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

Abstract

A photosensitive surface treatment agent containing a compound represented by formula (M1). (In formula (M1), R1 is a hydrogen atom or a tert-butoxycarbonyl group or an ester-based protecting group, R2 is a hydrogen atom or an alkyl group having 1-6 carbon atoms, m is an integer of 1 or more, and X is a halogen atom or an alkoxy group. # imgabs0 #

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 producing a transistor.

[0002] This application claims priority based on Japanese Tokugan Application No. 2022-131902 filed in Japan on August 22, 2022, the contents of which are incorporated herein by reference. Background Art

[0003] In recent years, in the manufacture of micro devices such as semiconductor elements, integrated circuits, and devices for organic EL displays, methods have been proposed in which patterns having different surface properties are formed on a substrate and the micro devices are produced by utilizing the difference in surface properties.

[0004] As a pattern forming method utilizing the difference in surface characteristics on a substrate, for example, there is a method of forming a region where a chemically active substituent is generated on a part of the substrate. This method can make a metal material, an organic material, or an inorganic material adhere closely to a part of the substrate.

[0005] As a technology for making a metal material adhere to a substrate to form a metal film, there is an electroless plating process. For example, Patent Document 1 discloses a technology for forming fine wiring by electroless plating. Specifically, Patent Document 1 discloses a method of etching from a state where one side is plated or performing light patterning based on liftoff using a catalyst activation layer and a photoresist.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2006-2201 Summary of the invention

[0009] A first aspect of the present invention is a photosensitive surface treatment agent including a compound represented by the following formula (M1).

[0010] [Chemistry 1]

[0011]

[0012] (In formula (M1), R 1 is a hydrogen atom or a tert-butoxycarbonyl group or an ester protective group, R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m is an integer greater than 1, and X is a halogen atom or an alkoxy group). BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 It is a schematic diagram for explaining the pattern forming method of this embodiment.

[0014] Figure 2 This is a schematic diagram for explaining the method for manufacturing the transistor of this embodiment.

[0015] Figure 3A These are optical microscope images of L / S = 100 / 100 and 5 / 5 processed in the above-mentioned production 1 to 4 of the plated wiring on the PET substrate.

[0016] Figure 3B This is an optical microscope image of L / S = 1 / 1 to 9 / 9 um processed in the above-mentioned production 3 of the plated wiring on the PET substrate.

[0017] Figure 4A It is the molecular structure of the resin film on the PET substrate.

[0018] Figure 4B This is an overall image of the PET substrate processed in the production 5 of the plated wiring described above. DETAILED DESCRIPTION

[0019] <Photosensitive surface treatment agent>

[0020] The photosensitive surface treatment agent of the present invention contains a compound represented by the following formula (M1).

[0021] [Chemistry 2]

[0022]

[0023] (In formula (M1), R 1 is a hydrogen atom or a tert-butoxycarbonyl group or an ester protective group, R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m is an integer greater than 1, and X is a halogen atom or an alkoxy group).

[0024] In formula (M1), R 1 It is a hydrogen atom, a tert-butoxycarbonyl group or an ester protecting group.

[0025] Examples of the ester-based protecting group include acetyl (Ac), pivaloyl (Pv), propoxycarbonyl, tert-butoxycarbonyl, and benzoyl.

[0026] As long as it is a structure for protecting a hydroxyl group, it is not particularly limited to these, and for example, acetal protecting groups such as methoxymethyl (MOM), methoxyethoxymethyl (MEM), 2-tetrahydropyranyl (THP), methyl, tert-butyl (tBu) trityl (Tr), benzyl (Bn), p-methoxybenzyl, trimethylsilyl (TMS), triethylsilyl (TES), tert-butyldimethylsilyl (TBDMS) and other ether protecting groups, and any protecting group described in Greene's Protective Groups in Organic Synthesis 5th Edition (2014, published by John Wiley & Sons, Inc.), and any deprotection conditions can be applied.

[0027] Among these, R 1 Preferred is tert-butoxycarbonyl.

[0028] In formula (M1), R 2 It 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 methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, hexyl and cyclohexyl.

[0029] In formula (M1), m is an integer greater than or equal to 1, 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.

[0030] X is preferably an alkoxy group. Examples of the alkoxy group of X include -O-(CH3) and -O-(CH2)n(CH3). n is a natural number of 1 to 3.

