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

Abstract

A photosensitive surface treatment agent containing a compound represented by formula (M1). In formula (M1), R1 is a linear, branched or cyclic alkyl group having 1-6 carbon atoms, and Y1 is a linear or branched alkylene group having 1-4 carbon atoms, or a single bond. The carbon atom at the terminal of the alkyl group of R1 may be bonded to the carbon atom of the alkylene group constituting Y1 to cause R1 and Y1 to form a ring. (In the formula, R1 represents a hydrogen atom or an alkyl group having 1-6 carbon atoms, R2 represents a hydrogen atom or an alkyl group having 1-6 carbon atoms, R3 and R4 each independently represent an alkyl group having 1-3 carbon atoms, n0 represents an integer of 0 or more, and X represents a halogen atom or an alkoxy group. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to 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.

[0002] This application claims priority based on Japanese Tokugan Application No. 2022-131901 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 comprising a compound represented by the following formula (M1).

[0010] [Chemistry 1]

[0011]

[0012] (In formula (M1), R 1 is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, 1 R is a linear or branched alkylene group having 1 to 4 carbon atoms, or a single bond. 1 The terminal carbon atom of the alkyl group may be connected to the 1 The carbon atom of the alkylene group is bonded to make R 1 and Y 1 Form a ring.

[0013] R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 3 and R 4 Each independently represents an alkyl group having 1 to 3 carbon atoms, n0 is an integer greater than 0, and X is a halogen atom or an alkoxy group). BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 It is a schematic diagram for explaining the pattern forming method of this embodiment.

[0015] Figure 2 This is a schematic diagram for explaining the method for manufacturing the transistor of this embodiment.

[0016] Figure 3A This is the overall image of the resolution map drawn on the polyimide substrate and the quartz substrate.

[0017] Figure 3B is an optical microscope image of a resolution map depicted on a quartz substrate.

[0018] Figure 3C This is an optical microscope image of L / S = 3 / 3 to 10 / 10 μm drawn on a quartz substrate.

[0019] Figure 3D These are optical microscope images of L / S = 1 / 1 to 8 / 8 μm drawn on a quartz substrate. DETAILED DESCRIPTION

[0020] <Photosensitive surface treatment agent>

[0021] The photosensitive surface treatment agent of the present embodiment contains a compound represented by the following formula (M1).

[0022] [Chemistry 2]

[0023]

[0024] (In formula (M1), R 1 is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, 1 R is a linear or branched alkylene group having 1 to 4 carbon atoms, or a single bond. 1 The terminal carbon atom of the alkyl group may be connected to the 1 The carbon atom of the alkylene group is bonded to make R 1 and Y 1 Form a ring.

[0025] R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 3 and R 4Each independently represents an alkyl group having 1 to 3 carbon atoms, n0 is an integer greater than 0, and X is a halogen atom or an alkoxy group).

[0026] (R 1 )

[0027] In formula (M1), R 1 It is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl and tert-butyl.

[0028] (Y 1 )

[0029] In formula (M1), Y 1 Y is a linear or branched alkylene group having 1 to 4 carbon atoms. 1 Examples include methylene [-CH2-], ethylene [-(CH2)2-], trimethylene [-(CH2)3-], tetramethylene [-(CH2)4-], and the like. 1 Examples include -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, and -C(CH3)(CH2CH3)-.

[0030] In formula (M1), Y 1 Can be a single key.

[0031] R 1 The terminal carbon atom of the alkyl group may be connected to the 1 The carbon atom of the alkylene group is bonded to make R 1 and Y 1 Form a ring.

[0032] In this case, R 1 and Y 1 The ring formed is, for example, piperidinyl.

[0033] That is, formula (M1) may be the following formula (M1)-A.

[0034] [Chemistry 3]

[0035]

[0036] (In formula (M1), R 1 is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, 12 It is a linear or branched alkylene group having 1 to 4 carbon atoms. 12 The terminal carbon atom of the alkyl group is 12 The carbon atoms of the alkylene group are bonded to form a ring.

[0037] R 2is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 3 and R 4 Each independently represents an alkyl group having 1 to 3 carbon atoms, n0 is an integer greater than 0, and X is a halogen atom or an alkoxy group).

[0038] (R 2 )

[0039] 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 methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, hexyl, and cyclohexyl. Among them, isopropyl or cyclohexyl is preferred, and isopropyl is more preferred.

[0040] (R 3 and R 4 )

[0041] R 2 and R 3 Each independently represents an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include methyl group, ethyl group and propyl group, and methyl group or ethyl group is preferred, and methyl group is more preferred.

[0042] (n0)

[0043] In the formula (M1), n0 is an integer of 0 or more, preferably 1 or more and 6 or less, and more preferably 1 or more and 4 or less.

[0044] (X)

[0045] In formula (M1), 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.

[0046] 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.

[0047] Specific examples of the compound represented by formula (M1) are described below.

[0048] [Chemistry 4]

[0049]

[0050] [Chemistry 5]

[0051]

[0052] [Chemistry 6]

[0053]

[0054] [Chemistry 7]

[0055]

[0056] [Chemistry 8]

[0057]

[0058] If a photosensitive surface treatment agent containing a compound represented by formula (M1) is applied to a substrate and irradiated with light, the nitrobenzyl group is detached, SiX3 is closely attached to the substrate, and amines are generated on the surface of the substrate. Metallic materials, organic materials, or inorganic materials can be closely attached to the portion where amines are generated. The amines generated by the compound represented by formula (M1) are primary amines (-NH2) or secondary amines (-NH-).

[0059] In the compound represented by formula (M1), R 1 is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. 1 The larger the group of the compound is, the faster the photolysis rate of the nitrobenzyl group is.

[0060] Furthermore, the compound represented by formula (M1) has R 1 Since it is a structure as described above, the reverse reaction after photodecomposition is unlikely to occur. The reverse reaction after photodecomposition is a reaction in which the nitrobenzyl group that has been separated after photodecomposition is bonded again.

