A method for producing a photophilic / repellent pattern forming agent, a substrate having a photophilic / repellent pattern forming agent on its surface, and an article having a photophilic / repellent pattern on at least a part of its surface

Abstract

To provide a new method that forms a lyophilic-repellent pattern using a repellent polymer that changes into lyophilic one by photocatalytic activity.SOLUTION: A lyophilic-repellent pattern forming agent contains a photocatalyst, and contains a polymer containing a repeating unit derived from a fluorine-containing compound of a specific structure.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a repellent pattern forming agent, a substrate having a repellent pattern forming agent on a surface thereof, and a method for producing an article having a repellent pattern on at least a portion of its surface. [Background technology]

[0002] A method for producing a pattern formation body has been proposed, which comprises arranging a photocatalyst-containing layer side substrate having at least a photocatalyst-containing layer and a substrate for a pattern formation body having at least a property change layer whose properties change due to the action of the photocatalyst in the photocatalyst-containing layer so that the photocatalyst-containing layer and the property change layer are in contact with each other, exposing the substrate to light to change the properties of the property change layer in the exposed area, and then removing the photocatalyst-containing layer side substrate to obtain a pattern formation body having a pattern with changed properties on the property change layer (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2000-249821 A Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present disclosure is to provide a new method for forming a liquid-philic / liquid-repellent pattern using a liquid-repellent polymer that becomes liquid-philic due to photocatalytic activity. [Means for solving the problem]

[0005] Section 1. A photophilic / repellent pattern forming agent containing a photocatalyst, The following general formula (1): The following general formula (2-1) and / or (2-2) A phobic / philic pattern forming agent comprising a polymer containing a repeating unit derived from a fluorine-containing compound represented by the formula: [ka] (In the formula, X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or CFX 1 X 2 Group (where X 1 and X 2 are the same or different and each is a hydrogen atom, a fluorine atom, or a chlorine atom; a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a linear or branched alkyl group having 1 to 20 carbon atoms; Y is a direct bond, a hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom, -CH 2 CH 2 N(R 1 )SO 2 - group (wherein R 1 is an alkyl group having 1 to 4 carbon atoms, with the right end of the formula bonding to Rf and the left end bonding to O.) 2 CH(OY 1 )CH 2 - group (wherein Y 1 is a hydrogen atom or an acetyl group, and the right end of the formula is bonded to Rf and the left end is bonded to O.) or -(CH 2 ) n SO 2 - group (n is 1 to 10, and the right end of the formula is bonded to Rf and the left end is bonded to O), Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, or a fluoropolyether group having a molecular weight of 400 to 5,000; [ka] (In the formula, W 1 is a fluorine atom, or a perfluoroalkyl or perfluoroalkoxy group having 1 to 3 carbon atoms; W 2 and W 3 each independently represents a perfluoroalkyl group having 1 to 6 carbon atoms which may contain a fluorine atom or an oxygen atom, W 2 and W 3A ring structure may be formed by: [ka] (In the formula, W 4 and W 5 Each of W is independently a perfluoroalkyl group having 1 to 8 carbon atoms which may contain a fluorine atom or an oxygen atom. 4 and W 5 A ring structure may be formed by Section 2. Item 2. The repellent pattern forming agent according to item 1, further comprising a non-fluorinated solvent. Section 3. The photocatalyst is titanium oxide (TiO 2 Item 3. The repellent pattern forming agent according to item 1 or 2, wherein Section 4. 4. The photophilic / repellent pattern forming agent according to any one of items 1 to 3, wherein the polymer contains 45% by mass or more of elemental fluorine. Section 5. 4. The photophilic / repellent pattern forming agent according to any one of items 1 to 3, wherein the polymer is a fluorine-containing polymer containing less than 45% by mass of elemental fluorine, and the content of a fluorine-containing solvent in the solvent is less than 30% by mass. Section 6. Item 6. A substrate having the affinity / repellency pattern forming agent according to any one of items 1 to 5 on its surface. Section 7. Item 7. An organic and / or inorganic patterned conductor having the substrate according to item 6. Section 8. Item 8. An article having the patterned conductor according to item 7. Section 9. Item 9. The article according to item 8, which is at least one article selected from an organic transistor, an organic EL display, an organic EL lighting device, and an organic solar cell. Section 10. A method for producing an article having a repellent pattern on at least a portion of a surface thereof, comprising the steps of: A step of forming an affinity / repellency pattern by irradiating the surface to which the affinity / repellency pattern forming agent according to any one of items 1 to 5 has been applied with electromagnetic waves in a pattern shape. A manufacturing method comprising: Section 11. A composition containing a photocatalyst and a polymer having a structural unit based on a compound represented by general formula (1): [ka] (In the formula, X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or CFX 1 X 2 Group (where X 1 and X 2 are the same or different and each is a hydrogen atom, a fluorine atom, or a chlorine atom; a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a linear or branched alkyl group having 1 to 20 carbon atoms; Y is a direct bond, a hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom, -CH 2 CH 2 N(R 1 )SO 2 - group (wherein R 1 is an alkyl group having 1 to 4 carbon atoms, with the right end of the formula bonding to Rf and the left end bonding to O.) 2 CH(OY 1 )CH 2 - group (wherein Y 1 is a hydrogen atom or an acetyl group, and the right end of the formula is bonded to Rf and the left end is bonded to O.) or -(CH 2 ) n SO 2 - group (n is 1 to 10, and the right end of the formula is bonded to Rf and the left end is bonded to O), Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, or a fluoropolyether group having a molecular weight of 400 to 5,000. Effect of the Invention

[0006] It is possible to provide a new method for forming a lyophilic / repellent pattern using a lyophobic polymer that changes to lyophilic due to photocatalytic activity. [Brief description of the drawings]

