Photosensitive surface treatment agent, pattern-forming substrate, laminate, transistor, pattern-forming method, and method for manufacturing a transistor

Abstract

To provide a photosensitive surface treatment agent.SOLUTION: A photosensitive surface treatment agent includes a compound expressed with a following formula (M1) (in the formula (M1), R1 denotes a hydrogen atom, a tert-butoxycarbonyl group or an ester-based protective group, R2 denotes a hydrogen atom or an alkyl group having 1-6 carbon atoms, m denotes an integer of 1 or larger, and X denotes a halogen atom or an alkoxy group. [Chem.1].SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive surface treatment agent, a pattern-forming substrate, a laminate, a transistor, a pattern-forming method, and a method for manufacturing a transistor. [Background technology]

[0002] In recent years, methods have been proposed for manufacturing microdevices such as semiconductor elements, integrated circuits, and devices for organic EL displays by forming patterns with different surface properties on a substrate and utilizing these differences in surface properties to create microdevices.

[0003] One method of pattern formation that utilizes differences in surface properties on a substrate is to create a region on the substrate in which chemically active substituents are generated. This method allows metallic, organic, or inorganic materials to adhere closely to a portion of the substrate.

[0004] One technique for forming a metal film by adhering a metal material to a substrate is electroless plating. For example, Patent Document 1 discloses a technique for forming fine wiring by electroless plating. Specifically, Patent Document 1 discloses a method using a catalyst activation layer and a photoresist to perform photopatterning by etching or lift-off after plating the entire surface. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2006-2201 [Overview of the project]

[0006] A first aspect of the present invention is a photosensitive surface treatment agent comprising a compound represented by the following formula (M1).

[0007] [ka] (In formula (M1), R 1 is a hydrogen atom, a tert-butoxycarbonyl group, or an ester-based protecting group, R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m is an integer of 1 or more, and X is a halogen atom or an alkoxy group.)

Brief Description of the Drawings

[0008] [Figure 1] It is a schematic diagram for explaining the pattern formation method of this embodiment. [Figure 2] It is a schematic diagram for explaining the manufacturing method of the transistor of this embodiment. [Figure 3A] Optical microscope images of L / S = 100 / 100 and 5 / 5 processed on a PET substrate by the above plating wiring manufacturing steps 1 to 4. [Figure 3B] Optical microscope images of L / S = 1 / 1 to 9 / 9 μm processed on a PET substrate by the above plating wiring manufacturing step 3. [Figure 4A] It is the molecular structure of the resin film on the PET substrate. [Figure 4B] It is an overall image of the PET substrate processed by the above plating wiring manufacturing step 5.

Mode for Carrying Out the Invention

[0009] <Photosensitive Surface Treatment Agent> The photosensitive surface treatment agent of the present invention contains a compound represented by the following formula (M1).

[0010]

Chemical Formula

[0011] In formula (M1), R 1is a hydrogen atom, a tert-butoxycarbonyl group, or an ester-based protecting group.

[0012] Examples of the ester-based protecting group include an acetyl (Ac) group, a pivaloyl (Pv) group, a propoxycarbonyl group, a tert-butoxycarbonyl group, and a benzoyl group.

[0013] As long as it is a structure for protecting a hydroxyl group, it is not particularly limited thereto. For example, acetal-based protecting groups such as methoxymethyl (MOM), methoxyethoxymethyl (MEM), and 2-tetrahydropyranyl (THP), ether-based protecting groups such as methyl, tert-butyl (tBu), trityl (Tr), benzyl (Bn), p-methoxybenzyl, trimethylsilyl (TMS), triethylsilyl (TES), and t-butyldimethylsilyl (TBDMS), and any other protecting groups described in Greene’s Protective Groups in Organic Synthesis 5th Edition (published by John Wiley & Sons, Inc. in 2014), as well as any deprotection conditions, can be applied.

[0014] Among these, from the viewpoints of stability, high reactivity in protection and deprotection, and simplicity of synthesis, R 1 is preferably a tert-butoxycarbonyl group.

[0015] In formula (M1), R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a hexyl group, and a cyclohexyl group.

[0016] In formula (M1), m is an integer of 1 or more, and X is a halogen atom or an alkoxy group. Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0017] X is preferably an alkoxy group. Examples of alkoxy groups for X include -O-(CH3) and -O-(CH2)n(CH3), where n is a natural number between 1 and 3.

[0018] In formula (M1), R 1 When a photosensitive surface treatment agent containing a compound in which is a tert-butoxycarbonyl group is applied to a substrate, SiX3 adheres to the substrate and a resin film is formed, as shown below. This resin film has suppressed photosensitivity because the hydroxyl group is protected by a tert-butoxycarbonyl group (hereinafter sometimes referred to as "Boc" in the formula).