[0061] 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 fine metal pattern with a line width of 3 μm or less can be formed on the substrate surface without using a photoresist process, a development process, or an etching process.

[0062] One embodiment of the present invention is a photosensitive surface treatment agent including a polymer compound represented by the following formula (P1).

[0063] [Chemistry 9]

[0064]

[0065] (In formula (P1), R 1 is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, 1 is a linear or branched alkylene group having 1 to 4 carbon atoms, or a single bond, 2 It is a group formed by removing two hydrogen atoms from an aromatic ring having 6 to 15 carbon atoms. 1 The terminal carbon atom of the alkyl group may be connected to the 1 The carbon atom of the alkylene group is bonded to make R 1 and Y 1 Form a ring.

[0066] R2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 3 and R 4 are each independently an alkyl group having 1 to 3 carbon atoms, R 5 is a hydrogen atom or a methyl group, n0, n1, and n2 are each independently an integer greater than 0, and m is a natural number).

[0067] In formula (P1), about R 1 , R 2 , R 3 , R 4 , R 5 , Y 1 , Y 2 The descriptions of n0, n1, and n2 are the same as above, and m is a natural number.

[0068] The polymer compound represented by formula (P1) preferably has a substituent represented by the following formula (1x) bonded to at least one terminal of the main chain. In the following formula (1x), * indicates a bonding position to a terminal of the main chain of the polymer compound represented by formula (P1).

[0069] [Chemistry 10]

[0070]

[0071] The following is a polymer compound (P1)-A in which a substituent represented by the above formula (1x) is bonded to the terminal of the main chain of the polymer compound represented by the formula (P1).

[0072] [Chemistry 11]

[0073]

[0074] Other specific examples of the polymer compound represented by formula (P1)-A are described below.

[0075] [Chemistry 12]

[0076]

[0077] [Chemistry 13]

[0078]

[0079] [Chemistry 14]

[0080]

[0081] [Chemistry 15]

[0082]

[0083] [Chemistry 16]

[0084]

[0085] The number average molecular weight of the polymer compound represented by formula (P1) is preferably 300 to 100,000, and more preferably 2,000 to 40,000. These can be measured by gel permeation chromatography (GPC) or matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-Tof-MS).

[0086] <Method for producing compound>

[0087] The compound represented by formula (M1) can be produced by the following method.

[0088] In the following description of the production method, the description of each symbol in the formula is the same as the above.

[0089] The compound represented by formula (M1) can be produced by a step including synthesizing an active intermediate from an alcohol and reacting the intermediate with a primary or secondary amine.

[0090] Examples of the reactive intermediate include a reactive intermediate (e.g., carboxylic acid chloride) obtained by activating benzyl alcohol with phosgene as shown in the following reaction formula (R)-1, a reactive intermediate (e.g., oxycarbonylimidazole) obtained by activating benzyl alcohol with carbonyl imidazole as shown in the following reaction formula (R)-2, and a reactive intermediate (e.g., oxycarbonyloxysuccinimide) obtained by activating benzyl alcohol with carbonyloxysuccinimide as shown in the following reaction formula (R)-4. The following reactions (R)-1, (R)-2, and (R)-4 show the use of a compound containing R 1 A method for preparing a compound represented by formula (M1) by using a secondary amine compound containing R 1 After the primary amine compound is formed into carbamate, R is introduced into the nitrogen in accordance with the production method described below. 1 , thereby producing the compound represented by formula (M1).

[0091] [Chemistry 17]

[0092]

[0093] As the starting material shown in the above reaction (R)-1, for example, the compound (R) of CAS No. 42855-00-5 can be mentioned. 2 H), CAS No.363135-50-6 (R 2 is Me).

[0094] Compound CAS No.42855-00-5 (R 2The synthesis method of H) is disclosed in Chemical Science (2016), 7 (3), 1891-1895. R can be prepared by the same method as disclosed in Chemical Science (2016), 7 (3), 1891-1895. 2 A compound having a desired alkyl group.

[0095] [Chemistry 18]

[0096]

[0097] As the starting material represented by the above reaction (R)-2, for example, the compound (R) of CAS No. 188305-03-5 can be mentioned. 2 H), CAS No.2097130-00-0(R 2 is Me).

[0098] Compound CAS No. 2097130-00-0 (R 2 The synthesis method of Me) is disclosed in Organic Letters (2017), 19 (7), 1618-1621. R can be prepared by the same method as disclosed in Organic Letters (2017), 19 (7), 1618-1621. 2 A compound having a desired alkyl group.

[0099] [Chemistry 19]

[0100]

[0101] In addition, the compound represented by formula (M1) can be produced by reacting an active intermediate obtained by activating benzyl alcohol with formyl chloride or carbonate with an amino compound having a terminal double bond to form nitrobenzyl carbamate, and then reacting the reactant with a metal catalyst or a trialkoxysilane such as trimethoxyhydrogensilane.

[0102] The following reaction formula (R)-5 is an example of using a compound containing an allyl group as an amino compound containing a terminal double bond.

[0103] [Chemistry 20]

[0104]

[0105] The following reaction formula (R)-6 is an example of using a compound containing a vinyl group as an amino compound containing a terminal double bond.

[0106] [Chemistry 21]

[0107]

[0108] The compound represented by formula (M1) can be prepared by reacting an active intermediate obtained by activating benzyl alcohol with formyl chloride, carbonate or the like with an aminosilane compound containing a primary amine to form nitrobenzyl carbamate, and then reacting the reactant with a silane compound containing R 1 It is produced by reacting with iodine or an alkyl compound having a leaving group.

[0109] The following reaction formula (R)-7 is a 1 Examples of reactions with iodine compounds.

[0110] [Chemistry 22]

[0111]

[0112] The following reaction formula (R)-8 is a 1 An example of reaction with a compound having a tosyloxy group. It should be noted that the tosyloxy group is removed during the reaction.

