Compounds, polymer compounds, photosensitive surface treatment agents, laminates, pattern-forming substrates, transistors, pattern-forming methods, and methods for manufacturing transistors.

Abstract

To provide a compound.SOLUTION: This compound is represented by general formula (M1). In formula (M1), Y is a linear or branched C1-C10 alkyl group, a polymerizable group-containing group, or a group represented by [SiX3-Y11-*]. Y11 is a linear or branched C1-C4 alkylene group, X is a halogen atom or an alkoxy group, and * is a bonding site with an N atom. R1 is a hydrogen atom or a methyl group. R2 is a hydrogen atom or a C1-C6 alkyl group. R3 and R4 are each independently a C1-C3 alkyl group or a fluoroalkyl group. n=2.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a compound, a polymer compound, a photosensitive surface treatment agent, a laminate, a substrate for pattern formation, a transistor, a pattern formation method, and a method for manufacturing a transistor. Background Art

[0002] In recent years, in the manufacture of fine devices such as semiconductor elements, integrated circuits, and devices for organic EL displays, methods have been proposed for forming patterns with different surface properties on a substrate and producing fine devices by utilizing the difference in surface properties.

[0003] As a pattern forming method utilizing the difference in surface properties on a substrate, for example, there is a method of forming a region where chemically active substituents are generated on a part of the substrate. By this method, a metal material, an organic material, or an inorganic material can be adhered to a part of the substrate.

[0004] Electroless plating is a known technique for adhering a metal material onto a substrate to form a metal film. For example, Patent Document 1 discloses a technique for forming fine wiring by electroless plating. Specifically, Patent Document 1 discloses that using a catalyst activation layer and a photoresist, photopatterning is performed by etching or lift-off from a state where the entire surface is plated. Prior Art Documents Patent Documents

[0005] Patent Document 1 Japanese Unexamined Patent Publication No. 2006-2201 Summary of the Invention

[0006] One aspect of the present invention is a compound represented by the following formula (M1).

[0007] Chemical Formula (In formula (M1), Y is a linear or branched alkyl group having 1 to 10 carbon atoms, a polymerizable group-containing group, or [SiX3-Y 11 This is the base represented by -*]. 11 R is a linear or branched alkylene group having 1 to 4 carbon atoms, X is a halogen atom or an alkoxy group, and * is a bond site with the N atom. 1 R is a hydrogen atom or a methyl group. 2 R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 3 , R 4 Each of these is independently an alkyl group or fluoroalkyl group having 1 to 3 carbon atoms. (n=2.) [Brief explanation of the drawing]

[0008] [Figure 1] This is a schematic diagram illustrating the pattern formation method of this embodiment. [Figure 2] This is a schematic diagram illustrating the manufacturing method of the transistor according to this embodiment. [Modes for carrying out the invention]

[0009] <Compound> One aspect of the present invention is a compound represented by the following formula (M1).

[0010] [ka]

[0011] In formula (M1), Y is a linear or branched alkyl group having 1 to 10 carbon atoms, and a linear or branched alkyl group having 1 to 5 carbon atoms is preferred for Y. Specifically, Y can be a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc.

[0012] In formula (M1), the polymerizable group-containing group of Y is [CH2=(CR 11)-C(=O)-O-(Y 11 )-*] include groups represented by . R 11 is a hydrogen atom or a methyl group, and Y 11 is a linear or branched alkylene group having 1 to 4 carbon atoms, and * is a bonding site to the N atom.

[0013] In formula (M1), when Y is a group represented by "SiX3-Y 11 -*", 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, an iodine atom, and the like.

[0014] Y 11 includes a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], and the like. Further, Y 1 includes -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, and the like.

[0015] X is preferably an alkoxy group. Examples of the alkoxy group for X include -O-(CH3) and -O-(CH2)n12(CH3). n12 is a natural number of 1 to 3.

[0016] In formula (M1), R 1 is a hydrogen atom or a methyl group.

[0017] In formula (M1), R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. As the alkyl group for R 2 , an alkyl group having 1 to 3 carbon atoms is preferred, a methyl group, an ethyl group, and an isopropyl group are more preferred, and an isopropyl group is even more preferred.

[0018] In formula (M1), R 3 , R 4 are each independently an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group. R 3 , R 4Preferably, the alkyl group is a linear or branched alkyl group having 1 to 3 carbon atoms, specifically a methyl group, an ethyl group, or a propyl group. R 3 , R 4 When is a fluoroalkyl group, it may be a partially fluorinated linear or branched alkyl group having 1 to 3 carbon atoms, or it may be a perfluoroalkoxy group. In this embodiment, a partially fluorinated fluorinated alkoxy group is preferred.

[0019] In equation (M1), n=2.