[0019] [ka]

[0020] By deprotecting the resin film, the tert-butoxycarbonyl group is removed, as shown below, generating a hydroxyl group and resulting in a photosensitive resin film.

[0021] [ka]

[0022] When the resulting photosensitive resin film is irradiated with light, the nitrobenzyl group is removed, and amines are generated on the substrate surface. Metallic, organic, or inorganic materials can be adhered to the areas where the amines are generated.

[0023] According to the photosensitive surface treatment agent of this embodiment, by placing a metal material in the amine generation area formed on the substrate surface, a metal pattern with a line width of 5 μm or less can be formed on the substrate surface without using a photoresist process, a development process, or an etching process.

[0024] [ka]

[0025] In the state of the resin film, the photosensitivity is suppressed, so after applying the photosensitive surface treatment agent to the substrate, it can be stably stored without the progress of photodegradation. According to the present invention, it is possible to apply the photosensitive surface treatment agent to the substrate and store it, and deprotect and use it immediately before pattern formation.

[0026] In formula (M1), R 1 When using a photosensitive surface treatment agent containing a compound in which R is a tert-butoxycarbonyl group, the deprotection method is specifically deprotection using hydrolysis under acidic conditions such as hydrochloric acid or trifluoroacetic acid.

[0027] In formula (M1), R 1 When using a photosensitive surface treatment agent containing a compound in which R is an ester-based protecting group, the deprotection method is specifically deprotection using hydrolysis under acidic conditions or basic conditions, or hydride reduction.

[0028] Specific examples of the compound represented by formula (M1) are shown below.

[0029] [Chemical formula]

[0030] [Method for producing compound] The compound represented by formula (M1) can be produced by the following method. First, 6-bromo-4-hydroxymethyl-7-hydroxycoumarin is synthesized by the method described in the examples.

[0031] When the compound represented by formula (M1) is a compound in which R 1 is a hydrogen atom, by reacting an aminosilane compound with 6-bromo-4-hydroxymethyl-7-hydroxycoumarin, a compound represented by formula (M1) in which R 1 is a hydrogen atom can be synthesized.

[0032] When the compound represented by formula (M1) is such that R 1If the compound is a tert-butoxycarbonyl group, first, 6-bromo-4-hydroxymethyl-7-hydroxycoumarin is reacted with a compound containing a tert-butoxycarbonyl group to synthesize 6-bromo-7-tert-butoxycarbonyloxy-4-hydroxymethylcoumarin.

[0033] Compounds containing a tert-butoxycarbonyl group include, for example, 1-tert-butoxy-2-tert-butoxycarbonyl-1,2-dihydroisoquinoline, di-tert-butyldicarbonate, 1-tert-butoxycarbonyl-1,2,4-triazole, N-(tarto-butoxycarbonyloxy)phthalimide, N-tarto-butoxycarbonyliimidazole, and tert-butylphenyl carbonate.

[0034] By reacting 6-bromo-7-tert-butoxycarbonyloxy-4-hydroxymethylcoumarin with an aminosilane compound, R 1 This allows for the synthesis of compounds represented by formula (M1), which has a tert-butoxycarbonyl group.

[0035] The compound represented by formula (M1) is R 1 If the compound is an ester protecting group, first, 6-bromo-4-hydroxymethyl-7-hydroxycoumarin is reacted with a compound containing an ester protecting group precursor to synthesize an intermediate.

[0036] Examples of compounds containing ester protecting groups include acetyl chloride, acetic anhydride, pivaloyl chloride, pivalic anhydride, benzoyl chloride, and benzoic anhydride.

[0037] By reacting the resulting intermediate with an aminosilane compound, R 1 Compounds represented by formula (M1), in which is an ester protecting group, can be synthesized.

[0038] In one embodiment of the present invention, the photosensitive surface treatment agent comprises a compound represented by the above formula (M1).

[0039] In one embodiment of the present invention, the photosensitive surface treatment agent may contain a solvent. By dissolving it in a common organic solvent such as an alcohol-based solvent, an ester-based solvent, a hydrocarbon-based aromatic solvent, an amine-based solvent, a ketone-based solvent, a glycol ether-based solvent, or an ether-based solvent, it can be used as a suitable surface treatment agent.

[0040] Examples of alcohol-based solvents include isopropyl alcohol (IPA) and n-butyl alcohol (n-butanol).

[0041] Examples of ester solvents include ethyl acetate (EAC), butyl acetate (NBAC), n-propyl acetate (NPAC), and 3-methoxy-3-methylbutyl acetate.