[0113] [Chemistry 23]

[0114]

[0115] Does not include R 1 The carbamate compound can be prepared by reacting benzyl alcohol with a compound containing isocyanate. The following reaction formula (R)-10 is an example of reacting benzyl alcohol with an isocyanate compound containing a trialkoxysilyl group. 1 In the carbamate compound, R 1 , thereby the compound represented by formula (M1) can be produced.

[0116] [Chemistry 24]

[0117]

[0118] <Method for producing polymer compound>

[0119] The compound represented by formula (P1) can be produced by the following method.

[0120] In the following description of the production method, the description of each symbol in the formula is the same as the above.

[0121] The precursor of the polymer compound represented by the formula (P1) is prepared by reacting an active intermediate obtained by activating benzyl alcohol with phosgene as shown in the following reaction formula (PR)-1 with a 1 The invention is produced by reacting an amino methacrylate compound.

[0122] The precursor of the polymer compound represented by the formula (P1) is prepared by reacting an active intermediate obtained by activating benzyl alcohol with carbonyloxyimidazole as shown in the following reaction formula (PR)-2 with a 1 The invention is produced by reacting an amino methacrylate compound.

[0123] The precursor of the polymer compound represented by the formula (P1) is prepared by reacting an active intermediate obtained by activating benzyl alcohol with carbonyloxysuccinimide as shown in the following reaction formula (PR)-4 with a 1 The invention is produced by reacting an amino methacrylate compound.

[0124] The following reaction shows the use of 1 The method for producing the compound represented by formula (P1) is not limited to this method, and a secondary amine compound not containing R may also be used. 1 After the primary amine compound is formed into carbamate, R is introduced into the nitrogen in accordance with the production method described below. 1 , thereby producing the compound represented by formula (P1).

[0125] [Chemistry 25]

[0126]

[0127] The P1 precursor, which is a precursor of the polymer compound represented by formula (P1), is produced by reacting an active intermediate obtained by activating benzyl alcohol using formyl chloride, carbonate, etc., as shown in the following reaction formula (PR)-5, with an amino alcohol compound to form nitrobenzyl carbamate, which is then reacted with methacrylic acid to produce the product.

[0128] The P1 precursor, which is a precursor of the polymer compound represented by formula (P1), is manufactured by reacting an active intermediate obtained by activating benzyl alcohol using formyl chloride, carbonate, etc., as shown in the following reaction formula (PR)-6, with an amino alcohol compound to form nitrobenzyl carbamate, and then reacting it with methacryloyl chloride to manufacture it.

[0129] [Chemistry 26]

[0130]

[0131] The precursor of the polymer compound represented by formula (P1) is prepared by reacting an active intermediate obtained by activating benzyl alcohol with formyl chloride, carbonate or the like with a reaction mixture containing R 1 It is produced by reacting with an amino compound having a polymerizable functional group such as methacrylate.

[0132] The P1 precursor, which is a precursor of the polymer compound represented by formula (P1), is as shown in the following reaction formula (PR)-8. When the stability of the polymerizable functional group is reduced due to the nucleophilicity caused by the amino group, the amino group is activated by forming a salt or introducing a protecting group in the reaction system, thereby stabilizing the production of the P1 precursor.

[0133] [Chemistry 27]

[0134]

[0135] Does not include R 1 The carbamate compound can be produced by reacting benzyl alcohol with a compound containing isocyanate. The following reaction formula (R)-11 is an example of reacting benzyl alcohol with an isocyanate compound containing a trialkoxysilyl group. 1 In the carbamate compound, R 1 , thereby the compound represented by formula (M1) can be produced.

[0136] [Chemistry 28]

[0137]

[0138] P1 is produced by reacting a P1 precursor including a polymerizable functional group with various polymerization initiators such as a radical polymerization initiator and an anionic polymerization initiator.

[0139] Examples of this reaction are shown in the following reaction formulas (PR)-9 to (PR)-11.

[0140] [Chemistry 29]

[0141]

[0142] The polymerization of P1 is not particularly limited, and can be carried out by free radical polymerization, anionic polymerization, etc. Among them, free radical polymerization is preferred from the perspective of ease of control. From the perspective of obtaining arbitrary solubility by controlling the molecular weight, controlled free radical polymerization is more preferred among free radical polymerization.

[0143] As controlled radical polymerization, chain transfer agent method, living radical polymerization as a kind of living polymerization, etc. can be cited, and living radical polymerization with easy control of molecular weight distribution is further preferred. It should be noted that as living radical polymerization, there are nitroxide radical polymerization (NMP), atom transfer radical polymerization (ATRP), reversible addition fragmentation chain transfer method (RAFT), etc., and from the aspect of temperature and versatility, atom transfer radical polymerization (ATRP) is particularly preferred.

[0144] In addition to widening the molecular weight distribution from low molecular weight to high molecular weight to obtain arbitrary film-forming properties, from the perspective of productivity and economy, conventional free radical polymerization with chain transfer reaction is preferred. It should be noted that, when free radical polymerization is used, a polymerization initiator known in the past can be appropriately used. In addition, the free radical polymerization initiator can be used alone or in combination of two or more, and a commercially available product can also be used directly.

[0145] For example, an azo polymerization initiator can be used, which is a compound having an azo group (-N=N-) and capable of generating N2 and free radicals. Specifically, azo nitrile, azo ester, azo amide, azo amidine, azo imidazoline, etc. can be cited. More specifically, for example, 2,2'-azobis(2-amidinopropane) dihydrochloride, 4,4'-azobis(4-cyanovaleric acid), 2,2'-bis(2-imidazoline-2-yl)-2,2'-azopropane dihydrochloride, 2,2'-bis(2-imidazoline-2-yl)-2,2'-azopropane, 2,2'-azobis[N-(2-hydroxyethyl)-2-methylpropionamide], 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile) (ADBN) can be cited. Among them, 2,2'-azobisisobutyronitrile (AIBN) and 2,2'-azobis(2,4-dimethylvaleronitrile) (ADBN) are preferred, and 2,2'-azobisisobutyronitrile (AIBN) is particularly preferred.