[0031] If R in formula (M1) is included 1 A photosensitive surface treatment agent of a tert-butoxycarbonyl compound is applied to a substrate, and as shown below, SiX3 adheres to the substrate to form a resin film. The hydroxyl group of the resin film is protected by a tert-butoxycarbonyl group (hereinafter, sometimes described as "Boc" in the formula), so that the photosensitivity is suppressed.

[0032] [Chemistry 3]

[0033]

[0034] By subjecting the resin film to a deprotection treatment, as shown below, the tert-butoxycarbonyl group is removed to generate a hydroxyl group, thereby forming a photosensitive resin film.

[0035] [Chemistry 4]

[0036]

[0037] When the obtained photosensitive resin film is irradiated with light, the nitrobenzyl groups are released, and amines are generated on the substrate surface, and a metal material, an organic material, or an inorganic material can be brought into close contact with the portion where the amines are generated.

[0038] According to the photosensitive surface treatment agent of this embodiment, by arranging a metal material in the amine generating part 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.

[0039] [Chemistry 5]

[0040]

[0041] Since the photosensitivity is suppressed in the state of the resin film, after the photosensitive surface treatment agent is applied to the substrate, it can be stably stored without being photodecomposed. According to the present invention, the photosensitive surface treatment agent can be applied to the substrate in advance and stored, and then deprotected and used just before patterning.

[0042] In the formula (M1), R 1 In the case of a photosensitive surface treatment agent that is a compound having a tert-butoxycarbonyl group, the deprotection method is specifically deprotection by hydrolysis under acidic conditions such as hydrochloric acid or trifluoroacetic acid.

[0043] In the formula (M1), R 1 In the case of a photosensitive surface treatment agent having an ester-based protective group, the deprotection method is specifically deprotection using hydrolysis under acidic or alkaline conditions, or hydrogenation reduction.

[0044] Specific examples of the compound represented by formula (M1) are shown below.

[0045] [Chemistry 6]

[0046]

[0047] <Method for producing compound>

[0048] The compound represented by formula (M1) can be produced by the following method.

[0049] First, 6-bromo-4-hydroxymethyl-7-hydroxycoumarin was synthesized by the method described in Examples.

[0050] The compound represented by formula (M1) is R 1 In the case of a compound in which a hydrogen atom is present, R can be synthesized by reacting an aminosilane compound with 6-bromo-4-hydroxymethyl-7-hydroxycoumarin. 1 The compound represented by the formula (M1) is a hydrogen atom.

[0051] The compound represented by formula (M1) is R 1 In the case of a compound containing 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.

[0052] Examples of the compound containing a tert-butoxycarbonyl group include 1-tert-butoxy-2-tert-butoxycarbonyl-1,2-dihydroisoquinoline, di-tert-butyl dicarbonate, 1-tert-butoxycarbonyl-1,2,4-triazole, N-(tert-butoxycarbonyloxy)phthalimide, N-tert-butoxycarbonylimidazole, and tert-butylphenyl carbonate.

[0053] R can be synthesized by reacting an aminosilane compound with 6-bromo-7-tert-butoxycarbonyloxy-4-hydroxymethylcoumarin. 1 The compound represented by the formula (M1) is a tert-butoxycarbonyl group.

[0054] The compound represented by formula (M1) is R 1 In the case of a compound having an ester-based protective group, first, 6-bromo-4-hydroxymethyl-7-hydroxycoumarin is reacted with a compound containing an ester-based protective group precursor to synthesize an intermediate.

[0055] Examples of the compound containing an ester-based protecting group include acetyl chloride, acetic anhydride, pivaloyl chloride, pivalic anhydride, benzoyl chloride, and benzoic anhydride.

[0056] By reacting an aminosilane compound with the obtained intermediate, R 1 The compound represented by the formula (M1) is an ester-based protecting group.

[0057] In one embodiment of the present invention, the photosensitive surface treatment agent is composed of the compound represented by the above formula (M1).

[0058] In one embodiment of the present invention, the photosensitive surface treatment agent may contain a solvent and can be used as a preferred surface treatment agent by being dissolved in a common organic solvent such as an alcohol solvent, an ester solvent, a hydrocarbon aromatic solvent, an amine solvent, a ketone solvent, a glycol ether solvent, or an ether solvent.

[0059] Examples of the alcohol solvent include isopropyl alcohol (IPA) and n-butanol.