[0042] Examples of hydrocarbon aromatic solvents include toluene, xylene, benzene, ethylbenzene, and trimethylbenzene.

[0043] Examples of amine-based solvents include N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), and N,N-dimethylacetamide (DMAC).

[0044] Examples of ketone-based solvents include methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), diisobutyl ketone (DIBK), methyl isopropyl ketone (MIPK), cyclohexanone, cyclopentanone (CPN), cycloheptanone, and acetone.

[0045] Examples of glycol ether solvents include methylcellosolve, butycellosolve, ethylene glycol mono-t-butyl ether (ETB), propylene glycol monomethyl ether (PGME), and proether solvents such as pyrene glycol monomethyl ether acetate (PGMEA) and 3-methoxy-3-methyl-1-butanol (MMB).

[0046] Other solvents include halogenated solvents containing chlorine or fluorine, such as chloroform, chlorobenzene, and fluoroalkyl ethers. These may be used individually or in combination of two or more.

[0047] Organic solvents can be appropriately selected according to conditions such as pollution, solubility, volatility, attack on substrates and undercoats, and the film deposition equipment and methods.

[0048] From the viewpoint of enhancing the reactivity between the primer and the photosensitive surface treatment agent, or between the molecules of the photosensitive surface treatment agent, alcohol-based, ether-based, and hydrocarbon-based solvents are preferred as the solvents included, with hydrocarbon-based solvents, and toluene being particularly preferred.

[0049] Furthermore, to enhance reactivity, any acidic or basic compound may be included during film formation. This can be appropriately selected depending on the film formation conditions, with acidic compounds such as hydrochloric acid, acetic acid, and nitric acid being particularly preferred, and acetic acid being preferred among these as it allows film formation while maintaining Boc.

[0050] <Pattern Formation Method> The pattern formation method of this embodiment comprises the steps of: applying the photosensitive surface treatment agent of this embodiment onto a substrate to form a resin film; deprotecting the resin film to form a photosensitive resin film; irradiating the photosensitive resin film with light of a predetermined pattern to form amine generation regions in the exposure region; and placing an electroless plating catalyst in the amine generation region and performing electroless plating. The following describes each process with reference to the diagrams.

[0051] As shown in Figure 1(a), the photosensitive surface treatment agent of this embodiment is applied to the substrate 11 to obtain a resin film 10a. Suitable coating methods include, for example, spin coating, dip coating, die coating, spray coating, roll coating, microgravure, lip coating, inkjet, applicator coating, and brush coating. Alternatively, coating may be applied using printing methods such as flexographic printing or screen printing.

[0052] In addition, as shown in Figure 1(a), a process to dry the solvent by means of heat or reduced pressure may be added to this process.

[0053] The resin film is deprotected to form a photosensitive resin layer 10. Specifically, the deprotection treatment is a hydrolysis treatment under acidic conditions using hydrochloric acid, sulfuric acid, hydrofluoric acid, antimonate hexafluoride, or trifluoroacetic acid. The deprotection treatment may be carried out in the liquid phase or in the solid phase by contacting a gel or film. The gel or film may be in the form of a single sheet or a roll. As a result, a photosensitive surface treatment layer 10 is formed on the substrate 11, as shown in Figure 1(b). The deprotection treatment may be performed immediately after the formation of the resin film, or it may be performed immediately before exposure to improve the storage stability of the resin film.

[0054] Next, as shown in Figure 1(c), a photomask 13 having an exposure area of ​​a predetermined pattern is prepared. The exposure method is not limited to using a photomask; other methods such as projection exposure using an optical system such as a lens or mirror, or maskless exposure using a spatial light modulation element or laser beam can be used. The photomask 13 may be provided in contact with the photosensitive surface treatment layer 10, or it may be provided in a non-contact manner.

[0055] The surface of the photosensitive resin layer may be exposed while immersed in any liquid during exposure, or exposed after immersion. The type of liquid is not particularly limited, but water, alcohol-based solvents, or ketone-based solvents can be selected. These may be used individually or in combination of two or more.

[0056] Basic compounds may be added to increase the acid dissociation constant (Ka) and create any desired basic solution. Basic compounds can be selected from alkali metal carbonates such as sodium bicarbonate and potassium carbonate, alkali metal hydrides such as sodium hydride and sodium tetraborohydride, alkali metal hydroxides such as cesium hydroxide, lithium hydroxide, sodium hydroxide, and potassium hydroxide, quaternary ammonium salts such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), and tetrabutylammonium hydroxide (TBAH), metal alkoxides such as sodium methoxide and potassium t-butoxide, metal amides such as lithium diisopropylamide (LDA) and potassium hexamethyldisilazide (KHMDS), metal alkyls such as alkyllithium and alkylaluminum, nitrogen-containing aliphatic compounds such as pyridine, tetraethylamine, DBU, DBN, and imidazole, and nitrogen-containing heterocyclic compounds. These may be used individually or in combination of two or more.