[0007] [Figure 1] 1 is a graph showing the relationship between UV exposure time (accumulated light amount) and water contact angle in Examples 1 to 3 and Comparative Example 1. [Diagram 2] 1 is a graph showing the relationship between UV exposure time (accumulated light amount) and water contact angle in Example 4 and Comparative Example 2. [Diagram 3] 1 is a graph showing the relationship between UV exposure time (accumulated light amount) and water contact angle in Examples 5 to 7 and Comparative Example 3. [Figure 4] 1 is a graph showing the relationship between UV exposure time (accumulated light amount) and water contact angle in Examples 9 to 10 and Comparative Example 5. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] In this disclosure, "(meth)acrylic acid" is used as a general term for "acrylic acid" and "methacrylic acid." 1. Repellent pattern forming agent A photophilic / repellent pattern forming agent containing a photocatalyst, The following general formula (1): The following general formula (2-1) and / or (2-2) The present invention relates to a photophilic / phobic pattern forming agent comprising a polymer having a repeating unit derived from a fluorine-containing compound represented by the formula: [ka] (In the formula, X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or CFX 1 X 2 Group (where X 1 and X 2 are the same or different and each is a hydrogen atom, a fluorine atom, or a chlorine atom; a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a linear or branched alkyl group having 1 to 20 carbon atoms; Y is a direct bond, a hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom, -CH 2 CH2 N(R 1 )SO 2 - group (wherein R 1 is an alkyl group having 1 to 4 carbon atoms, with the right end of the formula bonding to Rf and the left end bonding to O.) 2 CH(OY 1 )CH 2 - group (wherein Y 1 is a hydrogen atom or an acetyl group, and the right end of the formula is bonded to Rf and the left end is bonded to O.) or -(CH 2 ) n SO 2 - group (n is 1 to 10, and the right end of the formula is bonded to Rf and the left end is bonded to O), Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, or a fluoropolyether group having a molecular weight of 400 to 5,000; [ka] (In the formula, W 1 is a fluorine atom, or a perfluoroalkyl or perfluoroalkoxy group having 1 to 3 carbon atoms; W 2 and W 3 each independently represents a perfluoroalkyl group having 1 to 6 carbon atoms which may contain a fluorine atom or an oxygen atom, W 2 and W 3 A ring structure may be formed by: [ka] (In the formula, W 4 and W 5 Each of W is independently a perfluoroalkyl group having 1 to 8 carbon atoms which may contain a fluorine atom or an oxygen atom. 4 and W 5 A ring structure may be formed by

[0009] In the conventional method such as that in Patent Document 1, it is necessary to prepare a photocatalyst-containing layer side substrate having a photocatalyst-containing layer for each shape of the affinity-repellency pattern, specifically, a photomask having a photocatalyst-containing layer, and there was a problem that the affinity-repellency pattern forming process becomes complicated. By using the affinity-repellency pattern forming agent of the present disclosure, it is possible to easily form lyophilic regions in a predetermined pattern shape on the treated surface, and further, by applying a functional ink to this treated surface by a printing method, it is possible to achieve a state in which the ink is applied position-selectively only to the lyophilic regions.

[0010] In the case of the lyophilic / repellent pattern forming agent of the present disclosure, it is also possible to selectively chemically bond a functional material to the functional groups in the liquid repellent polymer that are generated as the polymer changes to be lyophilic.

[0011] 1.1 Fluorine-containing polymer (1) The fluorine-containing polymer (1) is a polymer containing repeating units derived from the fluorine-containing compound represented by the above general formula (1).

[0012] The fluoropolymer (1) changes from liquid repellency to liquid affinity when exposed to electromagnetic waves. This change occurs when the fluoroalkyl groups of the fluoropolymer (1) change to hydrophilic groups such as carboxylic acid or hydroxyl groups.

[0013] In the above general formula (1), the fluoroalkyl group represented by Rf is an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and also includes a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.

[0014] Although not particularly limited, in the fluorine-containing compound represented by the above general formula (1), Rf is preferably a linear or branched fluoroalkyl group having 2 to 6 carbon atoms, and particularly preferably a linear or branched perfluoroalkyl group having 4 to 6 carbon atoms, in view of the low environmental load derived from long-chain fluoroalkyl group-containing compounds.

[0015] When Rf is a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, the substituent at the α-position represented by X in the above general formula (1) is preferably a methyl group, an alkyl group other than a hydrogen atom, or a halogen atom, from the viewpoint of improving liquid repellency. Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom and a chlorine atom are preferred.

[0016] Specific examples of the fluorine-containing compound represented by the above general formula (1) are as follows.

[0017] [ka]

[0018] [ka]

[0019] [C10] Rf-SO 2 (CH 2 ) 3 -OCO-CH=CH 2 CH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -S-Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf CH 2 =C(-F)-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf CH 2=C(-Cl)-C(=O)-O-(CH 2 ) 2 -S-Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -S-(CH 2 ) 2 -Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -SO 2 -Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 2 -SO 2 -(CH 2 ) 2 -Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 3 -S-Rf CH 2 =C(-Cl)-C(=O)-O-(CH 2 ) 3 -SO 2 -Rf CH 2 =C(-CH 3 )-C(=O)-O-(CH 2 ) 2 -Rf CH 2 =C(H)-C(=O)-O-(CH 2 ) 2 -Rf

[0020] The fluorine-containing polymer (1) may be a polymer containing a repeating unit derived from one type of fluorine-containing compound represented by the above-mentioned general formula (1), or may be a polymer containing repeating units derived from two or more types of fluorine-containing compounds represented by the above-mentioned general formula (1).

[0021] In the fluorine-containing polymer (1), the proportion of repeating units derived from the fluorine-containing compound represented by general formula (1) in all repeating units is preferably from 50 mol % to 100 mol %, more preferably from 60 mol % to 90 mol %.

[0022] The fluorine-containing polymer (1) may further contain a repeating unit derived from a compound different from the fluorine-containing compound represented by the above general formula (1). The compound serving as the base of such a repeating unit is not limited.

[0023] An example of such a compound is a (meth)acrylic acid ester represented by the following general formula (2). CH 2 =C(R 1 )COOR 2 (2) (In the formula, R 1 is H or CH 3 and R 2 is a group having a saturated alkyl group having 4 to 20 carbon atoms and a ratio of carbon atoms to hydrogen atoms of 0.58 or more.