[0020] The compound represented by formula (M1) has two dinitrobenzyl groups. When light is shone on the compound represented by formula (M1), the dinitrobenzyl groups are removed and an amine is generated. Metallic, organic, or inorganic materials can be attached to the area where the amine is generated. The amine generated from the compound represented by formula (M1) is either a primary amine (-NH2) or a secondary amine (-NH-).

[0021] The compound represented by formula (M1) has a higher photoreaction efficiency (Φ365) than the compound having a mononitrobenzyl group. In this specification, photoreaction efficiency (Φ365) is the ratio of the photodecomposition rate constant (k) to the absorbance (A365), and is an index indicating the efficiency of the reaction in relation to absorbed light. Specifically, the photoreaction efficiency (Φ) is calculated by the following formula. Photoreaction efficiency (Φ365) = Photodecomposition rate constant (k) / Absorbance (A365)

[0022] A higher value of the photoreaction efficiency (Φ365) obtained from the above formula indicates a higher efficiency of the reaction in response to the received light, meaning that the elimination reaction of the protecting group proceeds more easily even with a small amount of exposure.

[0023] Through our investigations, we found that compounds represented by formula (M1) that have a dinitrobenzyl group have a higher photoreaction efficiency than compounds that have a mononitrobenzyl group. This is thought to be because the increase in nitro groups and structural changes enhance the effect of the nitro groups in the photoreaction. In this chemical structure, upon exposure to light, a six-membered ring transition state is formed from the hydrogen at the benzylic position to the oxygen of the nitro group, and the transfer of the hydrogen at the benzylic position to the oxygen of the nitro group is the first step in photodegradation. The positional relationship with the hydrogen at the benzylic position and the conformation are important for obtaining the effect of the nitro group. The improved photoreaction efficiency compared to mononitrobenzyl groups is presumed to be because compounds containing dinitrobenzyl groups have an effective conformation for hydrogen transfer.

[0024] Furthermore, our investigations revealed that, among the compounds represented by formula (M1), the compound having a dinitrobenzyl group exhibits a higher photodegradation rate than the compound having a mononitrobenzyl group.

[0025] Formula (M1) is preferably one of the following formulas (M1)-1, (M1)-2, or (M1)-3. In the following equations (M1)-1, (M1)-2, and (M1)-3, the explanation of each symbol is the same as the explanation of the symbols in equation (M1) above.

[0026] [ka]

[0027] Specific examples of compounds represented by formula (M1) are shown below.

[0028] [ka]

[0029] [ka]

[0030] [ka]

[0031] [ka]

[0032] [ka]

[0033] [ka]

[0034] <Method for producing compound (M1)> The compound represented by formula (M1) can be produced by the following method. In the following description of the manufacturing method, n=2, and the explanation for each sign is the same as the explanation for each sign in formula (M1) above.

[0035] The compound represented by formula (M1) can be produced by the steps of producing dinitro intermediate 1 or dinitro intermediate 2, and introducing Y into the obtained dinitro intermediate 1 or dinitro intermediate 2.

[0036] [ka]

[0037] Dinitro intermediate 1 is obtained by the reaction shown in (R)-1 below.

[0038] [ka]

[0039] Dinitro intermediate 2 is obtained by the reaction shown in (R)-2 below.

[0040] [ka]

[0041] The following is an example of a reaction in which Y is introduced into the obtained dinitro intermediate 1 or 2 to produce compound (M1).

[0042] [ka]

[0043] In the formula, "Y-NCO" is an alkyl isocyanate. The alkyl group of the alkyl isocyanate is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc.

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] [ka]

[0048] [ka]

[0049] <Method for producing compound (M1)-1> The compound represented by formula (M1)-1 can be produced by the steps of producing dinitro intermediate 1-1 or dinitro intermediate 2-1, and by introducing Y into the obtained dinitro intermediate 1-1 or dinitro intermediate 2-1.

[0050] [ka]

[0051] Dinitro intermediate 1-1 is obtained by the reaction shown in (R)-1-1 below.

[0052] [ka]

[0053] Dinitro intermediate 2-1 is obtained by the reaction shown in (R)-2-1 below.

[0054] [ka]

[0055] The following is an example of a reaction in which Y is introduced into the obtained dinitro intermediate 1-1 or dinitro intermediate 2-1 to produce compound (M1)-1.

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] <Method for producing compound (M1)-2> The compound represented by formula (M1)-2 can be produced by the steps of producing dinitro intermediate 1-2 or dinitro intermediate 2-2, and introducing Y into the obtained dinitro intermediate 1-2 or dinitro intermediate 2-2.

[0063] [ka]

[0064] Dinitro intermediates 1-2 are obtained by the reaction shown in (R)-1-2 below.