[0146] From the perspective of reducing the risk of dissolution / peeling in a plating bath or the like and ensuring solubility during film formation, the number average molecular weight of the polymer compound synthesized in this way is preferably 300 to 100,000, which is a degree that allows wet film formation, more preferably 1,000 to 90,000, and further preferably 2,000 to 40,000. In addition, for the same reason, the peak of the molecular weight distribution is preferably in the range of 1,000 to 90,000, and further preferably 2,000 to 40,000. They can be measured by gel permeation chromatography (GPC).

[0147] In one embodiment of the present invention, the photosensitive surface treatment agent is composed of the compound represented by the above formula (M1).

[0148] In one embodiment of the present invention, the photosensitive surface treatment agent is composed of the polymer compound represented by the above formula (P1).

[0149] In one embodiment of the present invention, the photosensitive surface treatment agent is composed of the compound represented by the above formula (M1) and the polymer compound represented by the above formula (P1).

[0150] In one embodiment of the present invention, the photosensitive surface treatment agent may contain a solvent and can be used as a suitable 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.

[0151] Examples of the alcohol solvent include isopropyl alcohol (IPA) and n-butanol.

[0152] Examples of the ester solvent include ethyl acetate (EAC), butyl acetate (NBAC), n-propyl acetate (NPAC), and 3-methoxy-3-methylbutyl acetate.

[0153] Examples of the hydrocarbon aromatic solvent include toluene, xylene, benzene, ethylbenzene, and trimethylbenzene.

[0154] Examples of the amine solvent include N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), and N,N-dimethylacetamide (DMAC).

[0155] 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.

[0156] 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).

[0157] As other solvents, halogen-based solvents containing chlorine or fluorine can be cited, such as chloroform, chlorobenzene, fluoroalkyl ether, etc. They can be used alone or in combination of two or more. The organic solvent can be appropriately selected based on conditions such as environmental pollution, solubility, volatility, corrosion to the substrate and base, film forming equipment and film forming method.

[0158] In the present invention, by making the photosensitive surface treatment layer poorly soluble, it becomes insoluble in cleaning liquids, plating liquids, solvents used in multilayer film formation, etc., and thus can improve cleaning resistance and process resistance in wiring and lamination steps.

[0159] In the case of a photosensitive surface treatment agent composed of the compound represented by the above formula (M1), from the perspective of improving the reactivity between the primer and the photosensitive surface treatment agent and between the molecules of the photosensitive surface treatment agent, the solvent contained therein is preferably an alcohol-based, ether-based, or hydrocarbon-based solvent, and a hydrocarbon-based solvent is particularly preferred, among which toluene is preferred.

[0160] In order to further improve the above reactivity, any acidic or basic compound may be included during film formation, and may be appropriately selected according to the film formation conditions, and acidic compounds such as hydrochloric acid, acetic acid, and nitric acid are particularly preferred, and acetic acid is preferred among them.

[0161] In the case of a photosensitive surface treatment agent composed of the compound represented by the above formula (P1), the solvent contained therein is preferably an ester-based or ketone-based solvent, particularly preferably a ketone-based solvent, and among them, cyclopentanone is preferred, from the viewpoint of solubility and film-forming property.

[0162] The concentration of the compound represented by the above formula (M1) or the polymer compound represented by the above formula (P1) contained in the photosensitive surface treatment agent can be appropriately selected according to the film-forming conditions, and is preferably 0.001 to 10 mass %, more preferably 0.01 to 2 mass %, and particularly preferably 0.1 to 0.3 mass % from the viewpoint of storage stability and economic efficiency.

[0163] <Pattern Formation Method>

[0164] 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 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.

[0165] Hereinafter, each process will be described with reference to the drawings.

[0166] like Figure 1 As shown in (a), the photosensitive surface treatment agent 10a of the present embodiment is applied onto a substrate 11.

[0167] As coating method, for example, coating methods such as spin coating, dip coating, die coating, spray coating, roller coating, micro gravure coating, lip coating, ink jet coating, applicator coating, brush coating can be used. In addition, it is also possible to apply by printing methods such as flexographic printing and screen printing. In addition, it is also possible to make SAM film and LB film.

[0168] 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.

[0169] Therefore, if Figure 1 As shown in (b), a photosensitive surface treatment agent layer 10 is formed on a substrate 11.

[0170] Then, if Figure 1As shown in (c), a photomask 13 having an exposure area of ​​a predetermined pattern is prepared. As an exposure method, it is not limited to the means using a photomask, and means such as projection exposure using an optical system such as a lens or a reflector, and maskless exposure using a spatial light modulation element, a laser beam, 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.

[0171] 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.

[0172] 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.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] 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), gold (Au), and copper (Cu).

[0177] 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.

[0178] Through the above steps, a wiring pattern can be formed on a predetermined substrate using the photosensitive surface treatment agent of the present embodiment.

[0179] <Method for manufacturing transistor>

[0180] 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.

[0181] 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.

[0182] 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.

[0183] like Figure 2 As 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).

[0184] 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).

[0185] 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).

[0186] 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.

[0187] 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.

[0188] 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.

[0189] 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.

[0190] <Laminated body>

[0191] The present embodiment is a laminate including the photosensitive surface treatment agent of the present embodiment described above.

[0192] 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.

[0193] <Transistor>

[0194] This embodiment is a transistor including the photosensitive surface treatment agent of this embodiment.

[0195] 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.

[0196] Example

[0197] 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.

[0198] <Example 1>

[0199] 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropanol was synthesized by the reaction shown below.

