particular, an organo having a long-chain alkyl group having about 6 to 18 carbon atoms. Polysiloxane is preferred. By forming the pattern forming layer with such an organopolysiloxane, it is possible to obtain a pattern forming layer that can easily change the wettability of the surface by selective exposure. In the above general formula, the number of carbon atoms of the group represented by the symbol “Y” is preferably in the range of 1 to 20, and the alkoxy group represented by the symbol “X” is a methoxy group, an ethoxy group, or a propoxy group. A butoxy group is preferred.

  Specific examples of the raw material of the above-mentioned organopolysiloxane include (a) methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane, (b) Ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrit-butoxysilane, (c) n-propyltrichlorosilane, n-propyltribromosilane, n-propyl Trimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxysilane, n-propyltri-t-butoxysilane, (d) n-hexyltrichlorosilane, n-hexyltribromosilane, n-hex Rutrimethoxysilane, n-hexyltriethoxysilane, n-hexyltriisopropoxysilane, n-hexyltrit-butoxysilane, (e) n-decyltrichlorosilane, n-decyltribromosilane, n-decyltrimethoxy Silane, n-decyltriethoxysilane, n-decyltriisopropoxysilane, n-decyltri-t-butoxysilane, (f) n-octadecyltrichlorosilane, n-octadecyltribromosilane, n-octadecyltrimethoxysilane, n- Octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltri-t-butoxysilane, (g) phenyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, fluoro Nyltriisopropoxysilane, phenyltri-t-butoxysilane, (h) tetrachlorosilane, tetrabromosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane, (i) dimethyldichlorosilane, dimethyl Dibromosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, (j) diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, (k) phenylmethyldichlorosilane, phenylmethyldibromosilane, Phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, (l) trichlorohydrosilane, tribromohydrosilane, trimethoxyhydrosilane, triethoxyhydrosilane, triiso Propoxyhydrosilane, tri-t-butoxyhydrosilane, (m) vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltrit-butoxysilane, (n) trifluoropropyltrichloro Silane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltriisopropoxysilane, trifluoropropyltrit-butoxysilane, (o) γ-glycidoxypropylmethyl Dimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-g Lysidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane, (p) γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyl Trimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltriisopropoxysilane, γ-methacryloxypropyltri-butoxysilane, (q) γ-aminopropylmethyldimethoxysilane, γ- Aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltrit-butoxysilane, (r) γ-mercap Propylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltri-t-butoxysilane, ( s) β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, (t) the silicon compounds shown in the above (a) to (s) Examples thereof include partial hydrolysates, and (u) a mixture of silicon compounds selected from the silicon compounds shown in the above (a) to (t).

  Further, organopolysiloxane having a fluoroalkyl group can also be used as a material for the pattern forming layer. Specific examples of this organopolysiloxane include hydrocondensation products of fluoroalkyl silanes and co-hydrolysis condensates of two or more fluoroalkyl silanes, generally known as fluorine-based silane coupling agents Can be used.

  The material of the pattern forming layer can contain the surfactant, monomer, oligomer, prepolymer or the like already described as an optional component of the fluorine-containing photocatalytic active layer, if necessary.

  The pattern forming layer may have a self-supporting property, that is, a strength capable of being handled alone, or may not have a self-supporting property. The film thickness of the pattern forming layer can be appropriately selected according to the intended use of the pattern forming body, etc., but from the relationship such as the speed of change in surface properties (wetting properties) due to the photocatalytic action described above, The film thickness is preferably about 0.001 to 1 μm, and more preferably about 0.01 to 0.1 μm. When the pattern forming layer does not have self-supporting property, the pattern forming layer is formed on a desired substrate. Although there is no restriction | limiting in particular about the base material used at this time, The thing with favorable adhesiveness with a to-be-patterned layer is preferable. Specific examples include those formed of glass, ceramic, metal, plastic, and the like, and those having a layer formed of glass, ceramic, metal, plastic, and the like. Which substrate is used can be appropriately selected according to the intended use of the pattern forming body.

  The pattern forming layer is prepared by, for example, preparing a coating composition by dissolving or dispersing the above-described raw materials in a solvent, applying the coating composition on a substrate to form a coating film, and then drying the coating film. Can be obtained. The solvent used for the preparation of the coating composition is preferably an alcoholic organic solvent such as ethanol or isopropanol. In applying the coating composition, various application methods such as spin coating, spray coating, dip coating, roll coating, and bead coating can be applied. When the coating composition contains an ultraviolet curable component, the pattern forming layer can be formed by irradiating the coating film with ultraviolet rays and performing a curing treatment.