[0024] In the general formula (2), specific examples of the saturated alkyl group having 4 to 20 carbon atoms and a ratio of carbon atoms to hydrogen atoms of 0.58 or more include isobornyl, bornyl, and fensil (all of which are C 10 H 17 , carbon atom / hydrogen atom = 0.58), adamantyl (C 10 H 15 , carbon atom / hydrogen atom = 0.66), and norbornyl (C 7 H 12 and the like. These bridged hydrocarbon rings may be directly bonded to the COO group, or may be bonded to the COO group via a linear or branched alkylene group having 1 to 5 carbon atoms. At least one or more hydrogen atoms of these bridged hydrocarbon rings may be substituted with a hydroxyl group or an alkyl group (having 1 to 5 carbon atoms, for example).

[0025] In the general formula (2), R2 However, those having 1 to 20 carbon atoms are preferred.

[0026] Specific examples of the (meth)acrylic acid ester represented by the general formula (2) include (meth)acrylates having an isobornyl group, (meth)acrylates having a norbornyl group, and (meth)acrylates having an adamantyl group. Among these, examples of the (meth)acrylates having an isobornyl group include isobornyl methacrylate and isobornyl acrylate, and examples of the (meth)acrylates having a norbornyl group include 3-methyl-norbornylmethyl (meth)acrylate, norbornylmethyl (meth)acrylate, norbornyl (meth)acrylate, and 1,3,3-trimethyl-norbornyl (meth)acrylate. Examples of the (meth)acrylate having an adamantyl group include 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, and 1-adamantyl-α-trifluoromethyl (meth)acrylate. Among these, isobornyl methacrylate is preferred.

[0027] Examples of compounds which are the bases of the repeating units different from the repeating units derived from the fluorine-containing compound represented by the above general formula (1) and which are contained in the fluorine-containing polymer (1) include, in addition to the (meth)acrylic acid ester represented by the above general formula (2), methyl methacrylate, benzyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, etc.

[0028] The fluorine-containing polymer (1) is preferably a copolymer of a fluorine-containing compound represented by general formula (1) and a (meth)acrylic acid ester represented by general formula (2). In this case, the preferred mass ratio of the fluorine-containing compound represented by general formula (1) to the (meth)acrylic acid ester represented by general formula (2) is at least 50:50 and less than 100:0.

[0029] From the viewpoint of achieving excellent liquid repellency in regions where the repellent pattern forming agent of the present disclosure is not applied, or regions where the agent is applied but not irradiated with electromagnetic waves, the mass ratio of the fluorine-containing compound represented by general formula (1) to the (meth)acrylic acid ester represented by general formula (2) is preferably 95:5 to 75:25, and more preferably 90:10 to 80:20. These regions have excellent liquid repellency, and the region that changes to lyophilicity has excellent lyophilicity after the change, so that a large difference in wettability can be generated between the inside and outside of the boundary of the pattern.

[0030] On the other hand, from the viewpoint of being able to use a solvent having excellent dispersibility for the photocatalyst, the mass ratio of the fluorine-containing compound represented by general formula (1) to the (meth)acrylic acid ester represented by general formula (2) is preferably 75:35 to 40:60, and more preferably 70:30 to 50:50.

[0031] The compound which is the base of the repeating unit different from the repeating unit derived from the fluorine-containing compound represented by the above general formula (1) contained in the fluorine-containing polymer (1) is a compound represented by the following general formula (3): [ka] (In the formula, R 3 , R 4 and R 5 are the same or different and are alkoxy groups having 1 to 4 carbon atoms; R 6 is a group containing a radically polymerizable unsaturated bond. Examples of the alkoxysilyl group-containing radically polymerizable monomers represented by the formula: 3 , R 4 and R5 It is particularly preferred that all of R are methoxy groups or ethoxy groups. 6 Examples of the radically polymerizable unsaturated bond contained in R include a vinyl group and a (meth)acryloyl group. 6 R preferably has 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms. 6 In the formula, the radically polymerizable unsaturated bond may be directly bonded to the silicon atom, or may be bonded to the silicon atom via a linear or branched alkylene group or a carbonyl group having 1 to 12 carbon atoms and which may be interrupted by a hydrocarbon ring.

[0032] Specific examples of the alkoxysilyl group-containing radically polymerizable monomer represented by the general formula (3) include monomers represented by the following general formula: [ka]

[0033] In the above formulas, R 3 , R 4 and R 5 is the same as above, and R 6 is a hydrogen atom, a methyl group, or a chlorine atom, and n is an integer of 1 to 10.

[0034] The above-mentioned alkoxysilyl group-containing radical polymerizable monomers may be used alone or in combination of two or more.

[0035] The fluorine-containing polymer (1) may be a copolymer of a fluorine-containing compound represented by general formula (1), a (meth)acrylic acid ester represented by general formula (2), and an alkoxysilyl group-containing radical polymerizable monomer represented by general formula (3). In this case, the proportion of the alkoxysilyl group-containing radical polymerizable monomer represented by general formula (3) in all repeating units is preferably 0.5 mol % to 5 mol %.

[0036] The polymerization method is not particularly limited and can be appropriately selected. Radical polymerization is preferred as the polymerization method. The means for causing the radical polymerization reaction is not particularly limited and can be appropriately selected. Examples of the means for causing the radical polymerization reaction include polymerization by an organic or inorganic radical initiator, light, ionizing radiation, or heat. The mode of the polymerization reaction is not particularly limited and can be appropriately selected. Examples of the mode of the polymerization reaction include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. The weight average molecular weight (Mw) of the fluoropolymer (1) is preferably from 10,000 to 1,000,000.

[0037] The composition of the fluorine-containing polymer (1) is 1 H-NMR, 19 This can be confirmed by F-NMR, FT-IR, LC / MS, GC / MS, etc.

[0038] From the viewpoint of achieving excellent liquid repellency in an area where the phobic / repellent pattern forming agent of the present disclosure is not applied, or an area where the agent is applied but not irradiated with electromagnetic waves, the fluorine-containing polymer (1) is preferably a polymer containing 45% by mass or more of elemental fluorine. The upper limit is not particularly limited, but may be, for example, 99.9% by mass.

[0039] On the other hand, from the viewpoint of being able to use a solvent having excellent dispersibility of the photocatalyst, the fluorine-containing polymer (1) is preferably a polymer containing less than 45% by mass of fluorine element. The lower limit is not particularly limited, but may be, for example, 20% by mass.