[0200] [Chemistry 30]

[0201]

[0202] 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylacetone 20.0g (79.0mmol, 1.0eq) was added to a 1L eggplant flask, dissolved in tetrahydrofuran (THF) 200mL and methanol 100mL, sodium borohydride (NaBH4) 4.48g (118mmol, 1.5eq) was added little by little at 0℃ (ice water), stirred at 0℃ for 30min, and then stirred at room temperature for 2h. After concentration with an evaporator, it was diluted with ethyl acetate (300mL), washed with H2O (150mL×3), dried with anhydrous magnesium sulfate (MgSO4), filtered, concentrated, and vacuum dried (hot water bath 60℃), to obtain the target product 20.2g (79.0mmol, 100%) as a yellow viscous body.

[0203] Rf=0.50 (hexane:ethyl acetate=1:1), UV254, raw material Rf=0.57

[0204] 1 HNMR(CDCl3,400MHz)δ=0.96(6H,d,J=6.9Hz)-CH(CH3), 21.96-2.09(1H,m)-CH(CH3), 22.23(1H,d,J=4.6Hz)-OH3 .95(3H,s)-OCH3, 3.99(3H,s)-OCH3, 5.27(1H,dd,J=4.6,5.3Hz)Ar-CH, 7.21(1H,s)Ar-H(6), 7.56(1H,s)Ar-H(3)

[0205] Next, 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropyl N-succinimidyl carbonate was synthesized by the reaction shown below.

[0206] [Chemistry 31]

[0207]

[0208] In a 500 mL eggplant flask, add 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropanol 20.2g (79.0mmol, 1.0eq), dissolve in anhydrous acetonitrile 300mL, add triethylamine 33mL (238mmol, 3.0eq), N,N'-disuccinimidyl carbonate (DSC) 30.3g (118mmol, 1.5eq), and stir at room temperature for 20h under nitrogen atmosphere. After concentration with an evaporator, dilute with chloroform (300mL), wash with 0.5N HCl (150mL×3) and sat.NaCl (150mL) in sequence, dry with anhydrous magnesium sulfate (MgSO4), filter, concentrate, and vacuum dry to obtain 31.8g of light yellow powder. Suspend with ethyl acetate (100mL), filter, and vacuum dry to obtain 20.1g (53.1mmol, 67%) of light yellow white powder. (The filtrate was concentrated, suspended again with ethyl acetate, filtered, and dried in vacuo to obtain 6.62 g of a light brown solid).

[0209] Rf=0.35(hexane:ethyl acetate=1:1),UV254 Note: Raw material Rf=0.50

[0210] 1 H NMR (CDCl 3、 400MHz)δ=1.04(3H,d,J=6.9Hz)-CH(CH3)2, 1.11(3H,d,J=7.0Hz)-CH(CH3)2, 2.23-2.33(1H,m)-CH(CH3)2, 2.79(4H,s)-CH2CH2-, 3.96(3H,s)-OCH3, 4.06(3

[0211] H,s)-OCH3, 6.41(1H,d,J=4.9Hz)Ar-CH, 6.98(1H,s)Ar-H(6), 7.67(1H,s)gAr-H(3)

[0212] Next, 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropyl N-methyl-N-(3-(trimethoxysilyl)propyl)carbamate was synthesized by the reaction shown below.

[0213] [Chemistry 32]

[0214]

[0215] In a 100 mL two-necked eggplant flask, 1.00 g (2.52 mmol, 1.0 eq) of 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropyl N-succinimidyl carbonate, 20 mL of dry THF, and 0.50 mL (2.52 mmol, 1.0 eq) of trimethoxy[3-(methylamino)propyl]silane were added, and the mixture was stirred at room temperature for 2 hours under a nitrogen atmosphere. As TLC showed that the activated carbonate of the starting material remained, 0.50 mL (2.52 mmol, 1.0 eq) of trimethoxy[3-(methylamino)propyl]silane was added, and the mixture was stirred for 1 hour. As TLC showed that the reaction had progressed, the reaction solution was concentrated and vacuum dried to obtain a crude yield of 1.785 g of a light yellow viscous substance. The light yellow viscous substance was dissolved in chloroform and purified by silica gel column chromatography (φ=4.0cm, h=15cm, hexane:ethyl acetate:acetone:(MeO)4Si=50:25:25:1). The purified substance was concentrated and vacuum dried on a hot water bath (60°C) to remove (MeO)4Si, and 1.089g (2.29mmol, 91%) of the target substance was obtained as a light yellow viscous substance.

[0216] 1 H-NMR (CDCl3) 400MHzδ=0.61-0.66(m,2H), 1.01(d,3H,J=6.1Hz), 1.05(d,3H,J=6.9Hz), 1.60-1.72(m,2H), 2.17-2.22(m,1H) , 2.87-3.02(m,3H), 3.22-3.39(m,2H), 3.58(s,9H), 3.94(s,3H), 3.95(s,3H), 6.24(d,1H,J=4.9Hz), 6.89(s,1H), 7.62(s,1H)

[0217] 13 C-NMR (CDCl3) 100MHzδ=6.26, 17.1, 19.6, 21.1, 33.3, 33.8, 34.8, 50.6, 51.5, 56.2, 56.3, 76.3, 108.0, 108.9, 132.3, 140.6, 147.7, 153.0, 155.5

[0218] Next, cyclohexyl(4,5-dimethoxy-2-nitrophenyl)methylmethyl(3-(trimethoxysilyl)propyl)carbamate was synthesized by the reaction shown below.

[0219] [Chemistry 33]

[0220]

[0221] In a 10 mL two-necked test tube, add 0.155 g (0.355 mmol, 1.0 eq) of cyclohexyl (4,5-dimethoxy-2-nitrophenyl) methyl (2,5-dioxopyrrolidin-1-yl) carbonate, 2 mL of anhydrous THF, and 85.0 μL (0.431 mmol, 1.2 eq) of trimethoxy [3- (methylamino) propyl] silane, and stir at room temperature for 3 hours under a N2 atmosphere. After confirming the disappearance of the raw material by TLC, the reaction solution was concentrated and vacuum dried to obtain 0.247 g of a crude product of a yellow-brown viscous substance. Purify by silica gel column chromatography (hexane: ethyl acetate: acetone: tetramethoxysilane = 100: 20: 20: 1, φ = 2, h = 15), concentrate, and vacuum dry (hot water bath 60°C). After washing with hexane, concentrate and vacuum dry to obtain 0.074 g (0.144 mmol, 41%) of the target substance as a yellow solid.