(2) selective exposure step;
In the selective exposure step, the pattern forming layer is selectively exposed using the above-described photomask of the present invention to form a predetermined pattern (latent image) on the surface of the pattern forming layer. Hereinafter, the case where the pattern formation layer is selectively exposed using the photomask 10 (see FIG. 1A) shown in the first embodiment is taken as an example, and FIGS. The selective exposure process will be specifically described with reference to FIG. Note that since the photomask 10 has already been described, the same reference numerals as those used in FIG. 1A are used for the constituent members of the photomask 10 shown in FIGS. 2A and 2B. A description thereof will be omitted.

  First, as shown in FIG. 2A, the photomask 10 and the pattern formation layer 40 are formed in a predetermined manner so that the fluorine-containing photocatalytic active layer 7 and the pattern formation layer 40 in the photomask 10 face each other. Align to position. The illustrated pattern formation layer 40 is formed on a base material 45.

  In disposing the photomask 10 on the pattern forming layer 40, the distance d between the fluorine-containing photocatalytic active layer 7 in the light transmitting portion 5 and the pattern forming layer 40 in the photomask 10 is about 0 to 200 μm. It is preferable to select within the range. When this interval exceeds 200 μm, the exposure sensitivity and exposure accuracy (patterning accuracy) are likely to be greatly reduced.

  The patterning accuracy is high and the wettability within the pattern is different depending on the type of each of the fluorine-based compound and the photocatalyst contained in the fluorine-containing photocatalytic active layer 7, the content of the photocatalyst, or the material of the pattern forming layer 40. From the viewpoint of obtaining a pattern-formed body having a small unevenness, it is preferable to select the distance d within a range of about 0.2 to 20 μm. When the distance d is selected within this range, it is easy to obtain a pattern-formed body with high exposure sensitivity, in other words, it is easy to obtain a pattern-formed body by a relatively short exposure process.

  Next, as shown in FIG. 2B, the surface of the pattern forming layer 40 is selected by irradiating the pattern forming layer 40 with exposure light having a desired wavelength or a desired wavelength region from the outside of the photomask 10. Exposure. As the exposure light at this time, light having an excitation wavelength of the photocatalyst contained in the fluorine-containing photocatalytic active layer 7 or light in a wavelength region including light having this excitation wavelength is used, and the wavelength of the exposure light is used as the light source. Or according to a wavelength range, various artificial light sources, such as a mercury lamp, a metal hydride lamp, a xenon lamp, an excimer lamp, can be used, for example. The incident angle of the exposure light to the photomask 10 can be set to 0 °, for example. By this selective exposure, the photocatalyst in the region located in the light transmitting portion 5 in the fluorine-containing photocatalytic active layer 7 is excited to cause a photocatalytic reaction. In FIG. 2B, the exposure light is indicated by a plurality of arrows, and a part of the arrows is given a reference symbol “UV”.

  As shown in FIG. 2 (c), the photocatalytic reaction changes the wettability of the exposed region of the surface 40a of the pattern forming layer 40. In other words, the properties of the exposed region are changed. By changing from hydrophobic to hydrophilic, a pattern (latent image) 42 composed of the hydrophilic region 40 b is formed on the surface 40 a of the pattern forming layer 40. Thereby, the pattern formation body 50 which consists of layer 40A which is the to-be-patterned layer 40 after the predetermined pattern (latent image) was formed, and the base material 45 is obtained. In FIG. 2C, in order to make the location of the hydrophilic region 40b in the layer 40A easy to understand, each hydrophilic region 40b is thickened and smudged.

The above-described action mechanism of the photocatalytic reaction is not necessarily clear, but is considered to be an action mechanism schematically shown in FIGS. 3 (a) to 3 (b). That is, as shown in FIG. 3A, fluorine radicals (F ⁻ ) are generated from the fluorine-containing photocatalytic active layer 7 by the action of the photoexcited photocatalyst, and decomposition of oxygen and water in the air is promoted to activate active oxygen. (O ₂ ⁻ ) and active hydroxyl groups (—OH) are generated, and these attack the side chain (for example, alkyl side chain) SC on the surface 40 a of the pattern forming layer 40 to break the bond of the side chain SC. And as shown in FIG.3 (b), it is thought that here changes to the hydrophilic area | region 40b as a result of replacement | exchange and coupling | bonding with active oxygen etc. in the part into which the side chain SC was cut | disconnected.

  It is preferable that the surface free energy at the pattern (latent image) 42 formed on the surface of the pattern forming layer 40 and the surface free energy at the surface 40a around the pattern 42 be as large as possible. When the pattern forming layer 40 is formed of the above-described material, the pattern forming layer 40 having a surface free energy of about 25 mN / m or less at the stage before the selective exposure step can be obtained. In this case, it is preferable to select the exposure energy (irradiation intensity and irradiation time) in the selective exposure step so that the surface free energy in the pattern 42 is about 35 mN / m or more.