[0040] 1.2 Fluorine-containing polymer (2) The fluorine-containing polymer (2) is a polymer containing repeating units derived from the fluorine-containing compound represented by the above general formula (2-1) and / or (2-2) (the fluorine-containing compounds represented by the above general formulas (2-1) and (2-2) may be referred to as "fluorine-containing compound (2-1)" and "fluorine-containing compound (2-2)", respectively).

[0041] The fluoropolymer (2) changes from liquid repellency to liquid affinity when exposed to electromagnetic waves. This change occurs when the fluoroalkyl groups of the fluoropolymer (2) change to hydrophilic groups such as carboxylic acid or hydroxyl groups.

[0042] In the above general formula (2-1), W 2 and W 3 The cyclic structure formed by these may be, for example, a six-membered ring containing two ether oxygen atoms. In the above general formula (2-2), W 4 and W 5 Examples of the cyclic structure formed by this include a 5-membered ring containing one ethereal oxygen atom, and a 6-membered ring containing no ethereal oxygen atom.

[0043] As the fluorine-containing compound (2-1), from the viewpoint of liquid repellency, W 1 is a fluorine atom, and W 2 and W 3 are preferably perfluoromethyl groups having one carbon atom.

[0044] As the fluorine-containing compound (2-2), in terms of liquid repellency, W 4 and W 5 It is preferable that one of these groups is a fluorine atom and the other is a perfluoromethyl group having one carbon atom.

[0045] A specific example of the fluorine-containing compound (2-1) is perfluoro(2,2-dimethyl-1,3-dioxole) (PDD) represented by the following formula (2-1A).

[0046] [ka]

[0047] Further specific examples of the fluorine-containing compound (2-1) include compounds represented by the following formulas (2-1A) to (2-1C).

[0048] [ka]

[0049] Specific examples of the fluorine-containing compound (2-2) include perfluoro(2-methylene-1,3-dioxolane) represented by the following formula (2-2A) and perfluoro(2-methylene-4-methyl-1,3-dioxolane) (MMD) represented by the following formula (2-2B).

[0050] [ka]

[0051] The fluorine-containing polymer (2) preferably contains at least one of the repeating units derived from the fluorine-containing compound (2-1) and the fluorine-containing compound (2-2) in an amount of 10 mol % or more based on the total repeating units. When the fluorine-containing polymer (2) contains both repeating units derived from the fluorine-containing compound (2-1) and the fluorine-containing compound (2-2), it preferably contains the repeating units of both of them in total of 10 mol % or more.

[0052] The fluorine-containing polymer (2) may contain one type or two or more types of repeating units derived from the fluorine-containing compound (2-1). Also, the fluorine-containing polymer (2) may contain one type or two or more types of repeating units derived from the fluorine-containing compound (2-2).

[0053] The repeating units of the fluorine-containing polymer (2) may all be either repeating units derived from the fluorine-containing compound (2-1) or repeating units derived from the fluorine-containing compound (2-2), or the fluorine-containing polymer (2) may contain a repeating unit which does not fall into either of the repeating units derived from the fluorine-containing compound (2-1) or the fluorine-containing compound (2-2) (hereinafter also referred to as other repeating units).

[0054] The fluorine-containing polymer (2) preferably contains the repeating units derived from the fluorine-containing compound (2-1) and the fluorine-containing compound (2-2) in a proportion of 10 mol % or more, particularly preferably 50 mol % or more, based on the total repeating units. When the fluorine-containing polymer (2) contains other repeating units, the content of the other repeating units is preferably 90 mol % or less, particularly preferably 50 mol % or less, based on the total repeating units.

[0055] The other repeating units are not particularly limited and can be selected from a wide range, for example, perfluoroalkylene having 4 or 6 fluorine atoms (e.g., tetrafluoroethylene (TFE)), perfluorovinyl ether (e.g., perfluorobutenyl vinyl ether (BVE)), etc.

[0056] As the other repeating unit, from the viewpoint of improving liquid repellency, a repeating unit (C) derived from tetrafluoroethylene (TFE) or a repeating unit derived from a compound (3) represented by the following formula (3-1) or formula (3-2) is preferable.

[0057] [ka]

[0058] [ka]

[0059] In formula (3-1), X represents a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms. n is 0 or 1. In addition, in formula (3-2), Y represents a perfluoroalkyl group having 1 to 8 carbon atoms, or a perfluoroalkoxy group having 1 to 8 carbon atoms. When the fluorine-containing polymer (2) contains a repeating unit derived from the compound of formula (3-1) or formula (3-2), toughness can be imparted to the liquid-repellent layer obtained from the composition containing this fluorine-containing polymer (2).

[0060] The fluorine-containing polymer (2) can be obtained, for example, by homopolymerizing the fluorine-containing compound (2-1) or the fluorine-containing compound (2-2), or by copolymerizing the fluorine-containing compound (2-1) with the fluorine-containing compound (2-2). The polymer (B) can also be obtained by copolymerizing the fluorine-containing compound (2-1) and / or the fluorine-containing compound (2-2) with tetrafluoroethylene (TFE) or the compound (3).

[0061] The polymerization method is not particularly limited and can be appropriately selected. Radical polymerization is preferred as the polymerization method. The means for causing the radical polymerization reaction is not particularly limited and can be appropriately selected. Examples of the means for causing the radical polymerization reaction include polymerization by an organic or inorganic radical initiator, light, ionizing radiation, or heat. The mode of the polymerization reaction is not particularly limited and can be appropriately selected. Examples of the mode of the polymerization reaction include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.

[0062] The weight average molecular weight (Mw) of the fluoropolymer (2) is preferably from 10,000 to 1,000,000.

[0063] The composition of the fluorine-containing polymer (2) is 1 H-NMR, 19 This can be confirmed by F-NMR, FT-IR, LC / MS, GC / MS, etc.

[0064] 1.3 photocatalyst The photocatalyst may be any photocatalyst that can change the fluoropolymers (1) and (2) from liquid repellent to liquid repellent by its photocatalytic activity, and such photocatalysts can be appropriately selected from a wide range.

[0065] Examples of photocatalysts include titanium oxide (TiO 2 ), tungsten oxide, zinc oxide, and nitrogen-doped titanium oxide tin oxide (SnO 2 ), strontium titanate (SrTiO 3 ), Bismuth oxide (Bi2 O 3 ), and iron oxide (Fe 2 O 3 ) and the like. One or more of these may be selected and used in combination.