[0057] The liquid should not cause peeling, decomposition, or dissolution of the substrate, undercoat, or photosensitive surface treatment layer, and should have good cleaning and removal properties, and should have a liquid composition that yields a higher pKa. Among these, a liquid containing quaternary ammonium added to water or an alcohol-based solvent is preferred. An aqueous solution of tetrabutylammonium hydroxide (TBAH) is particularly preferred.

[0058] The purpose of increasing the pKa is to activate the hydroxyl group contained in hydroxycoumarin, thereby increasing the molar extinction coefficient and improving the photoreaction rate. By maintaining moderately basic conditions, it is possible to improve photoreactivity without damaging the photosensitive surface treatment layer.

[0059] Subsequently, as shown in Figure 1(c), UV light is irradiated onto the photosensitive surface treatment layer 10 via the photomask 13. This exposes the photosensitive surface treatment layer 10 in the exposure area of ​​the photomask 13.

[0060] As a result, as shown in Figure 1(d), an amine generation area 14 is formed in the exposed area, and an amine non-generation area 12 is formed in the unexposed area.

[0061] UV light can be exemplified by the i-line with a wavelength of 365 nm. Furthermore, the exposure amount and duration do not necessarily require complete deprotection; it is sufficient if only some amines are generated.

[0062] Next, as shown in Figure 1(e), an electroless plating catalyst is applied to the surface to form a catalyst layer 15. The electroless plating catalyst is a catalyst that reduces metal ions contained in the electroless plating solution, and examples include silver and palladium.

[0063] Amino groups are exposed on the surface of the amine generation section 14. These amino groups can capture and reduce the electroless plating catalyst described above. Therefore, the electroless plating catalyst is captured only on the amine generation section 14, forming the catalyst layer 15. Furthermore, the electroless plating catalyst can be one on which amino groups can be supported.

[0064] As shown in Figure 1(f), electroless plating is performed to form a plating layer 16. Examples of materials for the plating layer 16 include nickel-phosphorus (NiP) and copper (Cu).

[0065] In this process, the substrate 11 is immersed in an electroless plating bath to reduce metal ions on the catalyst surface and deposit a plating layer 16. At this time, a catalyst layer 15 supporting a sufficient amount of catalyst is formed on the surface of the amine generating section 14, so the plating layer 16 can be selectively deposited only on the amine generating section 14.

[0066] Through the above steps, it is possible to form a wiring pattern on a predetermined substrate using the photosensitive surface treatment agent of this embodiment.

[0067] <Transistor manufacturing method> Furthermore, a method for manufacturing a transistor using the plating layer 16 obtained by the above-described pattern formation method as the gate electrode will be explained with reference to Figure 2.

[0068] As shown in Figure 2(a), an insulating layer 17 is formed by a known method so as to cover the plating layer 16 and the amine-free areas 12 of the electroless plating pattern formed by the pattern formation method described above. The insulating layer 17 may be formed by applying a coating solution obtained by dissolving one or more resins such as UV-curable acrylic resin, epoxy resin, ene-thiol resin, or silicone resin in an organic solvent. The insulating layer 17 can be formed in a desired pattern by irradiating the coating film with ultraviolet light through a mask having openings corresponding to the area where the insulating layer 17 is to be formed. The amine-free areas 12 may be removed as needed before forming the insulating layer 17.

[0069] As shown in Figure 2(b), a photosensitive surface treatment layer 10 is formed on the insulating layer 17 in the same manner as the electroless plating pattern formation method described above, and an amine generation section 14 is formed in the area where the source electrode and drain electrode are formed.

[0070] As shown in Figure 2(c), in the same manner as the pattern formation method described above, a catalyst for electroless plating is supported on the amine generation section 14 to form a catalyst layer 15, and then electroless plating is performed to form a plating layer 18 (source electrode) and a plating layer 19 (drain electrode). Nickel-phosphorus (NiP) and copper (Cu) can be used as materials for the plating layers 18 and 19, but they may be formed from different materials than the plating layer 16 (gate electrode). Alternatively, gold (Au) may be deposited on the surface of nickel-phosphorus (NiP) or copper (Cu) by electroless gold plating.

[0071] As shown in Figure 2(d), a semiconductor layer 21 is formed between the plating layer 18 (source electrode) and the plating layer 19 (drain electrode).