  A pattern forming body can be obtained by sequentially performing the preparation process and the selective exposure process described above. This pattern forming body is used as a final product as it is, or as an intermediate product of other pattern forming bodies, depending on the material of the layer to be patterned. Function to form a functional part on the pattern formed on the surface of the pattern forming layer in the selective exposure process when the pattern formed body obtained by performing up to the selective exposure process is used as an intermediate product of another pattern forming body The sex part forming step can be performed.

  Here, the “functional part” in this specification refers to an optical function (light selective absorption, reflection, translucency, polarization, light selective transmission, nonlinear optical, fluorescence, phosphorescence, etc. Radiation luminescence, photochromic, light condensing, light diffusing, light shielding, etc.), magnetic function (hard magnetic, soft magnetic, non-magnetic, magnetic permeability, etc.), electrical / electronic function (conductive, insulating) , Piezoelectricity, pyroelectricity, dielectricity, etc.), chemical function (adsorption, desorption, catalyst, water absorption, oil absorption, ion conductivity, redox, electrochemical, electrochromic, etc.), It means a member responsible for a desired function such as a mechanical function (such as wear resistance), a thermal function (such as thermal conductivity, heat insulation, infrared radiation), or a biological function (such as biocompatibility or antithrombogenicity).

  There is a liquid crystal alignment substrate as one of the ones that can obtain a patterned product as a final product by sequentially performing the above-described preparation step and selective exposure step. Hereinafter, the liquid crystal alignment substrate will be described in detail.

<Pattern (liquid crystal alignment substrate)>
When a liquid crystal alignment substrate as a final product is obtained by sequentially performing the above-described preparation process and selective exposure process, the pattern forming layer is, for example, a vertical line for vertically aligning liquid crystals having negative dielectric anisotropy. An alignment film (hereinafter, this vertical alignment film is abbreviated as “VA alignment film”) is used.

  Since the surface of the alignment film for VA has hydrophobicity, a multi-domain liquid crystal display is formed by forming a hydrophilic pattern having a desired shape on the surface of the alignment film for VA by the selective exposure process described above. A liquid crystal alignment substrate plate provided with an alignment film used in the apparatus (hereinafter, this alignment film is abbreviated as “MD alignment film”) can be obtained. In this case, the alignment film for VA is formed on a predetermined substrate. Accordingly, in the preparation step, a liquid crystal alignment substrate provided with a VA alignment film is prepared.

  FIG. 4A is a schematic diagram showing an example of a planar arrangement of components on a liquid crystal alignment substrate provided with a VA alignment film, and FIG. 4B is a schematic diagram of the IV− shown in FIG. It is the schematic of a IV line cross section. The illustrated liquid crystal alignment substrate 120 is a substrate on the display surface side of a liquid crystal panel for display in an active matrix driving type vertical alignment liquid crystal display device using negative liquid crystal (liquid crystal having negative dielectric anisotropy). A light transmissive substrate 101, a color filter array 103, a light shielding layer (black matrix) 105, a transparent electrode pattern 107, and a VA alignment film 109 are used.

  A color filter array 103 and a light shielding layer 105 are formed on one surface of the light transmissive substrate 101, and a transparent electrode pattern 107 is formed so as to cover them. A VA alignment film 109 is formed so as to cover the transparent electrode pattern 107. In FIG. 4A, the transparent electrode pattern 107 and the alignment film 109 are not shown in order to make the arrangement of the color filter array 103 and the light shielding layer 105 easy to understand.

  The light transmissive substrate 101 is formed of, for example, glass or transparent plastic, and the color filter array 103 is formed by arranging a number of color filters of a desired color under a certain pattern. Each color filter can be formed of, for example, a resin (color resin) containing or dispersing a dye or pigment or a color filter ink.

  The illustrated color filter array 103 includes a red color filter 103R (hereinafter simply referred to as “color filter 103R”), a green color filter 103G (hereinafter simply referred to as “color filter 103G”), and a blue color filter 103B (hereinafter referred to as “color filter 103R”). , Simply referred to as “color filter 103B”) is a stripe-type color filter array arranged in a stripe pattern. Each of the color filters 103R, 103G, and 103B corresponds to one pixel. One color filter 103R, the adjacent color filter 103G, and the adjacent color filter 103B constitute one picture element. In addition to the stripe type, various types of color filter arrays called a mosaic type and a triangle type are known.

  The light shielding layer 105 is used to prevent light leakage (leakage light) from between pixels in the display liquid crystal panel and light deterioration of active elements in the active matrix drive type display liquid crystal panel. It is arranged around 103G and 103B. The light shielding layer 105 can be formed of a metal thin film having a light shielding property or a light absorbing property, such as a metal chromium thin film or a tungsten thin film. It is also possible to form the light shielding layer 105 with an organic material. The illustrated light shielding layer 105 has a large number of regions 105a for preventing light degradation and the like of the active element.