[0065] [ka]

[0066] In the reaction shown in (R)-1-1 and the reaction shown in (R)-1-2 above, both dinitro intermediates 1-1 and 1-2 are produced simultaneously. The product containing dinitro intermediates 1-1 and 1-2 can be purified by silica gel column chromatography to obtain dinitro intermediates 1-1 and 1-2, respectively.

[0067] Dinitro intermediate 2-2 is obtained by the reaction shown in (R)-2-2 below.

[0068] [ka]

[0069] The following is an example of a reaction in which Y is introduced into the obtained dinitro intermediate 1-2 or dinitro intermediate 2-2 to produce compound (M1)-2.

[0070] [ka]

[0071] [ka]

[0072] [ka]

[0073] [ka]

[0074] [ka]

[0075] [ka]

[0076] <Polymer compounds> One aspect of the present invention is a polymer compound comprising repeating units represented by the following formula (P1).

[0077] [ka] (In formula (P1), R 11 is a hydrogen atom or a methyl group, Y 11 R is a linear or branched alkylene group having 1 to 4 carbon atoms. 1 R is a hydrogen atom or a methyl group. 2 R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 3 , R 4 Each of these is independently an alkyl group or fluoroalkyl group having 1 to 3 carbon atoms. (n=2.)

[0078] In formula (P1), R 11 , Y 11 , R 1, R 3 , R 4 The explanation for this is the same as the explanation for each sign in formula (M1) above.

[0079] A polymer compound having repeating units represented by formula (P1) preferably has a substituent represented by the following formula (1x) attached to at least one of the ends of the main chain. In the following formula (1x), * represents the attachment site to the end of the main chain of the polymer compound having repeating units represented by formula (P1).

[0080] [ka]

[0081] A polymer compound (P1)-A is shown below as an example, in which a substituent represented by formula (1x) is attached to the end of the main chain of a polymer compound having repeating units represented by formula (P1).

[0082] [ka]

[0083] The repeating unit represented by formula (P1) is preferably one of the following formulas (P1)-1 to (P1)-3.

[0084] [ka]

[0085] <Method for producing polymer compound (P1)> By reacting a compound represented by formula (M1) containing polymerizable groups with various polymerization initiators such as radical polymerization initiators and anionic polymerization initiators, a polymer compound having repeating units represented by general formula (P1) can be obtained. An example of this reaction is described below.

[0086] [ka]

[0087] [ka]

[0088] [ka]

[0089] [ka]

[0090] The polymerization of the compound represented by formula (M1) containing a polymerizable group is not particularly limited, but it may be polymerized by radical polymerization, anionic polymerization, etc. Among these, radical polymerization is preferred from the viewpoint of ease of control. From the viewpoint of obtaining desired solubility by controlling the molecular weight, controlled radical polymerization is more preferred among radical polymerizations.

[0091] Examples of controlled radical polymerization methods include the chain transfer agent method and living radical polymerization, which is a type of living polymerization. Living radical polymerization is even more preferable because it allows for easy control of the molecular weight distribution. Examples of living radical polymerization methods include nitroxyl radical polymerization (NMP), atom transfer radical polymerization (ATRP), and reversible addition-cleavage chain transfer (RAFT). From the viewpoint of temperature and versatility, atom transfer radical polymerization (ATRP) is particularly preferred.

[0092] In addition to broadening the molecular weight distribution from low molecular weight to high molecular weight to obtain desired film-forming properties, radical polymerization involving chain transfer reactions is preferred from the viewpoints of productivity and economics. When using radical polymerization, conventionally known polymerization initiators can be used as appropriate. Furthermore, radical polymerization initiators may be used individually or in combination of two or more, or commercially available ones may be used as is.

[0093] For example, azo polymerization initiators, which are compounds having an azo group (-N=N-) and generating radicals with N2, can be used. Specifically, examples include azonitriles, azoesters, azoamides, azoamidines, and azoimidazolines. More specifically, examples include 2,2'-azobis(2-amidinopropane)dihydrochloride, 4,4'-azobis(4-cyanovaleric acid), 2,2'-bis(2-imidazolin-2-yl)-2,2'-azoprepanedihydrochloride, 2,2'-bis(2-imidazolin-2-yl)-2,2'-azoprepane, 2,2'-azobis[N-(2-hydroxyethyl)-2-methylpropionamide], 2,2'-azobisisobutyronitrile (AIBN), and 2,2'-azobis(2,4-dimethylvaleronitrile) (ADBN).

[0094] Among these, 2,2'-azobisisobutyronitrile (AIBN) and 2,2'-azobis(2,4-dimethylvaleronitrile) (ADBN) are preferred, and 2,2'-azobisisobutyronitrile (AIBN) is particularly preferred.