[0060] Examples of the ester solvent include ethyl acetate (EAC), butyl acetate (NBAC), n-propyl acetate (NPAC), and 3-methoxy-3-methylbutyl acetate.

[0061] Examples of the hydrocarbon aromatic solvent include toluene, xylene, benzene, ethylbenzene, and trimethylbenzene.

[0062] Examples of the amine solvent include N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), and N,N-dimethylacetamide (DMAC).

[0063] Examples of the ketone solvent include methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), diisobutyl ketone (DIBK), methyl isopropyl ketone (MIPK), cyclohexanone, cyclopentanone (CPN), cycloheptanone, and acetone.

[0064] Examples of the glycol ether solvent include methyl cellosolve, butyl cellosolve, ethylene glycol mono-tert-butyl ether (ETB), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), and 3-methoxy-3-methyl-1-butanol (MMB).

[0065] Examples of other solvents include halogen-based solvents containing chlorine or fluorine, such as chloroform, chlorobenzene, and fluoroalkyl ethers, etc. These may be used alone or in combination of two or more.

[0066] The organic solvent can be appropriately selected according to conditions such as environmental pollution, solubility, volatility, corrosiveness to the substrate and base, film forming equipment and film forming method.

[0067] From the viewpoint of improving the reactivity between the primer and the photosensitive surface treatment agent or between the molecules of the photosensitive surface treatment agent, the solvent contained is preferably an alcohol-based, ether-based or hydrocarbon-based solvent, particularly preferably a hydrocarbon-based solvent, and among them, toluene is preferred.

[0068] From the perspective of further improving reactivity, any acidic or basic compound may be included during film formation, and may be appropriately selected according to film formation conditions, with acidic compounds such as hydrochloric acid, acetic acid, and nitric acid being particularly preferred, and acetic acid being preferred because it can form a film while maintaining Boc.

[0069] <Pattern Formation Method>

[0070] The pattern forming method of the present embodiment comprises: a process of coating the above-mentioned photosensitive surface treatment agent of the present embodiment on a substrate to form a resin film; a process of deprotecting the resin film to form a photosensitive resin film; a process of irradiating the photosensitive resin film with a specified pattern light to form an amine generating area in the exposed area; and a process of configuring a catalyst for electroless plating in the amine generating area to perform electroless plating.

[0071] Hereinafter, each process will be described with reference to the drawings.

[0072] like Figure 1As shown in (a), the photosensitive surface treatment agent of the present embodiment described above is applied on a substrate 11 to obtain a resin film 10a.

[0073] As the coating method, for example, a coating method such as spin coating, dip coating, die coating, spray coating, roll coating, micro gravure coating, lip coating, ink jet coating, coater coating, brush coating, etc. can be used. In addition, coating can also be performed by a printing method such as flexographic printing and screen printing.

[0074] It should be noted that in this process, Figure 1 As shown in (a), a treatment for drying the solvent by, for example, heat, reduced pressure, or the like may be applied.

[0075] The resin film is subjected to a deprotection treatment to form a photosensitive resin layer 10. Specifically, the deprotection treatment is a hydrolysis treatment under acidic conditions such as hydrochloric acid, sulfuric acid, hydrofluoric acid, hexafluoroantimonate or trifluoroacetic acid. The deprotection treatment can be performed in a liquid phase or in a solid phase by contacting a gel or a film. The gel or the film can be in the form of a single sheet or a roll.

[0076] Therefore, if Figure 1 As shown in (b), a photosensitive surface treatment agent layer 10 is formed on a substrate 11.

[0077] The deprotection treatment may be performed immediately after the resin film is formed, or may be performed immediately before exposure in order to improve the storage stability of the resin film.

[0078] Then, if Figure 1 As shown in (c), a photomask 13 having an exposure area of ​​a predetermined pattern is prepared. The exposure method is not limited to the method using a photomask, and projection exposure using an optical system such as a lens or a reflector, maskless exposure using a spatial light modulation element, a laser beam, etc., etc. can be used. It should be noted that the photomask 13 can be set to contact with the photosensitive surface treatment agent layer 10, or it can be set to be non-contact.

[0079] During exposure, the surface of the photosensitive resin layer can be immersed in any liquid for exposure, or it can be exposed after immersion. The type of liquid is not particularly limited, and water or an alcohol solvent or a ketone solvent can be selected. They can be used alone or in combination of two or more.