  The transparent electrode pattern 107 is an electrode for forming a vertical electric field in the display liquid crystal panel, and is formed of a transparent electrode material such as indium tin oxide (ITO), indium oxide, or indium zinc oxide (IZO). The illustrated transparent electrode pattern 107 is used as a common electrode (common electrode) in a display liquid crystal panel, and has a quadrangular shape in plan view.

  The VA alignment film 109 corresponds to a pattern forming layer referred to in the method for producing a pattern forming body of the present invention, and becomes an MD alignment film through the selective exposure step described above. If necessary, a planarization layer may be formed so as to cover the color filter array 103 and the light shielding layer 105, and the VA alignment film 109 may be provided thereon.

  The liquid crystal alignment substrate as the final product forms a desired hydrophilic pattern on the surface of the VA alignment film 109 in the liquid crystal alignment substrate 120 described above by selective exposure using the photomask of the present invention, It can be obtained by making the alignment film 109 for VA into an alignment film for MD.

  FIG. 5 schematically shows an example of the arrangement of the hydrophilic regions 119b in the MD alignment film 119 obtained by forming a plurality of hydrophilic regions on the surface of the VA alignment film 109 shown in FIG. 4B. FIG. In the figure, the light shielding layer 105 under the MD alignment film 119 is also shown with hidden lines (broken lines) in order to make it easy to understand the relative positional relationship between each hydrophilic region 119b and the pixel.

  As shown in the drawing, a plurality of hydrophilic regions 119b are regularly formed on the surface of the MD alignment film 119, and the shape of each of the hydrophilic regions 119b in a plan view is a zigzag band shape. is there. As these hydrophilic regions 119b as a whole, one hydrophilic region 119b is used as a repeating unit, and this repeating unit is arranged in parallel in the scanning direction Ds (meaning the extending direction of the scanning line) in the display liquid crystal panel. It has the shape. Assuming that two linear sections adjacent to each other in the hydrophilic region 119b are represented by a reference symbol S, these two linear sections S and S respectively represent two pixels adjacent in the scanning direction Ds in plan view. Crossing diagonally above. One pixel corresponds to two linear sections S and S in two adjacent hydrophilic regions 119b and 119b, respectively. The angle (bending angle) θ between the two linear sections S, S connected to each other is preferably about 90 ° from the viewpoint of obtaining a display liquid crystal panel having excellent viewing angle characteristics. The periphery of each hydrophilic region 119b is a hydrophobic region 119a.

  The line width of each hydrophilic region 119b is four times the value of the cell gap when the cell gap (design value) of a display liquid crystal panel to be manufactured using a liquid crystal alignment substrate is used as a reference. It is preferable to make it about or less, and it is more preferable to make it about twice or less. Further, it is preferable that the line width be equal to or greater than the cell gap value.

  The liquid crystal alignment substrate provided with the MD alignment film 119 described above is one of the pattern forming bodies referred to in the present invention. The liquid crystal alignment substrate provided with the MD alignment film uses the VA alignment film 109 shown in FIG. 4B as a pattern forming layer in the pattern forming body manufacturing method of the present invention. In this photomask, except that the light transmission part is formed corresponding to the arrangement of the hydrophilic region 119b, it can be obtained by the method for producing the pattern forming body of the present invention already described.

  When a liquid crystal display panel is formed using a liquid crystal alignment substrate having the MD alignment film 119, the liquid crystal molecules on the hydrophilic region 119b and the liquid crystal molecules near the boundary between the hydrophilic region 119b and the hydrophobic region 119a are hydrophobic. The liquid crystal molecules on the conductive region 119a are more easily tilted and aligned. That is, the liquid crystal molecules on the hydrophilic region 119b and the liquid crystal molecules in the vicinity of the boundary between the hydrophilic region 119b and the hydrophobic region 119a start inclined alignment at a lower voltage than the liquid crystal molecules on the hydrophobic region 119a. To do.

  If the liquid crystal molecules on the hydrophilic region 119b and the liquid crystal molecules in the vicinity of the boundary between the hydrophilic region 119b and the hydrophobic region 119a are tilted before the liquid crystal molecules on the hydrophobic region 119a, local alignment distortion occurs. Arise. Since the liquid crystal is an elastic body, when local orientation distortion occurs, the liquid crystal is solved to maintain stability. For this reason, at least the liquid crystal molecules on the hydrophobic region 119a are tilted so as to follow the tilted alignment of the liquid crystal molecules in the vicinity of the boundary between the hydrophobic region 119a and the hydrophilic region 119b during halftone display. As a result, individual pixels can be multi-domained.