[0095] The polymer compound of this embodiment may consist of repeating units represented by formula (P1), or it may be a copolymer having other repeating units in addition to the repeating units represented by formula (P1) as needed. When the polymer compound of this embodiment is a copolymer containing repeating units other than the repeating units represented by formula (P1), the proportion of the other repeating units is, for example, 50 mol% or less, 40% or less, or 30 mol% or less, relative to the total amount (100 mol%) of all repeating units constituting the polymer compound.

[0096] Other repeating units include, for example, methyl acrylate, phenyl acrylate, benzyl acrylate, dimethoxynitrobenzylcarbonylaminoethyl acrylate, fluorenyl methoxycarbonylaminoethyl acrylate, methyl methacrylate, phenyl methacrylate, benzyl methacrylate, dimethoxynitrobenzylcarbonylaminoethyl methacrylate, and fluorenyl methoxycarbonylaminoethyl methacrylate.

[0097] The number-average molecular weight of a polymer compound having repeating units represented by formula (P1) is preferably 300 to 100,000, more preferably 1,000 to 90,000, and even more preferably 2,000 to 40,000, from the viewpoint of reducing the risk of dissolution and peeling in plating baths and ensuring solubility during film formation, so as to enable wet film formation. Similarly, the peak of the molecular weight distribution is in the range of 1,000 to 90,000, and even more preferably 2,000 to 40,000. These can be measured by gel permeation chromatography (GPC).

[0098] <Photosensitive surface treatment agent> In one embodiment of the present invention, the photosensitive surface treatment agent includes a compound represented by the above formula (M1). In another embodiment of the present invention, the photosensitive surface treatment agent may consist of a compound represented by the above formula (M1).

[0099] In one embodiment of the present invention, the photosensitive surface treatment agent includes a polymer compound having a repeating unit represented by the above formula (P1). In another embodiment of the present invention, the photosensitive surface treatment agent may consist of a polymer compound having a repeating unit represented by the above formula (P1).

[0100] In one embodiment of the present invention, the photosensitive surface treatment agent comprises a compound represented by the above formula (M1) and a polymer compound containing repeating units represented by the above formula (P1).

[0101] In one embodiment of the present invention, the photosensitive surface treatment agent may contain a solvent. By dissolving it in common organic solvents such as alcohol-based solvents, ester-based solvents, hydrocarbon-based aromatic solvents, amine-based solvents, ketone-based solvents, glycol ether-based solvents, and ether-based solvents, it can be used as a suitable surface treatment agent.

[0102] Examples of alcohol-based solvents include isopropyl alcohol (IPA) and n-butyl alcohol (n-butanol).

[0103] Examples of ester solvents include ethyl acetate (EAC), butyl acetate (NBAC), n-propyl acetate (NPAC), and 3-methoxy-3-methylbutyl acetate.

[0104] Examples of hydrocarbon aromatic solvents include toluene, xylene, benzene, ethylbenzene, and trimethylbenzene.

[0105] Examples of amine-based solvents include N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), and N,N-dimethylacetamide (DMAC).

[0106] 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.

[0107] Examples of glycol ether solvents include methyl cellosolve, butyl cellosolve, ethylene glycol mono-t-butyl ether (ETB), propylene glycol monomethyl ether (PGME), proether solvent pyrene glycol monomethyl ether acetate (PGMEA), and 3-methoxy-3-methyl-1-butanol (MMB).

[0108] 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. Organic solvents can be appropriately selected according to conditions such as pollution, solubility, volatility, attack on substrates and undercoats, and film deposition equipment and methods.

[0109] In this invention, by making the photosensitive surface treatment layer poorly soluble, it becomes insoluble in cleaning solutions, plating solutions, and solvents used in multilayer film formation, thereby improving cleaning resistance and process resistance during wiring and lamination processes.

[0110] In the case of a photosensitive surface treatment agent comprising the compound represented by the above formula (M1), from the viewpoint of improving the reactivity between the primer and the photosensitive surface treatment agent, and between the molecules of the photosensitive surface treatment agent, alcohol-based, ether-based, and hydrocarbon-based solvents are preferred as the solvents included, and hydrocarbon-based solvents, with toluene being particularly preferred. Furthermore, from the viewpoint of enhancing the above-mentioned reactivity, any acidic or basic compound may be included during film formation. This can be appropriately selected depending on the film formation conditions, and acidic compounds such as hydrochloric acid, acetic acid, and nitric acid are particularly preferred, with acetic acid being the most preferred among them.

[0111] In the case of a photosensitive surface treatment agent comprising a polymer compound having repeating units represented by the above formula (P1), from the viewpoint of solubility and film-forming properties, ester-based and ketone-based solvents are preferred as the solvent, and ketone-based solvents, particularly cyclopentanone, are preferred.