[0072] The semiconductor layer 21 may be formed, for example, by preparing a solution by dissolving an organic semiconductor material soluble in an organic solvent, such as TIPS pentacene (6,13-Bis(triisopropylsilylethynyl)pentacene), in the organic solvent, and then coating and drying the solution between the plating layer 18 (source electrode) and the plating layer 19 (drain electrode).

[0073] Alternatively, the semiconductor layer 21 may be formed by adding one or more insulating polymers, such as PS (polystyrene) or PMMA (polymethyl methacrylate), to the above solution, and then coating and drying the solution containing the insulating polymers.

[0074] When the semiconductor layer 21 is formed in this manner, an insulating polymer is concentrated and formed below the semiconductor layer 21 (on the side of the insulating layer 17). When polar groups such as amino groups are present at the interface between the organic semiconductor and the insulating layer, there is a tendency for transistor characteristics to deteriorate. However, by providing the organic semiconductor via the insulating polymer described above, the deterioration of transistor characteristics can be suppressed. In this way, it is possible to manufacture a transistor.

[0075] According to the method described above, there is no need to separately prepare a chemical resist or the like in the UV exposure process, and the process can be simplified to use only a photomask. Consequently, the process of removing the resist layer is also unnecessary. Furthermore, due to the catalytic reduction ability of amino groups, the catalyst activation process that is normally required can be omitted, resulting in significant cost reductions and time savings while enabling high-resolution patterning. In addition, since the dip-coating method can be used, it can be used very well in roll-to-roll processes.

[0076] Furthermore, the resin film protected by Boc is extremely stable against light, and since it does not require light-shielded storage or work in a yellow room from the state of the surface treatment agent to the film formation process and the resin film after formation, it achieves a significant improvement in workability and storage stability compared to the handling of general photosensitive materials. Since photosensitivity is obtained after the deprotection treatment that enables its development, the number of processes that require control against light can be greatly reduced, and the burden on workers can be reduced.

[0077] Furthermore, there are no particular restrictions on the structure of the transistor, and it can be appropriately selected according to the purpose. For example, top-contact / bottom-gate, top-contact / top-gate, and bottom-contact / top-gate transistors may be manufactured in the same manner.

[0078] <Laminate> This embodiment is a laminate containing the photosensitive surface treatment agent of the above embodiment. The laminate of this embodiment is a laminate in which a substrate and a metal pattern are laminated, and a photosensitive surface treatment agent is included in the unexposed areas where the pattern is not formed.

[0079] <Transistor> This embodiment is a transistor containing the photosensitive surface treatment agent of the above embodiment. The laminate of this embodiment is a transistor having a laminate in which a substrate and a metal pattern are stacked, and a photosensitive surface treatment agent is included in the unexposed areas where the pattern is not formed. [Examples]

[0080] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0081] <Example 1> The compound represented by (M1)-11 was obtained using the following synthesis scheme. First, 6-bromo-4-chloromethyl-7-hydroxycoumarin was synthesized by the reaction shown below.

[0082] [ka]

[0083] In a 1 L round-bottom flask, 20.0 g of 4-bromoresorcinol (106 mmol, 1.0 eq) was added and dissolved in 160 mL of methanesulfonic acid (MsOH). 26.1 g of ethyl 4-chloroacetate (159 mmol, 1.5 eq) was added, and the mixture was stirred at room temperature for 2 hours. The reaction solution was placed in an ice bath, 480 mL of cold water (3 times the amount of MsOH) was added, and the mixture was stirred at 0°C for 1 hour. The mixture was filtered through a membrane filter, washed with H2O, and vacuum-dried (in a 60°C water bath) to obtain 29.5 g (102 mmol, 96%) of the target product as a light brown powder.

[0084] 1 H NMR (CD3OD,400MHz): δ=4.82(2H,d,J=0.8Hz), 6.42(1H,t,J=0.8Hz), 6.85(1H,s), 7.95(1H,s)

[0085] Next, 6-bromo-4-hydroxymethyl-7-hydroxycoumarin was synthesized by the reaction shown below.

[0086] [ka]

[0087] In a 1 L round-bottom flask, 26.0 g of 6-bromo-4-chloromethyl-7-hydroxycoumarin (89.8 mmol, 1.0 eq), 130 mL of dimethylformamide (DMF), and 130 mL of 1 N HCl were added, and the mixture was stirred at 100°C for 15 hours under a nitrogen atmosphere. The reaction solution was placed in an ice bath, 390 mL of cold water was added, and the mixture was stirred at 0°C for 1 hour. The mixture was filtered through a membrane filter, washed with H2O, and vacuum-dried (in a 60°C water bath) to obtain 14.6 g (53.8 mmol, 60%) of the target product as a light brown powder.