  The arrangement and shape of the hydrophilic region in the MD alignment film are not limited to the arrangement and shape shown in FIG. 5. For example, (1) Hydrophobic regions on individual pixels in the display liquid crystal panel (2) The distribution form of the hydrophobic region on the pixel in the display liquid crystal panel is a plurality of types, and these distribution forms are pixels. Any arrangement and shape that appear in a substantially constant cycle in at least one of the column direction and the pixel row direction can be appropriately changed. The shape of each hydrophobic region defined by the hydrophilic region in plan view can be, for example, a triangle such as a regular triangle, a quadrangle such as a square, a hexagon such as a regular hexagon, or a circle. For example, if the shape of the hydrophilic region is made into a lattice shape, the shape of each hydrophobic region can be made into a quadrangle, and if made into a honeycomb shape, the shape of each hydrophobic region can be made into a hexagon. .

  Further, the liquid crystal alignment substrate provided with the MD alignment film is not limited to the one used as the display surface side substrate in the display liquid crystal panel, but is used as the back side substrate in the display liquid crystal panel. It may be. The configuration of the liquid crystal alignment substrate can be appropriately selected according to its use.

  As described above, in the method for producing a pattern formed body of the present invention, a functional part forming step for forming a functional part on the pattern formed on the surface of the pattern forming layer in the selective exposure step is performed as necessary. It can be carried out. In this case, the pattern forming body obtained by performing up to the selective exposure step is used as an intermediate product for obtaining another pattern forming body. Hereinafter, the functional part forming process which is an optional process will be described by giving a black matrix, a color filter array, and a microlens array as specific examples of the functional part.

<Functional part formation process>
[Black matrix and color filter array]
FIG. 6 is a cross-sectional view schematically showing an example of the arrangement of a black matrix and a color filter array that can be formed as a functional part. As shown in the drawing, the black matrix 140 and the color filter array 145 are both formed on one side of a light-transmitting substrate 131 via a base layer 133.

  The member 135 in which the base layer 133 is formed on one surface of the translucent substrate 131 is one of the pattern forming bodies manufactured by the manufacturing method of the present invention, and the base of the black matrix 140 in the surface of the base layer 133. At least one of the region and the region serving as the base of the color filter array 145 becomes a hydrophilic region through the selective exposure process described above. The underlayer 133 (hereinafter referred to as “precursor layer”) before selectively hydrophilizing the surface corresponds to the pattern forming layer referred to in the present invention.

  In addition, at least one of the black matrix 140 and the color filter array 145 formed on the base layer 133 corresponds to the functional portion described above. The member 150 on which the black matrix 140 and the color filter array 145 are formed is also one of the pattern forming bodies manufactured by the manufacturing method of the present invention.

  The color filter array 145 in the member 150 is composed of a red color filter array constituted by a large number of red color filters 145R arranged in a predetermined pattern and a large number of blue color filters 145G arranged in a predetermined pattern. A blue color filter array and a blue color filter array constituted by a large number of green color filters 145B arranged in a predetermined pattern are arranged in a predetermined pattern. The black matrix 140 is formed of a black resin, and is disposed so as to surround each of the red color filter 145R, the green color filter 145G, and the blue color filter 145B constituting the color filter array 145 in a plan view. .

  For example, a region where the black matrix 140 is to be formed on the surface of the precursor layer is selectively exposed to form a hydrophilic region, whereby the base layer 133 is obtained. The periphery of the hydrophilic region is a hydrophobic region. When a coating composition for forming the black matrix 140 made of black resin is applied on the base layer 133 thus formed, a coating film can be easily formed only on the hydrophilic region. Since the black matrix 140 is obtained by curing the above-described coating film, the target black matrix 140 made of black resin can be easily formed at a desired position.

  In this case, the hydrophilic region selectively formed on the surface of the base layer 133 corresponding to the shape of the black matrix 140 corresponds to the “pattern” in the method for manufacturing the pattern forming body of the present invention. The process of forming a coating film on the hydrophilic region with the coating composition for the black matrix 140 and curing the coating film to obtain the black matrix 140 corresponds to the functional part forming process.

  Without forming a hydrophilic region on the surface of the precursor layer, the black matrix 140 is formed on the precursor layer with an inorganic material such as metal chromium as in the conventional case, and then the color filter array 145 is formed on the surface of the precursor layer. A color filter array can also be formed after selectively exposing a region to be formed to make it a hydrophilic region. In this case, the selective exposure of the precursor layer and the formation of the color filter array are sequentially performed for each color filter array constituting the color filter array 145.

  That is, after performing selective exposure in accordance with the arrangement of the color filter array of the first color, the color filter array of this color is formed, and then selective exposure in accordance with the arrangement of the color filter array of the second color. After this, the color filter array of this color is formed, and finally, the color filter array of this color is formed after performing selective exposure according to the arrangement of the color filter array of the third color. The color filter array of each color can be obtained by applying a color filter ink or color resin of a desired color on a predetermined hydrophilic region by, for example, a printing method to form a coating film and curing the coating film. . Even in this case, since the coating film can be easily formed only on the hydrophilic region, it is easy to form a desired color filter array of a desired color at a desired position.