[0112] The concentration of the compound represented by formula (M1) or the polymer compound having repeating units represented by formula (P1) contained in the photosensitive surface treatment agent can be appropriately selected depending on the film formation conditions, but from the viewpoint of storage stability and economy, 0.001 to 10% by mass is preferred, more preferably 0.01 to 2% by mass, and among these, 0.1 to 0.3% by mass is preferred.

[0113] <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 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.

[0114] As shown in Figure 1(a), the photosensitive surface treatment agent 10a of this embodiment is applied to the substrate 11. 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. Coating may also be done by printing methods such as flexographic printing and screen printing. Furthermore, SAM films and LB films may be used.

[0115] 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.

[0116] As a result, a photosensitive surface treatment layer 10 is formed on the substrate 11, as shown in Figure 1(b).

[0117] 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.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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), gold (Au), and copper (Cu).

[0124] 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.

[0125] 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.

[0126] <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.

[0127] 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.

[0128] 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.

[0129] 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.

[0130] 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).

[0131] 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).

[0132] 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.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] <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.

[0137] <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]

[0138] 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.

[0139] The nitration of 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropanone was carried out by the reaction shown below, yielding intermediates A and B.

[0140] [ka]

[0141] 500 mg (1.97 mmol, 1.0 eq, MI457) of 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropanone was placed in a 100 mL wide-mouthed round-bottom flask. 33 mL (70.2 mol, 36 eq) of fuming HNO was slowly added dropwise over 5 minutes at 0°C (ice water), and the mixture was stirred at room temperature for 30 minutes. 45 mL of cold water was added to the reaction solution, and after stirring at 0°C for 1 hour, the mixture was filtered by suction using a membrane filter, rinsed with 45 mL of H2O, and vacuum dried to obtain 421 mg of a light brown solid. The mixture was purified by silica gel column chromatography (eluent hexane:ethyl acetate = 2:1), concentrated, and vacuum-dried to obtain 30 mg (0.10 mmol, 5%) of yellow oil A (intermediate A) as fraction 1 and 144 mg (purity 63%, equivalent yield 91 mg, 0.30 mmol, 15%) of pale yellow solid B (intermediate B) as fraction 2.

[0142] The measurement results for intermediates A and B are shown below. Intermediate A 1 H NMR (CDCl3) 1.23(6H, d), 2.82 (1H, m), 4.05 (3H, s), 4.07 (3H, s), 7.81 (1H, s). 13 C NMR (CDCl3) 18.33, 41.80, 57.14, 62 / 69, 109.67, 124.30. 140.79, 146.30, 153.48, 201.89. FTIR(NaCl) 1706, 1549, 1341, 1293 cm -1 . ESI MS 321.0730, calcd for C 12 H 14 N2O7Na [M + Na + 321.0699. Mp. 70.1-72.6℃ Intermediate B 1 H NMR (CDCl3) 1.23 (6H, d), 2.92 (1H, m), 4.00 (3H, s), 4.04 (3H, s), 6.87 (1H, s). 13 C NMR (CDCl3)18.54, 40.77, 57.24, 62.75, 111.03, 131.26, 134.63, 140.25, 142.46, 157.63, 203.96. ESI MS 321.0723, calcd for C 12 H 14 N2O7Na [M + Na+ 321.0699. Mp. 115.2-117.2 ℃

[0143] <Example 1> The intermediate A obtained above was reduced by the reaction shown below to obtain 1-(3,4-dimethoxy-2.6-dinitrophenyl)-2-methylprooan-1-ol.

[0144] [ka]

[0145] In a 20 mL round-bottom flask, 57 mg (0.19 mmol, 1.0 eq) of 1-(3,4-dimethoxy-2,6-dinitrophenyl)-2-methylpropanone was dissolved in 1 mL of tetrahydrofuran (THF) and 0.5 mL of methanol. At 0°C, 11 mg (0.29 mmol, 1.5 eq) of sodium tetrahydroborate was gradually added, and the mixture was stirred at 0°C for 30 minutes, followed by stirring at room temperature for 3 hours. After concentration under reduced pressure, ethyl acetate (2 mL x 5) and water (2 mL) were added for extraction. The solution was dried over anhydrous magnesium sulfate, filtered, concentrated, and vacuum-dried to obtain 46 mg of brown viscous material. This was purified by silica gel column chromatography (eluent hexane:ethyl acetate = 3:1), concentrated, and vacuum-dried to obtain 18 mg of yellow oil (purity 60%, 0.0036 mmol, yield 19%).

[0146] The measurement results for 1-(3,4-dimethoxy-2.6-dinitrophenyl)-2-methylprooan-1-ol are shown below. 1 H NMR (CDCl3) 0.74 (3H, d), 1.08 (3H, d), 2.07 (1H, m), 3.98 (3H, s), 4.00 (3H, s), 4.57 (1H, br), 7.46 (1H, s). 13C NMR (CDCl3) 19.26, 19.67, 33.79, 56.81, 62.46, 74.75, 110.26, 123.02, 144.35, 144.54, 145.88, 151.90. FTIR(NaCl) 3565, 2967, 1547, 1350, 1293 cm -1 . ESI MS 323.0883, calcd for C 12 H 16 N2O7Na [M + Na + 323.0855.