[0080] In order to improve the acid dissociation constant (Ka), an alkaline compound can be added to make an arbitrary alkaline solution. As the type of alkaline compound, it can be selected from alkali metal carbonates such as sodium bicarbonate and potassium carbonate, alkali metal hydrides such as sodium hydride and sodium borohydride, alkali metal hydroxides such as cesium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, quaternary ammonium salts such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), metal alkoxides such as sodium methoxide and potassium tert-butoxide, metal amides such as lithium diisopropylamide (LDA), potassium hexamethyldisilazide (KHMDS), alkyl metals such as alkyl lithium and alkyl aluminum, nitrogen-containing aliphatic compounds such as pyridine, tetraethylamine, DBU, DBN, imidazole, nitrogen-containing heterocyclic compounds, etc. They can be used alone or in combination of two or more.

[0081] The liquid preferably has a liquid composition that does not cause peeling or decomposition / dissolution of the substrate or base or the photosensitive surface treatment agent layer, has good cleaning removability, and can obtain a higher pKa, and a liquid having quaternary ammonium added to water or an alcohol solvent is preferred. A tetrabutylammonium hydroxide (TBAH) aqueous solution is particularly preferred.

[0082] The purpose of increasing the pKa is to activate the hydroxyl group contained in the hydroxycoumarin, which increases the molar absorption coefficient and improves the photoreaction rate. By setting the conditions to be moderately alkaline, the photoreactivity can be improved without damaging the photosensitive surface treatment agent layer.

[0083] Afterwards, if Figure 1 As shown in (c), the photosensitive surface treatment agent layer 10 is irradiated with UV light via the photomask 13. As a result, the photosensitive surface treatment agent layer 10 is exposed in the exposure area of ​​the photomask 13.

[0084] The results, such as Figure 1 As shown in (d), the amine generating portion 14 is formed in the exposed portion, and the amine non-generating portion 12 is formed in the unexposed portion.

[0085] UV light includes, for example, i-ray having a wavelength of 365 nm. The exposure amount and exposure time do not necessarily need to completely deprotect, and may be sufficient as long as some amines are generated.

[0086] Then, if Figure 1 As shown in (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 a plating solution for electroless plating, and examples thereof include silver and palladium.

[0087] The amino group is exposed on the surface of the amine generating part 14. The amino group can capture and reduce the electroless plating catalyst. Therefore, the electroless plating catalyst is captured only on the amine generating part 14 to form the catalyst layer 15. In addition, the electroless plating catalyst can use a catalyst that can support an amino group.

[0088] like Figure 1 As shown in (f), electroless plating is performed to form the plated layer 16. It should be noted that examples of the material of the plated layer 16 include nickel-phosphorus (NiP) and copper (Cu).

[0089] In this step, the substrate 11 is immersed in an electroless plating bath to reduce metal ions on the catalyst surface to deposit the plating layer 16. At this time, since the catalyst layer 15 carrying a sufficient amount of catalyst is formed on the surface of the amine generating part 14, the plating layer 16 can be selectively deposited only on the amine generating part 14.

[0090] Through the above steps, a wiring pattern can be formed on a predetermined substrate using the photosensitive surface treatment agent of the present embodiment.

[0091] <Method for manufacturing transistor>

[0092] Furthermore, using Figure 2 A method for manufacturing a transistor using the plated layer 16 obtained in the above <Pattern Formation Method> as a gate electrode will be described.

[0093] like Figure 2 As shown in (a), an insulator layer 17 is formed by a known method in such a manner as to cover the plating layer 16 of the electroless plating pattern formed by the above-mentioned pattern forming method and the amine non-generating portion 12. The insulator layer 17 can be formed, for example, by using a coating liquid obtained by dissolving one or more resins such as ultraviolet-curable acrylic resin, epoxy resin, ene-thiol resin, silicone resin, etc. in an organic solvent and applying the coating liquid. By irradiating the coating film with ultraviolet rays through a mask having an opening corresponding to the area where the insulator layer 17 is to be formed, the insulator layer 17 can be formed into a desired pattern. It should be noted that before forming the insulator layer 17, the amine non-generating portion 12 can also be removed as needed.

[0094] like Figure 2 As shown in (b), a photosensitive surface treatment agent layer 10 is formed on the insulating layer 17 in the same manner as the above-mentioned electroless plating pattern forming method, and an amine generating portion 14 is formed in the portion where the source electrode and the drain electrode are to be formed.