[0066] As a photocatalyst, TiO is extremely stable physically and chemically, has high photocatalytic activity, is non-toxic and environmentally friendly, and is made from inexpensive raw materials. 2 is preferred.

[0067] TiO 2 There are anatase and rutile types of zeolite, and the anatase type is preferred because of its high photocatalytic activity.

[0068] The smaller the primary particle size of the photocatalyst, the more effectively the photocatalytic reaction occurs, and the smaller the primary particle size of the photocatalyst is, the more preferable it is, and the average primary particle size of the photocatalyst is preferably 50 nm or less, and particularly preferably 20 nm or less. The average primary particle size of the photocatalyst is usually 5 to 300 nm.

[0069] The affinity / repellency pattern forming agent of the present disclosure preferably contains a photocatalyst in an amount of 10 to 5000 mass %, more preferably 100 to 1000 mass %, and even more preferably 300 to 700 mass %, based on the fluorine-containing polymer.

[0070] 1.4 solvent The repellent pattern forming agent of the present disclosure preferably comprises a solvent.

[0071] The solvent is preferably one which can dissolve the fluorine-containing polymers (1) and / or (2) and disperse the photocatalyst while suppressing aggregation. A fluorine-based solvent or a non-fluorine-based solvent may be used alone or in combination as a mixture of the two, as appropriate.

[0072] In either case where a fluorine-based solvent or a non-fluorine-based solvent is used alone, or where a mixture of these two is used as a solvent, the fluorine-based solvent may be used alone or in combination of two or more. In this case, the non-fluorine-based solvent may be used alone or in combination of two or more. In particular, from the viewpoint of dispersing the photocatalyst well, it is preferable that the philic / repellent pattern forming agent of the present disclosure contains a non-fluorine solvent.

[0073] The non-fluorine-based solvent is not particularly limited and can be appropriately selected from a wide range of solvents. Specific examples include isopropyl alcohol, ethanol, methanol, and butyl alcohol. As the non-fluorine-based solvent, isopropyl alcohol is preferred because of its excellent dispersibility in titanium oxide.

[0074] The fluorine-based solvent is not particularly limited and can be appropriately selected from a wide range of solvents.Specific examples include HFE7300, HFE7200, HFE7100 [all manufactured by 3M Japan Co., Ltd.], AC-6000, AE-3000 [all manufactured by AGC Co., Ltd.], hexafluoroacetone, hexafluoroisopropanol, m-xylene hexafluoride [all manufactured by Central Glass Co., Ltd.], etc.As the fluorine-based solvent, HFE7300, HFE7200, AC-6000 and m-xylene hexafluoride are preferred because of their high solubility in isopropyl alcohol.

[0075] In particular, when a polymer containing 45 mass% or more of fluorine element is used as the fluorine-containing polymers (1) and (2), it is preferable to use a mixture of a fluorine-based solvent and a non-fluorine-based solvent. In this case, the total content of the non-fluorine-based solvent in the entire solvent can be 3 mass% to 80 mass%, more preferably 20 mass% to 70 mass%, particularly preferably 40 mass% to 60 mass%.

[0076] In particular, when a polymer containing less than 45 mass % of fluorine element is used as the fluorine-containing polymers (1) and (2), the total content of the fluorine-containing solvents in the entire solvent is preferably less than 30 mass. Furthermore, it is particularly preferable to use a non-fluorine-containing solvent alone without containing a fluorine-containing solvent.

[0077] The surface tension of the solvent is preferably 13 to 23 mN / m, and particularly preferably 16 to 23 mN / m. The surface tension of the solvent is a value measured by the Wilhelmy method.

[0078] 1.5 Other Ingredients The repellent pattern forming agent of the present disclosure may further contain other components, such as a fluorescent agent and a pigment.

[0079] 1.6 Method for producing repellent pattern forming agent The method for producing the pattern forming agent of the present disclosure is not limited. The pattern forming agent of the present disclosure can be produced, for example, as follows.

[0080] First, a photocatalyst is dispersed in a solvent. Then, a polymer containing a repeating unit derived from a fluorine-containing compound is dispersed in the solvent in which the photocatalyst has been dispersed. By dispersing in this order, the dispersibility of the photocatalyst in the polymer is improved. This makes it possible to obtain a more uniform photophilic / repellent pattern forming agent compared to a case in which the order is changed.

[0081] 1.7 Purpose The lyophilic / repellent pattern forming agent of the present disclosure is used for forming a lyophilic / repellent pattern consisting of a region exhibiting lyophilicity to a functional ink and a region exhibiting lyophobicity to the same ink. More specifically, the lyophilic / repellent pattern forming agent of the present disclosure is used for (1) forming an organic and / or inorganic conductive pattern on a flexible substrate having excellent durability against bending and stretching, and (2) forming an organic and / or inorganic semiconductor or insulator pattern, etc.

[0082] The parent / repellent pattern forming agent of the present disclosure can be used to form a parent / repellent pattern by irradiating a pattern-wise electromagnetic wave on a treated surface to which it has been applied. The method of irradiating the electromagnetic wave in a pattern is generally a method of irradiating the entire surface of a substrate through a photomask on which a pattern is drawn, but is not limited thereto. For example, a maskless exposure device capable of drawing a pattern with ultraviolet LED light using a digital micromirror device (DMD) may be used.

[0083] 2. Base material The substrate of the present disclosure is a substrate having a repellent pattern forming agent on its surface.

[0084] Since the substrate of the present disclosure has a photophilic pattern forming agent on its surface, a photophilic pattern can be formed on the surface by irradiating electromagnetic waves in a pattern. By irradiating a metal substrate with electromagnetic waves and printing a conductive ink, an organic and / or inorganic patterned conductor can be produced. For this reason, the substrate of the present disclosure can be used as an advantageous article having a photophilic pattern formed on its surface. Such articles are not particularly limited and can be selected from a wide range. Specific examples of such articles may be devices having patterns of organic and / or inorganic conductors, semiconductors, or insulators. Specific examples of such articles include organic electronic devices such as organic transistors, organic EL displays, organic EL lighting, and organic solar cells.