  The hydrophilic region that is selectively formed on the surface of the underlayer 133 when forming the color filter array of each color corresponds to a “pattern” in the method for producing a pattern forming body of the present invention. Moreover, the process of forming the coating film by applying the color filter ink or the color resin and curing the coating film to obtain the color filter array of the desired color corresponds to the functional part forming process.

  When the color filter array 145 is formed in this manner, the overlap width between the color filters 145R, 145G, and 145B of the respective colors constituting the color filter array 145 and the black matrix 140 is small, or the color filters 145R, 145G, and 145B of the respective colors A color filter array 145 that does not substantially overlap with the black matrix 140 can be obtained. When the above overlap width in the color filter array 145 is small or does not substantially overlap, it is easy to form a transparent electrode pattern and alignment film with high flatness on the color filter array 145, so that the cell gap unevenness is small. It becomes easy to obtain a liquid crystal panel for display.

  When manufacturing the member 150 shown in FIG. 6, the black matrix 140 made of black resin is formed on the underlayer 133 as described above, and then the color filter array 145 is formed as described above. You can also In this case, the process of forming the black matrix 140 and the process of forming the color filter array 145 correspond to the functional part forming process.

  The color filter array formed as the functional part is not limited to the color filter array used in the display device for full color display. In the method for producing a pattern forming body of the present invention, it is possible to form various color filter arrays used for a display device or an imaging device as a functional part. The same applies to the case where a black matrix is formed as the functional part. For example, a liquid crystal alignment substrate can be obtained by forming a transparent electrode pattern so as to cover the black matrix 140 and the color filter array 145 shown in FIG. 6 and providing an alignment film thereon.

[Microlens array]
FIG. 7 is a cross-sectional view schematically showing an example of a microlens array that can be formed as a functional part. The illustrated microlens array 168 is formed by regularly arranging a large number of microlenses 168 a, and each microlens 168 a is formed on one side of a light-transmitting substrate 161 via a base layer 163. .

  The member 165 in which the base layer 163 is formed on one surface of the translucent substrate 161 is one of the pattern forming bodies manufactured by the manufacturing method of the present invention, and the base layer 163 is interposed on the translucent substrate 161. The member 170 on which the microlens array 168 is formed is also one of the pattern forming bodies manufactured by the manufacturing method of the present invention.

  Of the surface of the base layer 163, the region that is the base of the microlens 168a is a hydrophilic region. The periphery of the hydrophilic region is a hydrophobic region. The underlayer 163 (hereinafter referred to as “precursor layer”) before selectively hydrophilizing the surface corresponds to the pattern forming layer referred to in the present invention.

  Of the surface of the precursor layer, each region where the microlens 168a is to be formed is selectively exposed to form a hydrophilic region, whereby the base layer 163 is obtained. The periphery of each hydrophilic region is a hydrophobic region. When a coating composition for forming the microlens array 168 is applied on the base layer 163 thus formed, a coating film can be easily formed only on each hydrophilic region. At this time, when a certain amount or more of the coating composition is applied to the hydrophilic region, the periphery becomes a hydrophobic region. Therefore, the applied coating composition tries to stop in the hydrophilic region, and the periphery is hydrophobic. Compared to the case where there is no sex region, the entire coating film is raised. Since the microlens array 168 is obtained by curing each of the coating films, the individual microlens 168a can be easily formed at a desired position. In addition, the focal length of each microlens 168a can be controlled by adjusting the coating amount of the coating composition.

  When the microlens array 168 is formed in this manner, hydrophilic regions selectively formed on the surface of the base layer 163 corresponding to the shape of the microlens array 168 (arrangement of the individual microlenses 168a) This corresponds to the “pattern” in the method for producing a pattern forming body of the invention. The process of forming a coating film on the hydrophilic region with the coating composition for forming the microlens array 168 and curing the coating film to obtain the microlens array 168 corresponds to the functional part forming process.

  In addition, as a coating composition for forming the micro lens array 168, for example, a photosensitive resin composition or a thermosetting resin composition can be used. The shape of each microlens 168a in plan view is appropriately selected according to the use of the microlens array 168, such as a circle or a rectangle. The microlens array is used in various fields such as a display device, an imaging device, an optical communication device, an optical integrated circuit, and an image recognition device as a light condensing element, a stereoscopic display element, an optical coupling element, a light diffusing element, and the like. Therefore, the configuration of the base material 161 is appropriately selected according to the use of the microlens array 168 and the like. For example, by providing a microlens array on the back substrate of the display liquid crystal panel, a bright and clear liquid crystal display device can be obtained even when the illuminance of the backlight is lowered.

<Other forms>
The pattern forming body obtained by performing the selective exposure process described above can be used as an intermediate product for forming a functional part having a desired pattern made of, for example, an electroless plating film.