[0095] like Figure 2As shown in (c), similarly to the above-mentioned pattern forming method, a catalyst for electroless plating is supported on the amine generating portion 14, and after the catalyst layer 15 is formed, electroless plating is performed to form a plating layer 18 (source electrode) and a plating layer 19 (drain electrode). It should be noted that the materials of the plating layers 18 and 19 may also include nickel-phosphorus (NiP) and copper (Cu), but they may also be formed of a material different from that of the plating layer 16 (gate electrode), and gold (Au) may be precipitated by performing electroless plating of a different metal, such as gold, on the surface of nickel-phosphorus (NiP) and copper (Cu).

[0096] like Figure 2 As shown in (d) of FIG. 8 , a semiconductor layer 21 is formed between the plated layer 18 (source electrode) and the plated layer 19 (drain electrode).

[0097] The semiconductor layer 21 can also be formed by, for example, preparing a solution in which an organic semiconductor material soluble in an organic solvent such as TIPS pentacene (6,13-Bis(triisopropylsilylethynyl)pentacene) is dissolved in the organic solvent, and then applying and drying the solution between the plating layer 18 (source electrode) and the plating layer 19 (drain electrode).

[0098] Alternatively, the semiconductor layer 21 may be formed by adding one or more insulating polymers such as PS (polystyrene) and PMMA (polymethyl methacrylate) to the above solution, applying the solution containing the insulating polymer, and drying the solution.

[0099] When the semiconductor layer 21 is formed in this way, the insulating polymer is concentratedly formed below the semiconductor layer 21 (on the side of the insulator layer 17). When polar groups such as amino groups exist at the interface between the organic semiconductor and the insulator layer, there is a tendency for the transistor characteristics to be reduced, but by adopting a structure in which the organic semiconductor is provided via the insulating polymer, the reduction in transistor characteristics can be suppressed. As described above, a transistor can be manufactured.

[0100] According to the above method, there is no need to set up a chemical resist in the UV exposure process, and a simple process can be performed using only a photomask. Therefore, there is no need to remove the resist layer. In addition, the catalytic reduction ability of the amino group can also omit the activation treatment process of the catalyst that is usually required, and high-precision patterning can be performed while achieving significant cost reduction and time reduction. In addition, since the dip coating method can be used, it can also be used very appropriately in the roll-to-roll process.

[0101] In addition, the resin film protected by Boc is extremely stable to light. From the state of the surface treatment agent, the film-forming operation and the resin film after film-forming do not need to be stored in a light-shielding environment or in a yellow room. Therefore, compared with the treatment of general photosensitive materials, the workability and storage stability can be greatly improved. Since the photosensitivity is obtained after the deprotection treatment, the process of managing light can be greatly reduced, which can reduce the burden on the operator.

[0102] It should be noted that the structure of the transistor is not particularly limited and can be appropriately selected according to the purpose. For example, top contact / bottom gate type, top contact / top gate type, and bottom contact / top gate type transistors can also be manufactured in the same manner.

[0103] <Laminated body>

[0104] The present embodiment is a laminate including the photosensitive surface treatment agent of the present embodiment described above.

[0105] The laminated body according to the present embodiment is a laminated body in which a substrate and a metal pattern are laminated, and a photosensitive surface treatment agent is contained in an unexposed portion where a pattern is not formed.

[0106] <Transistor>

[0107] This embodiment is a transistor including the photosensitive surface treatment agent of this embodiment.

[0108] The laminated body of the present embodiment is a transistor including a laminated body in which a substrate and a metal pattern are laminated, wherein a photosensitive surface treatment agent is contained in an unexposed portion where a pattern is not formed.

[0109] Example

[0110] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

[0111] <Example 1>

[0112] The compound represented by (M1)-11 was obtained using the following synthesis scheme.

[0113] First, 6-bromo-4-chloromethyl-7-hydroxycoumarin was synthesized by the reaction shown below.