[0088] 1H NMR (CD3OD, 400 MHz): δ=4.77(2H,d,J=1.5Hz), 6.38(1H,t,J=1.5Hz), 6.84(1H,s), 7.81(1H,s)

[0089] Next, 6-bromo-7-tert-butoxycarbonyloxy-4-hydroxymethylcoumarin was synthesized by the reaction shown below.

[0090] [ka]

[0091] In a 100 mL round-bottom flask, 800 mg of 6-bromo-7-hydroxy-4-hydroxymethylcoumarin (2.95 mmol, 1.0 eq), 897 mg of 1-tert-butoxy-2-tert-butoxycarbonyl-1,2-dihydroisoquinoline (BBDI) (2.96 mmol, 1.0 eq), and 8 mL of anhydrous tetrahydrofuran (THF) were added and stirred at room temperature under a nitrogen atmosphere for 3 hours. Ethyl acetate (10 mL x 3) and 1N HCl (10 mL) were added for extraction, and the mixture was sequentially washed with saturated NaHCO3 aqueous solution (10 mL x 1) and saturated saline solution (10 mL x 1). The organic layer was dried over anhydrous MgSO4, filtered, concentrated, and vacuum-dried to obtain 990 mg of a brown solid. The sample was purified by column chromatography (100 cc silica gel, 3.0 cm in diameter, 15 cm in height) (suspended in developing solvent and charged; developing solvent chloroform:ethyl acetate = 5:1 (Rf 0.29, 300 mL)), concentrated, and vacuum dried to obtain 835 mg (2.25 mmol, 76%) of the target product as a white solid.

[0092] 1 H NMR (CD3OD, 400 MHz): δ= 1.55(9H,s), 4.59(1H,br s), 4.82(2H,d,J=1.6Hz), 6.58(1H,t,J=1.6Hz), 7.37(1H,s), 7.99(1H,s)

[0093] Next, the following reaction yielded 6-bromo-7-tert-butoxycarbonyloxycoumarin-4-ylmethyl 3-(triethoxysilyl)propylcarbamate ((M1)-11).

[0094] [ka]

[0095] In a 200 mL round-bottom flask, 1.00 g of 6-bromo-7-tert-butoxycarbonyloxy-4-hydroxymethylcoumarin (2.69 mmol, 1.0 eq) was dissolved in 10 mL of anhydrous tetrahydrofuran (THF). 0.75 mL of triethylamine (5.41 mmol, 2.0 eq) and 670 μL of 3-(triethoxysilyl)propyl isocyanate (2.71 mmol, 1.0 eq) were added, and the mixture was stirred at 55°C for 16 hours under a nitrogen atmosphere. The mixture was concentrated using an evaporator and vacuum-dried to obtain 1.66 g of a yellow viscous substance. The sample was purified by column chromatography (100cc silica gel, 3.0cm diameter, 15cm height) (dissolved in chloroform and charged, developing solvent chloroform:ethyl acetate:tetramethoxysilane = 100:5:1 (200mL)), concentrated, vacuum dried (water bath 50°C), rinsed with hexane, and vacuum dried to obtain 733mg (1.19 mmol, 44%) of the target product as a white powder.

[0096] 1 H NMR (CD3OD, 400 MHz): δ=0.58-0.66(2H,m), 1.20 (9H,t,J=7.0Hz)1.55(9H,s), 1.55-1.66(2H,m), 3.15 (2H,t,J=7.0Hz), 3.82(6H,q,J=7.0 Hz), 5.32(2H,d,J=1.2Hz), 6.48(1H,br s), 7.38(1H,s), 8.02(1H,s)

[0097] <Example 2> 6-bromo-7-hydroxycoumarin-4-ylmethyl 3-(triethoxysilyl)propylcarbamate (M1) was synthesized by the reaction shown below.

[0098] [ka]

[0099] In a 30 mL two-necked round-bottom flask, 200 mg of 6-bromo-7-hydroxy-4-hydroxymethylcoumarin (0.737 mmol, 1.0 eq), 4 mL of dry THF, 2 drops of dibutyltin dilaurate (DBTL) prepared using Pasteur (approx. 20 μL, approx. 0.05 eq), and 365 μL of 3-(triethoxysilyl)propyl isocyanate (1.48 mmol, 2.0 eq) were added and stirred at 60°C for 4 hours under a nitrogen atmosphere. The mixture was concentrated using an evaporator and vacuum-dried (water bath at 60°C) to obtain 560 mg of a brown viscous substance. The sample was purified by column chromatography (40 cc silica gel, 2.0 cm in diameter, 15 cm in height) (dissolved in chloroform and charged, developing solvent chloroform:ethyl acetate:tetramethoxysilane = 100:5:1 (120 mL)), concentrated, vacuum dried (water bath 50°C), rinsed with hexane, and vacuum dried to obtain 214 mg (0.412 mmol, 56%) of the target product, which is a yellow waxy substance.