[0147] Furthermore, model compound A(1-(3,4-dimethoxy-2,6-dinitrophenyl)-2-methylpropyl N-butylcarbamate) was synthesized by the reaction shown below.

[0148] [ka]

[0149] In a 10 mL ground-glass tube, 17 mg of 1-(3,4-dimethoxy-2,6-dinitrophenyl)-2-methylpropanol (60% purity, 0.034 mmol) was added and dissolved in 1 mL of dry tetrahydrofuran (THF). 5 μL of dibutyltin dilaurate (DBTL) (0.008 mmol, 0.2 eq) and 20 μL of butyl isocyanate (BuNCO) (0.75 mmol, 22 eq) were added, and the mixture was refluxed under a nitrogen atmosphere for 19 hours. The mixture was concentrated under reduced pressure and dried under vacuum to obtain 56 mg of a dark brown solid. This solid was purified by silica gel column chromatography (chloroform as the developing solvent), concentrated, and dried under vacuum to obtain 13 mg (0.030 mmol, yield 88%) of the target product (model compound A) as a yellow oil.

[0150] The measurement results for model compound A are shown below. 1H NMR (CDCl3) 0.88 (3H, t), 0.89 (3H, d), 0.93 (3H, d), 1.32 (2H, m), 1.47 (2H, m), 2.25 (1H, m), 3.12 (2H, m), 3.97 (6H, s), 4.68 (1H, br), 5.92 (1H, d), 7.52 (1H, s). 13 C NMR (CDCl3). 13.70, 18.21, 19.80, 19.98, 31.80, 33.18, 40.83, 56.73, 62.42, 74.89, 109.90, 121.37, 144.56, 144.76, 144.83, 151.86, 155.29 ESI MS 422.1571, calcd for C 17 H 25 N3O8Na [M + Na + 422.1539.

[0151] <Example 2> The intermediate B obtained above was reduced by the reaction shown below to obtain 1-(4,5-dimethoxv-2,3-dinitrophenyl)-2-methylpropan-1-ol.

[0152] [ka]

[0153] In a 50 mL round-bottom flask, 144 mg of 1-(4,5-dimethoxy-2,3-dinitrophenyl)-2-methylpropanone (63% purity, equivalent to 91 mg, 0.30 mmol, 1.0 eq) was dissolved in 2 mL of tetrahydrofuran (THF) and 1 mL of methanol. 17 mg of sodium tetrahydroborate (0.45 mmol, 1.5 eq) was gradually added at 0°C while stirring for 30 minutes, and then stirred at room temperature for 3 hours. After concentration under reduced pressure, ethyI acetate (2 mL x 5) and water (5 mL) were added for extraction. The mixture was dried over anhydrous magnesium sulfate, filtered, concentrated, and vacuum-dried to obtain 139 mg of brown viscous material. This material was purified by silica gel column chromatography (eluent hexane:ethyl acetate = 2:1), concentrated, and vacuum-dried to obtain 75 mg (0.25 mmol, 82%) of yellow oil (including the raw materials) as the target product.

[0154] The measurement results for 1-(4,5-dimethoxv-2,3-dinitrophenyl)-2-methylpropan-1-ol are shown below. 1 H NMR (CDCl3) 0.92 (3H, d), 0.97 (3H, d), 1.95 (1H, m), 2.21(1H, d), 3.99 (3H, s), 4.01 (3H, s), 4.87 (1H, br), 7.31 (1H, s). 13 C NMR (CDCl3). 16.83, 19.48, 34.70, 56.83, 62.62, 73.28, 111.71, 134.10, 135.89, 140.07, 140.94, 156.12. FTIR(NaCl) 3585, 2964, 1551, 1350, 1291 cm -1 . ESI MS 323.0873, calcd for C 12 H 16 N2O7Na [M + Na + 323.0855.

[0155] Furthermore, the model compound B(1-(4,5-dimethoxy-2,3-dinitrophenyl)-2-methylpropyl N-butylcarbamate) was synthesized by the reaction shown below.

[0156] [ka]

[0157] In a 10 mL ground-glass tube, 150 mg (0.50 mmol) of 1-(4,5-dimethoxy-2,3-dinitrophenyl)-2-methylpropan-1-ol was added and dissolved in 1.5 mL of dry tetrahydrofuran (THF). 15 μL (0.025 mmol, 0.05 eq) of dibutyltin dilaurate (DBTL) and 85 μL (0.75 mmol, 1.5 eq) of butyl isocyanate (BuNCO) were added, and the mixture was refluxed under a nitrogen atmosphere for 19 hours. The mixture was concentrated under reduced pressure and dried under vacuum to obtain 251 mg of a dark brown solid. The solid was purified by silica gel column chromatography (eluent hexane:ethyl acetate = 2:1), concentrated, and dried under vacuum. After rinsing with hexane, the solid was dried under vacuum to obtain 156 mg (0.39 mmol, 78%) of the target product (model compound B) as an orange solid.