[0114] [Chemistry 7]

[0115]

[0116] 20.0 g of 4-bromoresorcinol (106 mmol, 1.0 eq) was added to a 1L eggplant flask, dissolved in 160 mL of methanesulfonic acid (MsOH), and 26.1 g of ethyl 4-chloroacetoacetate (159 mmol, 1.5 eq) was added, and stirred at room temperature for 2 hours. The reaction solution was placed in an ice bath, 480 mL of cold water (3 times of MsOH) was added, and stirred at 0°C for 1 hour. Filtered with a membrane filter, washed with H2O, and vacuum dried (hot water bath 60°C) to obtain 29.5 g (102 mmol, 96%) of the target product as a light brown powder.

[0117] 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)

[0118] Next, 6-bromo-4-hydroxymethyl-7-hydroxycoumarin was synthesized by the reaction shown below.

[0119] [Chemistry 8]

[0120]

[0121] In a 1L eggplant flask, add 26.0g of 6-bromo-4-chloromethyl-7-hydroxycoumarin (89.8mmol, 1.0eq), 130mL of dimethylformamide (DMF), and 130mL of 1N HCl, and stir at 100°C for 15 hours under a nitrogen atmosphere. Put the reaction solution in an ice bath, add 390mL of cold water, and stir at 0°C for 1 hour. Filter with a membrane filter, wash with H2O, and vacuum dry (hot water bath 60°C) to obtain 14.6g (53.8mmol, 60%) of the target product as a light brown powder.

[0122] 1 H NMR (CD3OD, 400MHz): δ = 4.77 (2H, d, J = 1.5Hz), 6.38 (1H, t, J = 1.5Hz), 6.84 (1H, s), 7.81 (1H, s)

[0123] Next, 6-bromo-7-tert-butoxycarbonyloxy-4-hydroxymethylcoumarin was synthesized by the reaction shown below.

[0124] [Chemistry 9]

[0125]

[0126] In a 100 mL eggplant-shaped 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 for 3 hours under a nitrogen atmosphere. Ethyl acetate (10 mL × 3) and 1N HCl (10 mL) were added for extraction, and the mixture was washed with saturated aqueous NaHCO3 solution (10 mL × 1) and saturated brine (10 mL × 1) in sequence. The organic layer was dried over anhydrous MgSO4, filtered, concentrated, and dried in vacuo to obtain 990 mg of a brown solid. The product was purified by column chromatography (silica gel 100 cc, diameter 3.0 cm, height 15 cm) (suspended in a developing solvent and loaded, 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.

[0127] 1 H NMR (CD3OD, 400MHz): 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)

[0128] Next, 6-bromo-7-tert-butoxycarbonyloxycoumarin-4-ylmethyl 3-(triethoxysilyl)propylcarbamate ((M1)-11) was obtained by the reaction shown below.

[0129] [Chemistry 10]

[0130]

[0131] 1.00 g of 6-bromo-7-tert-butoxycarbonyloxy-4-hydroxymethylcoumarin (2.69 mmol, 1.0 eq) was added to a 200 mL eggplant flask, 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 stirred at 55°C for 16 hours under a nitrogen atmosphere. Concentrated with an evaporator and vacuum dried to obtain 1.66 g of a yellow viscous substance. The product was purified by column chromatography (silica gel 100 cc, diameter 3.0 cm, height 15 cm) (dissolved in chloroform and loaded, developing solvent chloroform: ethyl acetate: tetramethoxysilane = 100:5:1 (200 mL)), concentrated, vacuum dried (hot water bath 50°C), rinsed with hexane, and vacuum dried to obtain 733 mg (1.19 mmol, 44%) of the target product as a white powder.

[0132] 1 H NMR (CD3OD, 400MHz): 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=7.0Hz), 5.32(2H,d,J=1.2Hz), 6.48(1H,br s), 7.38(1H,s), 8.02(1H,s)

[0133] <Example 2>

[0134] 6-Bromo-7-hydroxycoumarin-4-ylmethyl 3-(triethoxysilyl)propylcarbamate (M1) was synthesized by the reaction shown below.

[0135] [Chemistry 11]

[0136]

[0137] In a 30 mL two-necked eggplant 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) (ca. 20 μL, ca. 0.05 eq) added with a Pasteur pipette, 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. Concentrated with an evaporator and vacuum dried (hot water bath 60°C) to obtain 560 mg of a brown viscous substance. The product was purified by column chromatography (silica gel 40 cc, diameter 2.0 cm, height 15 cm) (dissolved in chloroform and loaded, developing solvent chloroform: ethyl acetate: tetramethoxysilane = 100:5:1 (120 mL)), concentrated, vacuum dried (hot water bath 50°C), rinsed with hexane, and vacuum dried to obtain 214 mg (0.412 mmol, 56%) of the target product as a yellow wax.