[0085] 3. Method for manufacturing an article having a repellent pattern on at least a portion of its surface The manufacturing method of the present disclosure for an article having a parent-repellent pattern on at least a portion of its surface is a manufacturing method including a step of forming a parent-repellent pattern by irradiating electromagnetic waves in a pattern shape on the surface of an article to which the parent-repellent pattern forming agent has been applied.

[0086] The method of electromagnetic wave irradiation (irradiation is also called exposure) is not particularly limited, and can be selected from a wide range of methods that can change the properties of the pattern forming agent from liquid repellency to liquid affinity. Specific examples include ordinary ultraviolet rays (200 to 400 nm), vacuum ultraviolet rays (172 nm), electron beams, and soft X-ray synchrotron radiation.

[0087] The irradiation (exposure) time of the electromagnetic waves is preferably from 5 s to 300 min, and more preferably from 5 s to 200 min.

[0088] The cumulative light intensity of electromagnetic waves is 5 mJ / cm 2 ~300J / cm 2 is preferred, and 10 mJ / cm 2 ~200J / cm 2 is more preferable. When the substrate is covered with a photomask, the high concentration of ozone generated by the photocatalyst between the substrate and the photomask promotes lyophilization. Even when maskless exposure is used, the same effect can be obtained by covering the substrate with quartz glass.

[0089] A substrate coated with the lyophilic / repellent pattern forming agent of the present disclosure is irradiated with electromagnetic waves in a predetermined pattern shape to obtain a lyophilic / repellent pattern substrate, and then a functional ink is applied by a printing method to the lyophilic / repellent pattern substrate, whereby the functional ink spreads selectively in the position only in the patterned lyophilic regions. This principle makes it possible to manufacture high-definition functional material patterns at low cost. In the lyophilic / repellent pattern forming agent of the present disclosure, a functional group, such as a carboxylic acid, generated as a result of the agent changing to lyophilicity can be selectively chemically bonded to a functional material, such as silver. For example, a carboxylic acid extending from a polymer main chain as disclosed in JP 2015-044373 A can be generated by ordinary ultraviolet light (wavelength 200 to 400 nm) without using high-energy electromagnetic waves such as vacuum ultraviolet light (wavelength 172 nm).

[0090] Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims. EXAMPLES

[0091] The present disclosure will now be described in more detail with reference to Production Examples and Examples.

[0092] Production Example 1 [Phot-and-phobic pattern-forming agent (fluorine element concentration of fluoropolymer: 50% by mass, IPA content in solvent: 4.9% by mass)] In a four-neck flask, add perfluorohexyl methacrylate (CH 2 =C(CH 3 )COOCH 2 CH 2 C 6 F 13 30.625 g of Rf(C6) methacrylate (hereinafter sometimes abbreviated as "Rf(C6) methacrylate"), 4.375 g of isobornyl methacrylate (hereinafter sometimes abbreviated as "iBMA"), and perfluorobutyl ethyl ether (C 6 F 13 OCH 3 The reactor was charged with 66 g of HFE7300 (hereinafter sometimes abbreviated as "HFE7300"), purged with nitrogen for 10 minutes, and heated to 70° C. 0.149 g of azobisisobutyronitrile (hereinafter sometimes abbreviated as "AIBN") was added and reacted for 6 hours to obtain an Rf(C6) methacrylate / iBMA=100 / 14.3 (mass ratio) copolymer.

[0093] After cooling to room temperature, the fluoropolymer was precipitated with methanol and dried under reduced pressure. The molecular weight of the fluoropolymer obtained by the above method was measured by GPC using a fluorine-based solvent [HCFC225 / hexafluoroisopropanol=90 / 10 (by weight)] as an eluent, and the weight average molecular weight was 115,500.

[0094] 0.2 g of the above fluoropolymer was dissolved in 93.92 g of HFE7300, and then 5.88 g of "TKD-701" [manufactured by Teika Co., Ltd., 17% by mass IPA dispersion], a product in which photocatalytic titanium oxide was previously dispersed in IPA, was added (component ratio TiO 2 After uniformly dispersing the mixture, the mixture was irradiated with ultrasonic waves for 5 minutes in an ultrasonic cleaner to prepare a "philic / repellent pattern forming agent."

[0095] Production Example 2 [Phot-and-phobic pattern forming agent (fluorine element concentration of fluorine-containing polymer: 50% by mass, IPA content in solvent: 25% by mass)] A repellent pattern forming agent was prepared in the same manner as in Preparation Example 1, except that the amount of HFE7300 blended in the repellent pattern forming agent was changed from 93.92 g to 74.1 g and 24.7 g of IPA was newly added.

[0096] Production Example 3 [Phot-and-phobic pattern forming agent (fluorine element concentration of fluorine-containing polymer: 50% by mass, IPA content in solvent: 50% by mass)] A repellent pattern forming agent was prepared in the same manner as in Preparation Example 1, except that the amount of HFE7300 blended in the repellent pattern forming agent was changed from 93.92 g to 46.96 g and 46.96 g of IPA was newly added.

[0097] Reference example [Surface tension of IPA / HFE7300 mixed solvent] The surface tension of the IPA / HFE7300 mixed solvent was measured by the Wilhelmy method, and the results are shown in Table 1. The surface tension of the solvent used in the phobic / philic pattern forming agent in the examples of the present disclosure is in the range of 14 to 23 mN / m.

[0098] [Table 1]

[0099] Comparative Production Example 1 [Fluorine element concentration of fluoropolymer: 50% by mass, IPA content in solvent: 0% by mass, no titanium oxide] Comparative Production Example 1 was prepared by the same method as in Production Example 1 except that the amount of HFE7300 blended in the repellent pattern forming agent was changed from 93.92 g to 99.8 g and TKD-701 was not added.

[0100] Example 1 A "parent-repellent pattern forming agent coated substrate" was produced by spin-coating (2000 rpm, 25 seconds, no heat treatment) the parent-repellent pattern forming agent of Production Example 1 onto a silicon wafer (thickness 0.5 mm) cut to 23 mm square. Quartz glass was placed on top of this coated substrate, and a UV exposure device, Mask Aligner ES20d [manufactured by Minaga Electric Manufacturing Co., Ltd. and Nanotec Co., Ltd. Illuminance: 16.67 mW / cm 2 , UV wavelength: i (365 nm), h (405 nm), g (436 nm) line mixture, cumulative light dose 50 J / cm 2In increments of 150J / cm 2 The water contact angle (WCA (°)) was measured while irradiating the surface with UV light until 5 seconds after the droplet of 2 μL was deposited.