[0222] 1 H-NMR (CDCl3) 400MHz δ = 0.50-0.66 (m, 2H), 1.00-1.40 (m, 5H), 1.50-1.85 (m, 6H), 2.93 (d, 3H, J = 58.0Hz), 3 .10-3.45(m,2H), 3.56(d,9H,J=15.6Hz), 3.93(s,3H), 3.95(s,3H), 6.25(s,1H), 6.87(s,1H), 7.60(s,1H)

[0223] 13 C-NMR (CDCl3) 100MHzδ=6.00, 6.55, 20.7, 21.6, 26.1, 26.3, 27.8, 29.8, 33.9, 34.8, 43.0, 50.6, 51.5, 51.5, 56.3, 56.3, 76.0, 76.1, 108.0, 109.1, 132.0, 140.6, 147.7, 153.0, 155.5

[0224] 2-((tert-butoxycarbonyl)(methyl)amino)ethyl methacrylate (Boc-NMe-AEMA) was synthesized by the reaction shown below.

[0225] [Chemistry 34]

[0226]

[0227] In an argon atmosphere, 15 g (85.6 mmol, 1.0 eq.) of tert-butyl (2-hydroxyethyl) (methyl) carbamate (Boc-NMe-AE-OH), 75 ml of anhydrous dichloromethane, and 25.99 g (256.8 mmol, 3.0 eq.) of triethylamine were placed in a 500 mL four-necked flask and ice-cooled. A mixed solution of 13.42 g (128.4 mmol, 1.5 eq.) of methacryloyl chloride and 75 ml of dichloromethane was added dropwise to the reaction solution at an internal temperature below 20°C over 5 minutes.

[0228] As the addition was continued, the reaction solution changed from colorless and transparent to a light red suspension. The ice bath was removed and the mixture was stirred at room temperature for 1 hour. The disappearance of the raw material was confirmed by TLC (ethyl acetate / heptane = 1 / 1, ninhydrin) and GC. 90 mL (90 mmol, 1.05 eq.) of 1M NaOH aqueous solution was injected into the reaction solution to quench the reaction.

[0229] The organic layer was taken out, concentrated under reduced pressure at 40°C, and diluted with 300 mL of heptane. The heptane solution was washed three times with 90 mL of 1M NaOH aqueous solution and once with 30 g of 20% brine. The organic layer was dehydrated with sodium sulfate and concentrated under reduced pressure at 40°C to obtain 21.7 g of a crude red-orange oil.

[0230] This crude product was mixed with a crude product (Boc-NMe-AE-OH, 5 g) obtained by the same method of synthesis research, and diluted with 100 mL of heptane. The dilution was charged into 150 g of silica gel and column purified (development: heptane only → ethyl acetate / heptane = 1 / 5). After adding 30 mg of MEHQ (equivalent to 1000 ppm) to the fraction of the target product, the target product was obtained as a slightly yellow oil by concentration under reduced pressure.

[0231] Yield: 30.93 g, yield: 97.1%

[0232] 1 H-NMR(CDCl3)400MHzδ=1.45(s,9H),1.95(s,3H),2.92(m,3H),3.52(m,2H),4.25(m,2H),5.59(s,1H),6.13(s,1H)

[0233] 2-(Methylamino)ethyl methacrylate trifluoroacetate (Boc-NMe-AEMA-TFAsalt) was synthesized by the reaction shown below.

[0234] [Chemistry 35]

[0235]

[0236] In an argon atmosphere, 30.00 g (123.3 mmol, 1.0 eq.) of Boc-NMe-AEMA, 150 ml of dichloromethane, and 70.29 g (616.5 mmol, 5.0 eq.) of trifluoroacetic acid were added to a 300 mL eggplant-shaped flask at room temperature and stirred. The yellow hue of the reaction solution slightly thickened after the addition of trifluoroacetic acid.

[0237] After stirring at room temperature overnight, TLC (methanol / dichloromethane = 1 / 10, ninhydrin) and NMR were used to confirm the disappearance of the raw material. The reaction solution was concentrated under reduced pressure at 45°C to 63.0 g (crude yield 200%) and diluted with 60 mL of dichloromethane. The dilution was charged into 300 g of silica gel and column purified (development: only dichloromethane → methanol / dichloromethane = 1 / 2). After adding 30 mg of MEHQ (equivalent to 1000 ppm) to the target fraction, it was concentrated under reduced pressure to obtain the target as a slightly yellow oil.

[0238] Yield: 28.16 g, yield: 88.8%

[0239] 1 H-NMR(CDCl3)400MHzδ=1.93(s,3H),2.75(s,3H),3.31(br,2H),4.47(m,2H),5.64(s,1H),6.66(s,1H),9.69(br,2H)

[0240] 2-(((1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropoxy)carbonyl)(methyl)amino)ethyl methacrylate (NMe-iPrNBC-AEMA) was synthesized by the reaction shown below.