[0138] Rf=0.60(hexane:ethyl acetate=1:1)

[0139] Rf=0.25(chloroform:ethyl acetate=20:1)

[0140] 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 .0Hz), 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)

[0141] <Evaluation>

[0142] [Manufacturing of Plated Wiring 1]

[0143] A surface treatment agent containing the compound represented by Formula (M1)-11 is used to form a film on a substrate to produce a plated wiring.

[0144] 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 acetic acid was further added in a ratio to give an acetic acid concentration of 1.0% by mass, thereby obtaining a photosensitive surface treatment agent 1.

[0145] The photosensitive surface treatment agent 1 was placed in a 1.4L glass container, heated to 60°C using a hot water bath, and then the substrate was immersed for 90 minutes, thereby chemically bonding the compound represented by (M1)-11 to a PET substrate (VX-50TUH manufactured by Oike Advanced Film Co., Ltd.) having SiO2 film formed on the surface, and forming a resin film. Thereafter, the substrate was immersed in methanol and irradiated with 28kHz ultrasonic waves for 3 minutes, thereby removing the physically attached compound and obtaining a resin film with strong adhesion.

[0146] Thereafter, the resin film was immersed in a 50:50 mixed solution of a 35% hydrochloric acid aqueous solution and methanol at room temperature for 30 minutes to deprotect the film, thereby obtaining a photosensitive surface treatment agent layer.

[0147] By subjecting the resin film to a deprotection treatment, as shown below, the tert-butoxycarbonyl group of the compound represented by the formula (M1)-11 is removed to generate a hydroxyl group, thereby obtaining a photosensitive resin layer.

[0148] [Chemistry 12]

[0149]

[0150] Next, the substrate having the photosensitive surface treatment agent layer formed on the entire surface was subjected to a 250 mJ / cm 2 The photosensitive surface treatment agent layer was exposed to light with a wavelength of 365 nm to photosensitize the layer, thereby forming an amino group generating area in the exposed area and an amino group non-generating area in the unexposed area.

[0151] At this time, the substrate was immersed in a 0.2 mass % aqueous solution of tetrabutylammonium hydroxide (TBAH), and then exposed.

[0152] By impregnating the resin film, the hydroxyl group of the compound represented by formula (M1)-11 is activated by the base, and as the molar absorption coefficient increases, the photoreaction rate increases, thereby obtaining a highly sensitive photosensitive surface treatment agent layer.

[0153] Next, after washing with water, the surface was immersed in a catalyst colloid solution for electroless plating (Melplate Activator 7331, manufactured by Meltex) at room temperature for 3 minutes to allow the catalyst (Pd) to adhere to the amine generating part. After washing 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 allow nickel and phosphorus to precipitate on the catalyst to produce fine plated wiring.

[0154] [Manufacturing of Plated Wiring 2]

[0155] Change the exposure to 500mJ / cm 2, except for the above, the plated wiring was produced in the same manner as the method described in [Production of Plated Wiring 1].

[0156] [Manufacturing of Plated Wiring 3]

[0157] Change the exposure to 1000mJ / cm 2 , except for the above, the plated wiring was produced in the same manner as the method described in [Production of Plated Wiring 1].

[0158] [Manufacturing of Plated Wiring 4]

[0159] Change the exposure to 2000mJ / cm 2 , except for the above, the plated wiring was produced in the same manner as the method described in [Production of Plated Wiring 1].

[0160] [Manufacturing of Plated Wiring 5]

[0161] Without deprotecting the resin film, the wavelength of 365nm light was changed to 2000mJ / cm 2 The plated wiring was produced in the same manner as the method described in the above-mentioned [Production of Plated Wiring 1] except for exposure.

[0162] [Evaluation of Plated Wiring]

[0163] Figure 3A , Figure 3B 2 and 3 show optical microscope images (VHX-7000 manufactured by KEYENCE CORPORATION) of PET substrates subjected to the plating wiring process in Examples.

[0164] Figure 3A These are optical microscope images of L / S = 100 / 100 and 5 / 5 processed in the above-mentioned production 1 to 4 of the plated wiring on the PET substrate.

[0165] Figure 3B This is an optical microscope image of L / S = 1 / 1 to 9 / 9 um processed in the above-mentioned production 3 of the plated wiring on the PET substrate.