[0101] Examples 2 and 3, Comparative Example 1 The pattern-forming agent of Example 1 was replaced with the pattern-forming agents of Production Examples 2 and 3, and Comparative Production Example 1, which were used to prepare Examples 2, 3, and Comparative Example 1, respectively. Except for the above-mentioned substitutions, substrates coated with the pattern-forming agent were prepared in the same manner as in Example 1, and the water contact angles were measured while exposing the substrate to UV light.

[0102] The relationship between the UV exposure time (accumulated light amount) and the water contact angle in Examples 1 to 3 and Comparative Example 1 is shown in Table 2 and FIG.

[0103] [Table 2]

[0104] Production Example 4 [Phot-and-phobic pattern-forming agent (fluorine element concentration of fluorine-containing polymer: 34% by mass, IPA content in solvent: 100% by mass)] A four-neck flask was charged with 21 g of Rf(C6) methacrylate, 14 g of iBMA, and 66 g of IPA, and the flask was purged with nitrogen for 10 minutes and heated to 70° C. 0.149 g of AIBN was then added and reacted for 6 hours to obtain an Rf(C6) methacrylate / iBMA=3 / 2 (mass ratio) copolymer.

[0105] The polymer was isolated in the same manner as in Production Example 1, and the molecular weight was measured by GPC, and the weight average molecular weight was found to be 138,000.

[0106] 0.2 g of the above fluoropolymer was dissolved in 93.92 g of IPA, and then TKD-701, a product in which photocatalytic titanium oxide had been dispersed in IPA in advance, was added and uniformly dispersed. The mixture was then irradiated with ultrasonic waves for 5 minutes in an ultrasonic cleaner to prepare a photophilic / repellent pattern forming agent.

[0107] Comparative Production Example 2 [Fluorine element concentration of fluoropolymer: 34% by mass, IPA content in solvent: 100% by mass, no titanium oxide] Comparative Production Example 4 was prepared by the same method as in Production Example 4 except that the amount of IPA added to the repellent pattern forming agent was changed from 93.92 g to 99.8 g and TKD-701 was not added.

[0108] Example 4, Comparative Example 2 Except for replacing the phil-repellent pattern-forming agent of Example 1 with the phil-repellent pattern-forming agent of Production Example 4 or Comparative Production Example 2, a substrate coated with the phil-repellent pattern-forming agent was prepared in the same manner as in Example 1, and the water contact angle was measured while exposing the substrate to UV light.

[0109] The relationship between the UV exposure time (accumulated light amount) and the water contact angle in Example 4 and Comparative Example 2 is shown in Table 3 and FIG.

[0110] [Table 3]

[0111] Examples 5 to 7 [Phase-forming agent in which the fluorine-containing polymer is replaced from Rf(C6) methacrylate / iBMA copolymer to Teflon (registered trademark) AF] Except for replacing the fluorine-containing polymer Rf(C6) methacrylate / iBMA copolymer blended in the philic-phobic pattern-forming agents of Production Examples 1 to 4 with Teflon AF1600 (manufactured by DuPont), substrates coated with the philic-phobic pattern-forming agent were prepared in the same manner as in Examples 1 to 4, and UV exposure and water contact angles were measured.

[0112] Comparative Example 3 [Pattern-forming agent in which the fluorine-containing polymer is replaced from Rf(C6) methacrylate / iBMA copolymer to Teflon AF, IPA content in the solvent: 0% by mass, no titanium oxide] Except for changing the amount of IPA in Example 5 from 93.92 g to 99.8 g and not adding TKD-701, a photophilic / repellent pattern-forming agent-coated substrate was prepared in the same manner as in Example 5, and the water contact angle was measured while exposing the substrate to UV light.

[0113] The relationship between the UV exposure time (accumulated light amount) and the water contact angle in Examples 5 to 7 and Comparative Example 3 is shown in Table 4 and FIG.

[0114] [Table 4]

[0115] Example 8 and Comparative Example 4 [Printing of Ag nanometal ink on a photophilic / phobic pattern-formed substrate] The substrates coated with the affinity / repellency pattern forming agents prepared in Example 3 and Comparative Example 1 were irradiated with a cumulative light dose of 50 J / cm through a photomask on which lines and spaces with line widths of 50 μm to 500 μm and lengths of 2 cm were drawn. 2 A photophile-repellent pattern was created by exposing the substrate to UV light at 400 nm. Next, Ag nanometal ink was printed under the following conditions. Manufacturing method of Ag nano metal ink: Ag nanometal ink refers to a dispersion of silver nanowires (sometimes called silver particles) in ethanol in the range of 0.1 to 1 mass %, and is prepared by the method described in the paper by the inventor, Nano Research, February 2014, Volume 7, Issue 2, pp. 236-245. That is, it was chemically synthesized by reducing silver nitrate in an ethylene glycol (EG) solvent in which polyvinylpyrrolidone (PVP) and chloride ions are dissolved. First, a PVP solution was prepared by mixing 0.163 g of PVP (average molecular weight: 360k) with 22 g of EG solvent. A silver nitrate solution [solvent: EG 3 g, solute: silver nitrate (I)] and 2.8 g of iron chloride solution [solvent: EG, solute: iron chloride (III), concentration: 600 μmol / L] were added to the PVP solution in this order to prepare a pre-reaction mixed solution. The mixed solution was reacted at 110°C for 12 hours with a stirring speed of 60 rpm, and then the reaction solution was centrifuged three times and replaced with an ethanol solvent to prepare Ag nanometal ink. Equipment: 2-axis stage controller [Sigma Optical Machinery Co., Ltd.] Coating conditions: (S:Minimum)100pps=0.4mm / s (F:Maximum)100pps=0.4mm / s (R: acceleration / deceleration time) R=200ms As a result, when the photophilic / repellent pattern forming agent-coated substrate prepared in Example 3 (IPA content in the pattern forming agent solvent: 50% by mass) was used, good quality metal wiring with a line width of 100 μm or more was produced. On the other hand, when the photophilic / repellent pattern forming agent-coated substrate prepared in Comparative Example 1 (IPA content in the pattern forming agent solvent: 0% by mass, no titanium oxide) was used, the Ag nanometal ink could not be applied in a pattern.