  When forming a functional part having a desired pattern made of an electroless plating film, a hydrophilic region is formed in a predetermined pattern on the surface of the pattern formed body obtained by performing the selective exposure process. The pretreatment liquid for forming the thin film can be easily applied only on the hydrophilic region. As a result, it becomes easy to form a desired electroless plating film only on the hydrophilic region. According to this method, for example, a circuit pattern can be formed as the functional portion.

  In addition, the pattern forming body obtained by performing the selective exposure process is performed by using the difference between the adhesion strength of the vapor deposition film on the hydrophilic region and the adhesion strength of the vapor deposition film on the hydrophobic region. It can also be used as an intermediate product for forming a functional part having a desired pattern.

  When forming a functional portion of a desired pattern made of a vapor deposition film, first, a physical vapor phase is formed so as to cover the pattern (latent image) formed on the surface of the pattern forming body obtained by performing the selective exposure process. A vapor deposition film is formed by a growth (PVD) method, a chemical vapor deposition (CVD) method, or the like. Thereafter, an adhesive film or the like is once attached to the entire deposited film, and the attached adhesive film or the like is peeled off. At this time, since the adhesion strength of the vapor deposition film on the hydrophilic region is higher than the adhesion strength of the vapor deposition film on the hydrophobic region, the vapor deposition film is peeled off together with the adhesive film only on the hydrophobic region. Can be made. As a result, the functional part which consists of a vapor deposition film pattern of the shape corresponding to the shape of a hydrophilic region can be formed. Also by this method, for example, a circuit pattern can be formed as the functional part.

<Example 1>
First, a quartz glass substrate having a thickness of about 0.225 mm (0.09 inch) was prepared. Further, 1 wt% of fluorine-based silicone (TSL8223 manufactured by Toshiba Silicone) is added to a dispersion of anatase-type titanium oxide fine particles (ST-K03 (trade name) manufactured by Ishihara Sangyo Co., Ltd.) to form a fluorine-containing photocatalytic active layer. A coating composition was prepared.

  Next, the coating composition was spin-coated on one side of the quartz glass substrate to form a coating film having a thickness of 0.5 μm. Then, the said coating film was dried at 150 degreeC for 10 minute (s), and the fluorine-containing photocatalytic active layer with a film thickness of 0.5 micrometer was obtained. Hereinafter, the quartz glass substrate on which the fluorine-containing photocatalyst layer is formed is referred to as a “mask blank”.

  Separately from the production of the mask blank, an alkyl silicone (a 0.3: 1 (mass ratio) mixture of LS2820 manufactured by Shin-Etsu Chemical Co., Ltd. and TSL8114 manufactured by Toshiba Silicone Co., Ltd.) is prepared. A coating film having a film thickness of 70 nm was formed on one surface of the substrate by spin coating, and then the coating film was dried at 150 ° C. for 10 minutes to obtain a patterned layer having a film thickness of 70 nm. In the same manner, a total of six patterned layers were obtained.

Next, the surface of each pattern formation layer was exposed to ultraviolet rays having a wavelength range of 200 to 370 nm through the mask blank described above. At this time, the mask blank was arrange | positioned on a to-be-patterned layer so that a fluorine-containing photocatalytic active layer and a to-be-patterned layer might mutually oppose. The distance between the fluorine-containing photocatalytic active layer and the pattern forming layer was about 20 μm. The amount of exposure is set to 0 mJ / cm ² , 70 mJ / cm ² , 140 mJ / cm ² , 280 mJ / cm ² , 560 mJ / cm ² , or 840 mJ / cm ² for each pattern forming layer. The incident angle was set to 0 ° when any pattern forming layer was exposed.

The surface free energy of each pattern forming layer after exposure (including those with an exposure amount of 0 mJ / cm ² ) was determined as follows. That is, a plurality of types of liquids whose surface free energies are known are dropped on each pattern forming layer, and their contact angles are measured with a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) Said surface free energy was calculated | required from following formula (I) and formula (II). FIG. 8 shows the relationship between the surface free energy and the exposure amount thus determined.

<Comparative Example 1>
A mask blank was prepared using silicone not containing fluorine (LS5258 manufactured by Shin-Etsu Chemical Co., Ltd.) instead of the fluorine-based silicone used in Example 1, and the same conditions as in Example 1 were used using this mask blank. A total of six patterned layers were selectively exposed below (including those with an exposure amount of 0 mJ / cm ² ). And the surface free energy of the to-be-patterned layer after exposure was measured on the same conditions as Example 1. FIG. The results are also shown in FIG.

<Comparative example 2>
A mask blank was prepared using silicone not containing fluorine (LS2820 manufactured by Shin-Etsu Chemical Co., Ltd.) instead of the fluorine-based silicone used in Example 1, and the same conditions as in Example 1 were used using this mask blank. A total of six patterned layers were selectively exposed below (including those with an exposure amount of 0 mJ / cm ² ). And the surface free energy of the to-be-patterned layer after exposure was measured on the same conditions as Example 1. FIG. The results are also shown in FIG.