[0158] The measurement results for model compound B are shown below. 1 H NMR (CDCl3) 0.90 (3H, t), 0.91 (3H, d), 1.03 (3H, d), 1.32 (2H, m), 1.45 (2H, m), 2.18 (1H, m), 3.13 (2H, m), 3.93 (3H x 2, 2s), 4.76 (1H, br), 5.61 (1H, d), 6.97 (1H, s). 13 C NMR (CDCl3) 13.69, 17.88, 19.21, 19.86, 31.88, 33.39, 40.85, 56.71, 62.58, 76.04, 111.29, 131.17, 134.82, 140.45, 141.14, 155.28, 155.84. Anal. Calcd for C17H25N3O8: C 51.12, H 6.31, N 10.52%. Found: C 51.07, H6.20, N 10.42%. FTIR (KBr disk): 1693, 1557, 1359 cm-1. Mp 106.9 - 108.1 °C

[0159] <Comparative Example 1> The mononitro compound (Synthesis of 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropyl N-butylcarbamate) was produced by the reaction shown below.

[0160] [ka]

[0161] In a 200 mL round-bottom flask, 4.0 g (10 mmol) of 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropyl(2-methylene-5-oxopyrrolidin-1-yl)carbonate was added and dissolved in 40 mL of dry tetrahydrofuran (THF). 2 mL (20 mmol, 2 eq) of butylamine was added, and the mixture was stirred at room temperature under a nitrogen atmosphere for 3 hours. The mixture was concentrated under reduced pressure, dissolved in 80 mL of ethyl acetate, washed three times with 40 mL of water, dried over anhydrous magnesium sulfate, and then vacuum-dried to obtain 4.51 g of a pale yellow solid. The solid was purified by silica gel column chromatography (chloroform as the developing solvent), concentrated, and vacuum-dried to obtain 3.41 g (9.62 mmol, 96% yield) of the target mononitro compound.

[0162] 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropyl (2-methylene-5-oxopyrrolidin-1-yl)carbonate was synthesized by previously reported methods (as described in Non-Patent Documents 1 and 2 below). Note 1: Noriko Chikaraishi Kasuga, Yusuke Saito, Naomichi Okamura, Tatsuya Miyazaki, Hikaru Satou, Kazuhiro Watanabe, Takaki Ohta, Shu-hei Morimoto, Kazuo Yamaguchi, Influences of alpha-substituent in 2-nitrobenzyl-protected esters on Both photocleavage rate and subsequent photoreaction of the generated 2-nitrosoketones: A novel photorearrangement of 2-nitrosoketones, J. Photochem. Photobiol. A: Chem., 2016, 321, 41-47. Product 2:Takuma Igari and Kazuo Yamaguchi, 2-Nitrobenzylcarbamate-Bearing Alkylphosphonic Acid Derivative Forms Photodegradable Self-Assembled Monolayer That Enables Fabrication of a Patterned Amine Surface, Chem. Lett. 2017, 46(8)1220–1222.

[0163] The snowflake snowflakes are covered. 1 H-NMR (CDCl3) 0.90 (3H, t), 0.99 (6H, m), 1.31 (2H, sext), 1.46 (2H, quint), 2.14 (1H, Sept), 3.14 (2H, m), 3.94 (6H, s), 4.76 (1H, t), 6.23 (1H, d), 6.90 (1H,s), 7.61 (1H,s) 13C-NMR(CDCl3) 13.71, 17.20, 19.43, 19.88, 32.04, 33.34, 40.78, 56.33, 75.74, 107.97, 108.94, 132.17, 140.65, 147.76, 153.02, 155.73 FTIR(KBr) 3303, 1685, 1518, 1274 cm -1

[0164] <Photolysis rate constant k(s -1 ) measurement> Model compound A, model compound B, and mononitro compound obtained above were each dissolved in acetonitrile to prepare 0.1 mM solutions. Using a high-pressure mercury lamp, filtered through a 365nm bandpass filter and a water filter, the wavelength is 365nm and the illuminance is 25mW / cm². 2 The light was irradiated for 5, 10, 15, 20, 25, and 30 seconds, and each measurement was performed using HPLC.

[0165] Peak area of ​​raw material obtained from HPLC measurement (S0: area before light irradiation, S t Substitute the area (area after t seconds of light irradiation) into the following formula to obtain the photodecomposition rate constant k(s) from the rate of reduction of the raw material. -1 We calculated the following. The results are shown in Table 1.