[0241] [Chemistry 36]

[0242]

[0243] Under argon atmosphere, iPrNBC-Osu 8g (20.18mmol), THF 288ml, TEA 3.5ml (25.23mmol, 1.25eq) were added to a 500ml four-necked flask to prepare a turbid light yellow solution. A 20 wt% methanol solution of Boc-NMe-AEMA-TFAsalt 29.85g was added dropwise. The turbidity of the solution gradually became thicker as the addition was added. It was stirred at room temperature, and the disappearance of the raw material was confirmed by TLC after 3.5 hours, and the reaction was completed. Distilled water (280ml) and ethyl acetate (280ml) were added to the reaction solution, stirred, and the organic layer was separated. The aqueous layer was extracted with ethyl acetate, and all the separated organic layers were combined. The organic layer was washed twice with 5% NaCl aq. The organic layer was dehydrated with sodium sulfate, and after removing the solid component, it was concentrated under reduced pressure at 30°C. The residue was diluted with ethyl acetate, the insoluble solid component was filtered out, and then concentrated to obtain a yellow liquid (10.2g). This was diluted with ethyl acetate (20 ml) and filled into a silica gel column (160 g). A gradient of 3 / 1→1 / 1→1 / 2 was used as an eluent of heptane / ethyl acetate. When the crude solution was developed with heptane / ethyl acetate = 3 / 1, a shallow spot was confirmed near the immediate upper side of the target (Rf = 0.22), so the column was eluted with a heptane / ethyl acetate gradient. The fraction of the target was concentrated to obtain a yellow liquid (5.20 g). The obtained yellow liquid was diluted with ethyl acetate, and MEHQ (0.52 mg, 100 ppm) was added and stored in a refrigerator.

[0244] Yield: 5.20 g, yield: 60.7%

[0245] 1 H-NMR(CDCl3)400MHzδ=1.02(m.6H),1.90(s,3H),2.21(m,1H),3.00(s,3H),3.51(m,3H), 3.94(s,6H),4.30(m,2H),5.55(s,1H),6.05(s,1H),6.25(m,1H),6.90(s,1H),7.60(s,1H)

[0246] Poly (2-(((1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropoxy)carbonyl)(methyl)amino)ethyl methacrylate (P-NMe-iPrNBC-AEMA) was synthesized by the reaction shown below.

[0247] [Chemistry 37]

[0248]

[0249] Under argon, add 2.45g (5.77mmol, 1.00eq.) of NMe-iPrNBC-AEMA and 4ml of DMF degassed for 30 minutes to a 50mL eggplant flask and dissolve it (yellow solution). After adding 47.5mg (0.289mmol, 0.05eq.) of azobisisobutyronitrile AIBN, heat to 65°C in 30 minutes, and heat and stir at this temperature for 36 hours. The completion of the reaction is determined by confirming the progress of the reaction by NMR. After the reaction solution is left to cool, it is dripped into methanol (60mL) with a Pasteur pipette and stirred for 20 minutes.

[0250] After the obtained slurry solution was centrifuged (10000rpm, 10min), the supernatant was removed, methanol (40mL) was added thereto, and after hand shaking and stirring, centrifugation was performed (10000rpm, 10min). After repeating the same operation once again, the obtained solid was dissolved in chloroform. It was added dropwise to methanol (60mL) with a Pasteur pipette and stirred for 20 minutes. After the obtained slurry solution was centrifuged (10000rpm, 10min), the supernatant was removed, methanol (40mL) was added thereto, after hand shaking and stirring, centrifugation was performed (10000rpm, 10min). After repeating the same operation once again, the obtained solid was dried under reduced pressure (60℃ / <1mmHg, 16h) to obtain 1.89g of the target P-NMe-iPrNBC-AEMA.

[0251] 1 H-NMR (CDCl3) 400MHzδ=0.80-0.99(br.9H),1.79-2.18(br,3H),2.91-3.07(br,3H),3.20-3.95(br,10H),6.22(br,1H),6.94(br,1H),7.54(br,1H)

[0252] GPC number average molecular weight Mn = 9041

[0253] The polymer (P1)-A11 shown below was synthesized.

[0254] [Chemistry 38]

[0255]

[0256] <Evaluation>

[0257] [Manufacturing of Plated Wiring 1]

[0258] A surface treatment agent containing the polymer compound represented by formula (P1)-A11 is used to form a film on a substrate to produce a plated wiring.

[0259] Cyclopentanone was added to the polymer compound represented by the formula (P1)-A11 synthesized in Example 1 to adjust the content to 0.2% by mass, thereby obtaining a photosensitive surface treatment agent 1.

[0260] The photosensitive surface treatment agent 1 was applied on a polyimide substrate (Upilex, manufactured by UBE Corporation) by spin coating (MS-A150 manufactured by Mikasa Corporation) at 1000 rpm, and then dried at 100° C. for 20 minutes to form a photosensitive surface treatment agent layer.

[0261] Next, the substrate having the photosensitive surface treatment agent layer formed on the entire surface was subjected to a 2000 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.

[0262] Next, the surface was immersed in a catalyst colloidal solution for electroless plating (Melplate Activato 7331, manufactured by Meltex) for 3 minutes at room temperature to allow the catalyst (Pd) to adhere to the amine generating part. After the surface was washed 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.

[0263] [Manufacturing of Plated Wiring 2]

[0264] A plated wiring was produced in the same manner as in the method described in [Production of Plated Wiring 1] above, except that the substrate was changed to a quartz substrate (manufactured by Shin-Etsu Chemical Co., Ltd., product name: VIOSIL-SQ).

[0265] [Evaluation of Plated Wiring]

[0266] Figure 3A to Figure 3D 1 and 2 show overall photographs and optical microscope (VHX-7000, manufactured by KEYENCE CORPORATION) images of a polyimide substrate and a quartz substrate subjected to a plating wiring process in Examples, respectively.

[0267] Figure 3A This is the overall image of the resolution map drawn on the polyimide substrate and the quartz substrate.

[0268] Figure 3B is an optical microscope image of a resolution map depicted on a quartz substrate.

[0269] Figure 3C This is an optical microscope image of L / S = 3 / 3 to 10 / 10 μm drawn on a quartz substrate.

[0270] Figure 3D These are optical microscope images of L / S = 1 / 1 to 8 / 8 μm drawn on a quartz substrate.

[0271] according to Figure 3A to Figure 3D It was confirmed visually and under a microscope that high-definition and good plated wiring could be formed by using a surface treatment agent containing a polymer compound represented by formula (P1)-A11.