<Evaluation>
As is clear from FIG. 8, when the mask blank produced in Example 1 was used, exposure was performed under the same exposure amount as compared with the case where the mask blank produced in Comparative Example 1 or Comparative Example 2 was used. Even so, the surface free energy of the patterned layer is increased. Further, the amount of exposure required to make the surface free energy of the pattern forming layer the same value is small.

  The mask manufactured in Example 1 is a mask blank and not a photomask. However, by providing a light shielding film pattern having a predetermined shape on the mask blank, for example, a photomask having the structure shown in FIG. 1C can be obtained. . Even when the pattern formation layer is selectively exposed using this photomask, the same result as shown in FIG. 8 is obtained, and a desired pattern formation body is formed with a relatively high exposure sensitivity. It will be easier to do. Further, it is considered that the same result can be obtained even if the photomask structure is the structure shown in FIG.

FIG. 1A is a schematic diagram showing an example of the basic cross-sectional structure of the photomask of the present invention, and FIG. 1B shows another example of the basic cross-sectional structure of the photomask of the present invention. FIG. 1C is a schematic diagram showing still another example of the basic cross-sectional structure of the photomask of the present invention. FIG. 2A to FIG. 2C are process diagrams for explaining a selective exposure process performed in the method for manufacturing a pattern molded body of the present invention. FIG. 3A to FIG. 3B are schematic views for explaining the action mechanism of the photocatalytic reaction, respectively. FIG. 4A is a schematic diagram showing an example of a planar arrangement of components in a liquid crystal alignment substrate provided with a vertical alignment film, and FIG. 4B is an IV-IV shown in FIG. It is the schematic of a line cross section. An example of the arrangement of the hydrophilic regions in the alignment film used in the multi-domain liquid crystal display device obtained by forming a plurality of hydrophilic regions on the surface of the vertical alignment film shown in FIG. FIG. It is sectional drawing which shows roughly an example of arrangement | positioning of the black matrix and color filter array which can be formed as a functional part in the functional part formation process which is an arbitrary process in the manufacturing method of the pattern formation body of this invention. It is sectional drawing which shows roughly an example of the micro lens array which can be formed as a functional part in the functional part formation process which is an arbitrary process in the manufacturing method of the pattern formation body of this invention. The graph which shows the relationship between the surface free energy of the to-be-patterned layer after exposure, and the amount of exposure when the to-be-patterned layer is exposed using the mask patterns manufactured in Examples, Comparative Examples 1 and 2, respectively. It is.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 11, 21 Light transmissive substrate 3, 13, 23 Light shielding film pattern 5, 15, 25 Light transmissive part 7, 17, 27 Fluorine containing photocatalytic active layer 10, 20, 30 Photomask 40 Pattern formation layer 40a Hydrophobic application Region 40b Hydrophilic region 50, 135, 150, 165, 170 Pattern forming body 119 Alignment film used in multi-domain liquid crystal display device 119a Hydrophobic region 119b Hydrophilic region 140 Black matrix 145 Color filter array 168 Micro lens array

Claims (8)

A photomask in which a light-shielding film pattern is formed on one side of a light-transmitting substrate and a light-transmitting portion is defined by the light-shielding film pattern
A photomask, wherein a fluorine-containing photocatalytic active layer containing a photocatalyst and a fluorine-based compound is formed so as to overlap the light transmitting portion in plan view.   The light shielding film pattern and the fluorine-containing photocatalytic active layer are formed on the same surface of the light-transmitting substrate, and the fluorine-containing photocatalytic active layer covers the light shielding film pattern. The photomask according to 1. A preparation step of preparing a pattern forming layer capable of changing the wettability of the surface by light irradiation, and a region in which the wettability has changed on the surface of the pattern forming layer by selectively exposing the pattern forming layer A method of manufacturing a pattern forming body comprising a selective exposure step of forming a pattern comprising:
In the selective exposure step, the photomask according to claim 1 or 2 is disposed so that the fluorine-containing photocatalytic active layer faces the pattern formation layer, and a surface of the pattern formation layer is selectively selected. A method for producing a pattern formed body, which comprises exposing.   The method for producing a pattern forming body according to claim 3, wherein in the preparing step, a layer whose surface property changes from hydrophobic to hydrophilic by light irradiation is prepared as the pattern forming layer.   5. The method for producing a pattern forming body according to claim 3, wherein the pattern forming layer is a liquid crystal alignment film.   Furthermore, the manufacturing of the pattern formation body of any one of Claims 3-5 including the functional part formation process which forms a functional part on the said pattern formed at the said selective exposure process. Method.   The method for producing a pattern forming body according to claim 6, wherein in the functional part forming step, a color filter array is formed as the functional part.   The method for manufacturing a pattern forming body according to claim 6, wherein in the functional part forming step, a microlens array is formed as the functional part.

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