[0100] Rf = 0.60 (Hexane:ethyl acetate = 1:1) Rf = 0.25 (chloroform:ethyl acetate = 20:1)

[0101] 1 H NMR (CD3OD, 400MHz): δ=0.58-0.66(2H,m), 1.20(9H, t,J=7.1Hz), 1.56-1.66(2H,m), 3.13(2H,t,J=7.0 Hz), 3.81(6H,q,J=7.1Hz), 5.27(2H,d,J=1.2Hz), 6.26(1H,t,J =1.2Hz), 6.84(1H,s), 7.84(1H,s)

[0102] <Rating> [Manufacturing of plated wiring 1] A surface treatment agent containing the compound represented by formula (M1)-11 was used to form a film on a substrate, and plated wiring was manufactured.

[0103] Toluene was added to the compound represented by formula (M1)-11 synthesized in Example 1 to adjust the concentration to 0.1% by mass, and then acetic acid was added in a proportion that resulted in an acetic acid concentration of 1.0% by mass to obtain photosensitive surface treatment agent 1.

[0104] Photosensitive surface treatment agent 1 was placed in a 1.4 L glass container, heated to 60°C using a water bath, and then the substrate was immersed for 90 minutes to chemically bond the compound represented by (M1)-11 to the PET substrate (manufactured by Oike Advanced Film Co., Ltd., VX-50TUH) on which an SiO2 film had been deposited on the surface, thereby forming a resin film. Subsequently, the substrate was immersed in methanol and irradiated with 28 kHz ultrasound for 3 minutes to physically remove the attached compound, resulting in a resin film with strong adhesion.

[0105] Subsequently, the resin film was deprotected by immersing it in a 50:50 mixed solution of 35% hydrochloric acid aqueous solution and methanol at room temperature for 30 minutes to obtain a photosensitive surface treatment layer. By deprotecting the resin film, the tert-butoxycarbonyl group of the compound represented by formula (M1)-11 was removed, as shown below, generating a hydroxyl group and yielding a photosensitive resin layer.

[0106] [ka]

[0107] Next, a photosensitive surface treatment layer was deposited over the entire substrate, and 365 nm light at a rate of 250 mJ / cm² was applied to it via a photomask. 2 The photosensitive surface treatment layer was exposed to light, forming amino group generation areas in the exposed areas and amino group non-generation areas in the unexposed areas.

[0108] In this procedure, the substrate was immersed in a 0.2% by mass aqueous solution of tetrabutyrammonium hydroxide (TBAH) before exposure. By immersing the resin film, the hydroxyl group of the compound represented by formula (M1)-11 is activated by the base, increasing the molar extinction coefficient and improving the photoreaction rate, resulting in a highly sensitive photosensitive surface treatment layer.

[0109] Next, after rinsing with water, the material was immersed in a colloidal catalyst solution for electroless plating (Melplate Activator 7331, manufactured by Meltex) at room temperature for 3 minutes to deposit the catalyst (Pd) onto the amine generating area. After rinsing the surface with water, it was immersed in an electroless plating solution (Melplate NI-867, manufactured by Meltex) at 73°C for 1 minute to deposit nickel-phosphorus on the catalyst and create a fine plated wiring.

[0110] [Manufacturing of plated wiring 2] Exposure dose: 500 mJ / cm² 2 Except for the change, the plated wiring was manufactured in the same manner as described in [Manufacturing of Plated Wiring 1] above.

[0111] [Manufacturing of plated wiring 3] Exposure dose: 1000 mJ / cm² 2 Except for the change, the plated wiring was manufactured in the same manner as described in [Manufacturing of Plated Wiring 1] above.

[0112] [Manufacturing of plated wiring 4] Exposure dose: 2000 mJ / cm² 2 Except for the change, the plated wiring was manufactured in the same manner as described in [Manufacturing of Plated Wiring 1] above.

[0113] [Manufacturing of plated wiring 5] Without deprotecting the resin film, the dry substrate was exposed to 365nm light at a rate of 2000mJ / cm². 2 The plated wiring was manufactured in the same manner as described in [Manufacturing of Plated Wiring 1] above, except that the exposure method was changed.