[0166] according to Figure 3A and Figure 3B It was possible to confirm visually and under a microscope that high-definition, good plated wiring was formed.

[0167] Figure 4A and Figure 4B 2 shows the results of the exposure and plating wiring treatment of the resin film in the examples. Figure 4A It is the molecular structure of the resin film on the PET substrate. Figure 4B This is an overall image of the PET substrate processed in the production 5 of the plated wiring described above.

[0168] according to Figure 4A and Figure 4B , even at 2000mJ / cm 2 Even when irradiated with light of wavelength 365 nm, the film was not deprotected and the generation of unintended amines was suppressed. As long as the film was in the form of a resin film, no unintended amines were generated. In other words, it was confirmed that the film had excellent light stability and did not require light shielding for storage.

[0169] Explanation of symbols

[0170] 11: substrate, 10a: photosensitive surface treatment agent, 10: photosensitive surface treatment agent layer, 13: photomask, 14: amino group generating part, 12: amino group non-generating part, 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 hydrogen atom or a tert-butoxycarbonyl group or an ester protective group, R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m is an integer greater than 1, and X is a halogen atom or an alkoxy group. 2 . A pattern-forming substrate having a surface chemically modified with the photosensitive surface treatment agent according to claim 1 . 3 . A laminate comprising the photosensitive surface treatment agent according to claim 1 . A transistor comprising the photosensitive surface treatment agent according to claim 1 .

5. A pattern forming method, comprising: A step of coating the photosensitive surface treatment agent according to claim 1 on a substrate to form a resin film; The process of removing the protection of the resin film to prepare a photosensitive resin film; a step of irradiating the photosensitive resin film with light of a predetermined pattern; and A step of performing electroless plating on at least a portion of the region irradiated with the predetermined pattern light.

6. A pattern forming method, comprising: A step of coating the photosensitive surface treatment agent according to claim 1 on a substrate to form a resin film; The process of removing the protection of the resin film to prepare a photosensitive resin film; a step of irradiating the photosensitive resin film with light of a predetermined pattern; and A step of disposing a catalyst for electroless plating in at least a part of the region irradiated with the predetermined pattern light and performing electroless plating.

7. A pattern forming method, comprising: A step of coating the photosensitive surface treatment agent according to claim 1 on a substrate to form a resin film; The process of removing the protection of the resin film to prepare a photosensitive resin film; irradiating the photosensitive resin film with light of a predetermined pattern to form an amine generating region in the exposed region; and A step of disposing an electroless plating catalyst in the amine generating region and performing electroless plating.

8. A pattern forming method, comprising: A step of coating the photosensitive surface treatment agent according to claim 1 on a substrate to form a resin film; The process of removing the protection of the resin film to prepare a photosensitive resin film; The process of immersing the photosensitive resin film in an alkaline solution; After the photosensitive resin film is immersed in the alkaline solution, a step of irradiating the photosensitive resin film with a predetermined pattern of light to form an amine generating region in the exposed region; and A step of disposing an electroless plating catalyst in the amine generating region and performing electroless plating.

9. A pattern forming method, comprising: A step of coating the photosensitive surface treatment agent according to claim 1 on a substrate to form a resin film; The process of removing the protection of the resin film to prepare a photosensitive resin film; The process of immersing the photosensitive resin film in an alkaline solution; A step of irradiating the photosensitive resin film with light of a predetermined pattern while immersing the photosensitive resin film in the alkaline solution to form an amine generating region in the exposed region; and A step of disposing an electroless plating catalyst in the amine generating region and performing electroless plating.

10. The pattern forming method according to claim 8 or 9, wherein: The alkaline solution is a tetrabutylammonium hydroxide (TBAH) aqueous solution. 11 . A method for manufacturing a transistor, comprising the step of forming at least one of a source electrode, a drain electrode, or a gate electrode by the pattern forming method according to claim 5 .

12. A transistor comprising a compound represented by the following formula (M1), [Chemistry 2] In formula (M1), R 1 is a hydrogen atom or a tert-butoxycarbonyl group or an ester protective group, R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m is an integer greater than 1, and X is a halogen atom or an alkoxy group.

13. The transistor according to claim 12, wherein: The compound has a portion in which at least a part of the nitrobenzyl group is detached to generate an amino group.

Images