[0272] <Using the photolysis rate constant k(s) of the model compound -1 )'s review>

[0273] The following compounds (1) to (7) were respectively dissolved in acetonitrile to prepare 0.1 mM solutions.

[0274] The ultra-high pressure mercury lamp was used to irradiate the water filter with a wavelength of 365 nm and an illumination of 25 mW / cm 2 The light was applied for 5, 10, 15, 20, 25, and 30 seconds, and HPLC determination was performed respectively.

[0275] [Chemistry 39]

[0276]

[0277] [Chemistry 40]

[0278]

[0279] The peak areas of the raw materials obtained by HPLC (S0: area before light irradiation, S t : The area after t seconds of light irradiation) is substituted into the following formula, and the photolysis rate constant k (s) is calculated from the reduction rate of the raw material. -1 ). The results are shown in Table 1.

[0280] [Number 1]

[0281]

[0282] [Table 1]

[0283] <![CDATA[k(s -1 )]]> Compound (1) 0.041 Compound (2) 0.052 Compound (3) 0.048 Compound (4) 0.048 Compound (5) 0.044 Compound (6) 0.050 Compound (7) 0.046

[0284] Among the compounds (1) to (7), it was confirmed that the photodecomposition rates of the compounds (2) to (7) were higher than those of the compound (1).

[0285] The compound (1) is a compound represented by formula (M1) corresponding to R 1 The above results confirm that R 1 When it is a linear or branched alkyl group having 1 to 4 carbon atoms, 1The photolysis rate of the nitrobenzyl group is increased compared to the compound in which the group is a hydrogen atom.

[0286] The compound of (2) is a model compound of the polymer compound represented by formula (P1)-A11. The compounds of (3) to (7) have the same photolysis rate constant as the compound of (2). Therefore, it can be fully estimated that when the compounds (M1)-1 to (M1)-6 and the polymer compounds (P1)-A2 to (P1)-A6 exemplified above are used, the same effect as when the polymer compound represented by formula (P1)-A11 is used is exerted.

[0287] Explanation of symbols

[0288] 11: substrate, 10a: photosensitive surface treatment agent, 10: photosensitive surface treatment agent layer, 13: photomask, 14: amine generating portion, 12: amine non-generating portion, 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 linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, 1 is a linear or branched alkylene group having 1 to 4 carbon atoms, or a single bond; R 1 The terminal carbon atom of the alkyl group is 1 The carbon atom of the alkylene group is bonded to make R 1 and Y 1 It can also form a ring; R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 3 and R 4 Each independently represents an alkyl group having 1 to 3 carbon atoms, n0 is an integer greater than or equal to 0, and X represents a halogen atom or an alkoxy group.

2. A photosensitive surface treatment agent comprising a polymer compound represented by the following formula (P1), [Chemistry 2] In formula (P1), R 1 is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, 1 is a linear or branched alkylene group having 1 to 4 carbon atoms, or a single bond; 2 A group formed by removing two hydrogen atoms from an aromatic ring having 6 to 15 carbon atoms; R 1 The terminal carbon atom of the alkyl group is 1 The carbon atom of the alkylene group is bonded to make R 1 and Y 1 It can also form a ring; R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 3 and R 4 are each independently an alkyl group having 1 to 3 carbon atoms, R 5 is a hydrogen atom or a methyl group, n0, n1, and n2 are each independently an integer greater than 0, and m is a natural number.

3. The photosensitive surface treatment agent according to claim 2, further comprising a ketone solvent.

4. The photosensitive surface treatment agent according to claim 2 or 3, wherein The number average molecular weight of the polymer compound is 2,000 to 40,000.

5. The photosensitive surface treatment agent according to any one of claims 2 to 4, wherein At least one terminal of the polymer compound is a substituent represented by the following general formula (1x), [Chemistry 3] 6 . A laminate comprising the photosensitive surface treatment agent according to claim 1 . 7 . A pattern-forming substrate having a surface chemically modified with the photosensitive surface treatment agent according to claim 1 . 8 . A transistor comprising the photosensitive surface treatment agent according to claim 1 .

9. A pattern forming method, comprising: A step of coating a photosensitive surface treatment agent according to any one of claims 1 to 5 on a substrate to form 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.

10. A pattern forming method, comprising: A step of coating a photosensitive surface treatment agent according to any one of claims 1 to 5 on a substrate to form 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.

11. A pattern forming method, comprising: A step of coating a photosensitive surface treatment agent according to any one of claims 1 to 5 on a substrate to form 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. 12 . 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 9 .

13. A transistor comprising a compound represented by the following formula (M1) or a polymer compound represented by the following formula (P1), [Chemistry 4] In formula (M1), R 1 is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, 1 is a linear or branched alkylene group having 1 to 4 carbon atoms, or a single bond; R 1 The terminal carbon atom of the alkyl group is 1 The carbon atom of the alkylene group is bonded to make R 1 and Y 1 It can also form a ring; R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 3 and R 4 Each independently represents an alkyl group having 1 to 3 carbon atoms, n0 is an integer greater than 0, and X is a halogen atom or an alkoxy group; [Chemistry 5] In formula (P1), R 1 is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, 1 is a linear or branched alkylene group having 1 to 4 carbon atoms, or a single bond, 2 A group formed by removing two hydrogen atoms from an aromatic ring having 6 to 15 carbon atoms; R 1 The terminal carbon atom of the alkyl group is 1 The carbon atom of the alkylene group is bonded to make R 1 and Y 1 It can also form a ring; R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 3 and R 4 are each independently an alkyl group having 1 to 3 carbon atoms, R 5 is a hydrogen atom or a methyl group, n0, n1, and n2 are each independently an integer greater than 0, and m is a natural number.

14. The transistor according to claim 13, wherein The compound or polymer compound has a portion where at least a part of the nitrobenzyl groups are detached to generate amino groups.

Images