[0116] Examples 9 to 11 and Comparative Example 5 [Relationship between UV integrated light amount and water contact angle when the substrate is replaced from a silicon wafer to a film] The repellent pattern forming agent of Production Example 3 (IPA content in the solvent: 50% by mass) was applied to flexible resin films (1) PET film (film thickness: 100 μm), (2) diX-SR [paraxylylene-based polymer manufactured by KISCO Ltd.] evaporated PET film (film thickness: 100 μm), and (3) COP film (film thickness: 190 μm) instead of silicon wafers (Examples 1 to 3, Comparative Example 1), and UV irradiation and water contact angle measurement were performed in the same manner as in Example 1. These were designated as Examples 9, 10, and 11, respectively. Also, Comparative Production Example 1 (IPA content in the solvent: 0% by mass, TiO 2 A case where a polymeric pattern-forming agent having a molecular weight of 1000 g / cm or less (none) was applied to a PET film (film thickness 100 μm), UV irradiation was performed, and the water contact angle was measured in the same manner as in Example 1 was performed, which was defined as Comparative Example 5. The resin film was attached to a silicon wafer (φ10 cm) with double-sided tape, and the portion protruding from the Si wafer was cut off, after which the polymeric pattern-forming agent was spin-coated.

[0117] The results of the water contact angle when irradiated with UV are shown in Table 5 and Figure 4. Regardless of which resin film was used, the integrated light dose of 50 J / cm2 was the same as for the silicon wafer. 2 The surface became hydrophilic to the point where the water contact angle was generally 10° or less.

[0118] [Table 5]

[0119] Example 12, Comparative Example 6 [Printing of Ag nanometal ink onto a polymeric / repellent pattern-forming resin film] The photosensitive pattern forming agent-coated substrates prepared in Example 3 and Comparative Example 1 were irradiated with a cumulative light dose of 50 J / cm through a photomask on which lines and spaces with line widths of 50 μm to 500 μm and lengths of 2 cm were drawn. 2 A repellent pattern substrate was fabricated by exposing the substrate to UV light at 1000 rpm. Next, Ag nanometal ink was printed under the same conditions as in Example 8 and Comparative Example 4. As a result, when the photophilic / repellent pattern forming agent-coated substrate prepared in Example 3 (IPA content in the pattern forming agent solvent: 50% by mass) was used, good quality metal wiring with a line width of 100 μm or more was produced. On the other hand, when the photophilic / repellent pattern forming agent-coated substrate prepared in Comparative Example 1 (IPA content in the pattern forming agent solvent: 0% by mass, no titanium oxide) was used, the Ag nanometal ink could not be applied in a pattern.

Claims

1. A lyophilic / repellent pattern-forming agent containing a photocatalyst, which is used to change from liquid repellency to liquid affinity by irradiating a pattern-wise electromagnetic wave, thereby forming a lyophilic / repellent pattern, The following general formula (1): The following general formula (2-1) and / or (2-2) A photophilic / phobic pattern forming agent comprising a polymer containing a repeating unit derived from a fluorine-containing compound represented by the formula: 【Chemistry 1】 (In the formula, X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or CFX １ X ２ Group (wherein X １ and X ２ are the same or different and each is a hydrogen atom, a fluorine atom, or a chlorine atom; a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a linear or branched alkyl group having 1 to 20 carbon atoms; Y is a direct bond, a hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom, -CH ２ CH ２ N (R １ ) S.O. ２ - group (wherein R １ is an alkyl group having 1 to 4 carbon atoms, the right end of which is bonded to Rf and the left end of which is bonded to O.), —CH ２ CH (OY １ ) CH ２ - group (wherein Y １ is a hydrogen atom or an acetyl group, and the right end of the formula is bonded to Rf and the left end is bonded to O.) or -(CH ２ ) ｎ SO ２ - group (n is 1 to 10, and the right end of the formula is bonded to Rf and the left end is bonded to O), Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, or a fluoropolyether group having a molecular weight of 400 to 5,000; 【Chemistry 2】 (In the formula, W １ is a fluorine atom, or a perfluoroalkyl or perfluoroalkoxy group having 1 to 3 carbon atoms; W ２ and W ３ each independently represents a perfluoroalkyl group having 1 to 6 carbon atoms which may contain a fluorine atom or an oxygen atom; W ２ And W ３ A cyclic structure may be formed by: 【Chemistry 3】 (In the formula, W ４ and W ５ Each of W is independently a fluorine atom or a perfluoroalkyl group having 1 to 8 carbon atoms which may contain an oxygen atom. ４ And W ５ A ring structure may be formed by

2. The repellent pattern forming agent according to claim 1 , further comprising a non-fluorinated solvent.

3. The photocatalyst is titanium oxide (TiO ２ 3. The agent for forming a repellent pattern according to claim 1 or 2, wherein

4. 4. The agent for forming a phobic pattern according to claim 1, wherein the polymer contains 45% by mass or more of elemental fluorine.

5. The agent for forming a photophilic / repellent pattern according to any one of claims 1 to 3, wherein the polymer is a fluorine-containing polymer containing less than 45% by mass of elemental fluorine, and the content of a fluorine-containing solvent in the solvent is less than 30% by mass.

6. A substrate having a photophilic / repellent pattern formed on its surface by the photophilic / repellent pattern forming agent according to any one of claims 1 to 5.

7. An organic and / or inorganic patterned conductor having the substrate according to claim 6 .

8. An article comprising the patterned conductor according to claim 7.

9. The article according to claim 8 , which is at least one article selected from the group consisting of an organic transistor, an organic electroluminescence display, an organic electroluminescence lighting device, and an organic solar cell.

10. A method for producing an article having a repellent pattern on at least a portion of a surface thereof, comprising the steps of: A manufacturing method comprising the step of changing the liquid repellency of the surface to which the agent for forming a repellent pattern according to any one of claims 1 to 5 has been applied from liquid repellency to liquid affinity by irradiating the surface with electromagnetic waves in a pattern shape, thereby forming a repellent pattern.

Images