[0166]

number

[0167] <Molar extinction coefficient (ε 365 / M -1 cm -1 ) measurement> Model compound A, model compound B, and mononitro compound obtained above were each dissolved in acetonitrile to prepare 0.1 mM solutions. The solutions were placed in a quartz cell with a path length of 1 cm, and the molar extinction coefficient (ε) was calculated from the absorbance measured using a UV-Vis spectrophotometer (V-570, JASCO Corporation). 365 / M -1 cm -1 ) was calculated.

[0168] <Half-life (t 1 / 2 / s) Calculation> Half-life (t 1 / 2 / s) was calculated from the photolysis rate constant.

[0169] <Calculation of photoreaction efficiency (Φ365)> Photoreaction efficiency (Φ365) was calculated by the following method from the photolysis rate constant measured using a solution with a concentration of 0.1 mM and absorbance (A365). Photoreaction efficiency (Φ365) = Photolysis rate constant (k) / Absorbance (A365)

[0170]

Table 1

[0171] It was confirmed that model compounds A and B having a dinitrobenzyl group have photoreaction efficiency approximately 4 times or more higher than that of the mononitro compound having a mononitrobenzyl group. Furthermore, model compounds A and B having a dinitrobenzyl group had a faster photolysis rate than the mononitro compound having a mononitrobenzyl group. Further, when comparing model compounds A and B, it was confirmed that model compound B has a faster photolysis rate.

[0172] From the results of the above model compounds A and B, it can be sufficiently inferred that the compound represented by formula (M1) having a dinitrobenzyl group and the polymer compound represented by formula (P1) also exhibit the same effects of high photoreaction efficiency and improved photolysis rate.

Description of Reference Numerals

[0173] 11: substrate, 10a: photosensitive surface treatment agent, 10: photosensitive surface treatment agent layer, 13: photomask, 14: amine generation region, 12: amine non-generation region, 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 compound represented by the following general formula (M1). 【Chemistry 1】 (In formula (M1), Y is a linear or branched alkyl group having 1 to 10 carbon atoms, a polymerizable group-containing group, or [SiX ３ -Y １１ It is a base represented by -*. Y １１ R is a linear or branched alkylene group having 1 to 4 carbon atoms, X is a halogen atom or an alkoxy group, and * is a bond site with the N atom. １ R is a hydrogen atom or a methyl group. ２ R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ３ , R ４ Each of these is independently an alkyl group or fluoroalkyl group having 1 to 3 carbon atoms.

2. A polymer compound having repeating units represented by the following general formula (P1). 【Chemistry 2】 In Formula (P1), R １１ is a hydrogen atom or a methyl group, and Y １１ is a linear or branched alkylene group having 1 to 4 carbon atoms. R １ is a hydrogen atom or a methyl group. R ２ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ３ , R ４ are each independently an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group.)

3. A photosensitive surface treatment agent comprising the compound described in claim 1 or the polymer compound described in claim 2.

4. A laminate comprising the photosensitive surface treatment agent described in claim 3.

5. A pattern-forming substrate having a surface chemically modified using the photosensitive surface treatment agent described in claim 3.

6. A transistor comprising the photosensitive surface treatment agent described in claim 3.

7. A step of applying the photosensitive surface treatment agent described in claim 3 onto a substrate to form 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.

8. A step of applying the photosensitive surface treatment agent described in claim 3 onto a substrate to form 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.

9. A step of applying the photosensitive surface treatment agent described in claim 3 onto a substrate to form 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.

10. 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 7.

11. A transistor comprising a compound represented by the following formula (M1) or a polymer compound having repeating units represented by the following formula (P1). 【Transformation 3】 (In formula (M1), Y is a linear or branched alkyl group having 1 to 10 carbon atoms, a polymerizable group-containing group, or [SiX ３ -Y １１ It is a base represented by -*]. Y １１ R is a linear or branched alkylene group having 1 to 4 carbon atoms, X is a halogen atom or an alkoxy group, and * is a bond site with the N atom. １ R is a hydrogen atom or a methyl group. ２ R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ３ , R ４ Each of these is independently an alkyl group or fluoroalkyl group having 1 to 3 carbon atoms. 【Chemistry 4】 (In formula (P1), R １１ is a hydrogen atom or a methyl group, Y １１ R is a linear or branched alkylene group having 1 to 4 carbon atoms. １ R is a hydrogen atom or a methyl group. ２ R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ３ , R ４ Each of these is independently an alkyl group or fluoroalkyl group having 1 to 3 carbon atoms.

12. The transistor according to claim 11, wherein the compound or polymer compound has a portion in which at least some nitrobenzyl groups are removed to generate amino groups.

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