[0114] [Evaluation of plated wiring] Figures 3A and 3B show optical microscope (VHX-7000, manufactured by Keyence Corporation) images of PET substrates that underwent plating and wiring treatment in the example, respectively. Figure 3A shows optical microscope images of L / S = 100 / 100 and 5 / 5 processed on a PET substrate using the above-described plating wiring manufacturing methods 1 to 4. Figure 3B shows an optical microscope image of a plated wiring on a PET substrate processed in manufacturing step 3 above, with L / S = 1 / 1 to 9 / 9 μm.

[0115] Figures 3A and 3B clearly show, both visually and under a microscope, that high-resolution, well-plated wiring has been formed.

[0116] Figures 4A and 4B show the results of exposure and plating wiring treatment performed on the resin film in the example. Figure 4A shows the molecular structure of the resin film on the PET substrate. Figure 4B shows an overall view of the PET substrate processed in manufacturing step 5 of the plated wiring described above. From Figures 4A and 4B, light with a wavelength of 365 nm is used at a flow rate of 2000 mJ / cm². 2 Even after irradiation, the material remains unprotected, suppressing unintended amine generation. In other words, it was confirmed that the material has excellent light stability and does not require light-shielded storage. [Explanation of symbols]

[0117] 11: Substrate, 10a: Photosensitive surface treatment agent, 10: Photosensitive surface treatment agent layer, 13: Photomask, 14: Amino group generation area, 12: Amino group non-generation area, 15: Catalyst layer, 16: Plating layer, 17: Insulator layer, 18: Plating layer (source electrode), 19: Plating layer (drain electrode), 21: Semiconductor layer

Claims

1. A photosensitive surface treatment agent comprising a compound represented by the following formula (M1). 【Chemistry 1】 (In formula (M1), R １ is a tert-butoxycarbonyl group, R ２ (where m is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m is an integer of 1 or more, and X is a halogen atom or an alkoxy group.)

2. A pattern-forming substrate having a surface chemically modified using the photosensitive surface treatment agent described in claim 1, and comprising a compound represented by the following formula. 【Chemistry 2】

3. A laminate comprising a compound represented by the following formula. 【Transformation 3】

4. A transistor comprising a compound represented by the following formula between the source electrode and the drain electrode. 【Chemistry 4】

5. A step of applying the photosensitive surface treatment agent described in claim 1 onto a substrate to form a resin film, The process of deprotecting the aforementioned resin film and converting it into a photosensitive resin film, The steps include irradiating the photosensitive resin film with light of a predetermined pattern, A pattern forming method comprising the step of performing electroless plating on at least a portion of the irradiation area of ​​the predetermined pattern light.

6. A step of applying the photosensitive surface treatment agent described in claim 1 onto a substrate to form a resin film, The process of deprotecting the aforementioned resin film and converting it into a photosensitive resin film, The steps include irradiating the photosensitive resin film with light of a predetermined pattern, A pattern forming method comprising the steps of placing an electroless plating catalyst in at least a portion of the irradiation area of ​​the predetermined pattern light and performing electroless plating.

7. A step of applying the photosensitive surface treatment agent described in claim 1 onto a substrate to form a resin film, The process of deprotecting the aforementioned resin film and converting it into a photosensitive resin film, The process involves irradiating the photosensitive resin film with light of a predetermined pattern to form an amine generation region in the exposure region, A pattern forming method comprising the steps of placing an electroless plating catalyst in the amine generation region and performing electroless plating.

8. A step of applying the photosensitive surface treatment agent described in claim 1 onto a substrate to form a resin film, The process of deprotecting the aforementioned resin film and converting it into a photosensitive resin film, The process involves immersing the photosensitive resin film in a basic solution, The process involves immersing the photosensitive resin film in the aforementioned basic solution, then irradiating the film with light in a predetermined pattern to form an amine generation region in the exposure region, A pattern forming method comprising the steps of placing an electroless plating catalyst in the amine generation region and performing electroless plating.

9. A step of applying the photosensitive surface treatment agent described in claim 1 onto a substrate to form a resin film, The process of deprotecting the aforementioned resin film and converting it into a photosensitive resin film, The process involves immersing the photosensitive resin film in a basic solution, The process involves immersing the photosensitive resin film in the aforementioned basic solution while irradiating it with light of a predetermined pattern to form an amine generation region in the exposure region, A pattern forming method comprising the steps of placing an electroless plating catalyst in the amine generation region and performing electroless plating.

10. The pattern forming method according to claim 8 or 9, wherein the basic solution is an aqueous solution of tetrabutyrammonium hydroxide (TBAH).

11. A method for manufacturing a transistor, comprising the step of forming one or more electrodes, which are source electrodes, drain electrodes, or gate electrodes, by the pattern forming method described in claim 5 or 6.

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