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

Abstract

To provide a photosensitive surface treatment agent.SOLUTION: A photosensitive surface treatment agent includes a compound expressed with a following formula (M1) (in the formula (M1), R1 denotes a linear, branched-chain or cyclic alkyl group having 1-6 carbon atoms, and Y1 denotes a linear or branched-chain alkylene group having 1-4 carbon atoms, or a single bond. A carbon atom at a terminal of the alkyl group of the R1 may be bonded with a carbon atom composing the alkylene group of the Y1 so that the R1 and the Y1 may form a ring. R2 denotes a hydrogen atom or an alkyl group having 1-6 carbon atoms, R3 and R4 independently denote an alkyl group having 1-3 carbon atoms, n0 denotes an integer of 0 or larger, and X denotes a halogen atom or an alkoxy group. [Chem.1].SELECTED DRAWING: None

Description

[Technical Field]

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

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

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

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

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

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

[0007] [ka] (In formula (M1), R 4 is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and Y 1 is a linear or branched alkylene group having 1 to 4 carbon atoms, or a single bond. The carbon atom at the end of the alkyl group of R 1 is bonded to the carbon atom constituting the alkylene group of Y 1 so that R 1 and Y 1 may 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, n0 is an integer of 0 or more, and X is a halogen atom or an alkoxy group.)

Brief Description of Drawings

[0008] [Figure 1] It is a schematic diagram for explaining the pattern formation method of this embodiment. [Figure 2] It is a schematic diagram for explaining the manufacturing method of the transistor of this embodiment. [Figure 3A] It is an overall image of the resolution chart drawn on the polyimide substrate and the quartz substrate. [Figure 3B] It is an optical microscope image of the resolution chart drawn on the quartz substrate. [Figure 3C] It is an optical microscope image of L / S = 3 / 3 to 10 / 10 μm drawn on the quartz substrate. [Figure 3D] It is an optical microscope image of L / S = 1 / 1 to 8 / 8 μm drawn on the quartz substrate.

Embodiments for Carrying Out the Invention

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

[0010]

Chemical Formula

[0011] (R 1 ) In formula (M1), R 1 These are linear, branched, or cyclic alkyl groups having 1 to 6 carbon atoms. Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, and tert-butyl groups.

[0012] (Y 1 ) In equation (M1), Y 1 This is a linear or branched alkylene group having 1 to 4 carbon atoms. 1 Examples include methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], etc. Also, Y 1 Examples include -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, and -C(CH3)(CH2CH3)-. In equation (M1), Y 1 It may also be a single bond.

[0013] R 1 The terminal carbon atom of the alkyl group is Y 1 It bonds with the carbon atoms that make up the alkylene group, R 1 and Y 1They may form a ring. In this case, R 1 and Y 1 The ring formed is, for example, a piperidyl group. In other words, equation (M1) may also be equation (M1)-A below.

[0014] [ka] (In formula (M1), R 1 Y is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms. 12 R is a linear or branched alkylene group having 1 to 4 carbon atoms. 12 The terminal carbon atom of the alkyl group is Y 12 It forms a ring by bonding with the carbon atoms that make up the alkylene group. R 2 R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 3 and R 4 Each of these is independently an alkyl group having 1 to 3 carbon atoms, n0 is a non-negative integer, and X is a halogen atom or alkoxy group.

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

[0016] (R 3 and R 4 ) R 2 and R 3 Each of these is an alkyl group having 1 to 3 carbon atoms. Examples of alkyl groups having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group, with a methyl group or an ethyl group being preferred, and a methyl group being more preferred.

[0017] (n0) In formula (M1), n0 is an integer greater than or equal to 1 or greater than or equal to 6, and more preferably 1 or greater than or equal to 4.

[0018] (X) In formula (M1), X is a halogen atom or an alkoxy group. Examples of halogen atoms represented by X include fluorine, chlorine, bromine, or iodine atoms.

[0019] X is preferably an alkoxy group. Examples of alkoxy groups for X include -O-(CH3) and -O-(CH2)n(CH3), where n is a natural number between 1 and 3.

[0020] Specific examples of compounds represented by formula (M1) are listed below.

[0021] [ka]

[0022] [ka]

[0023] [ka]

[0024] [ka]

[0025] [ka]

[0026] When a photosensitive surface treatment agent containing the compound represented by formula (M1) is applied to a substrate and irradiated with light, the nitrobenzyl group is removed, SiX3 adheres to the substrate, and at the same time, an amine is generated on the substrate surface. Metallic materials, organic materials, or inorganic materials can be adhered to the areas 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-).

[0027] The compound represented by formula (M1) is R 1 This is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms. Therefore, R 1 This compound is bulkier than compounds in which the corresponding group is a hydrogen atom, and the rate of photodegradation due to the elimination of the nitrobenzyl group is improved.

[0028] Furthermore, the compound represented by formula (M1) is R 1 Because of the structure described above, the reverse reaction after photodegradation is unlikely to occur. The reverse reaction after photodegradation refers to the reaction in which the detached nitrobenzyl group reattaches after photodegradation.

[0029] According to the photosensitive surface treatment agent of this embodiment, by placing a metal material in the amine generation area formed on the substrate surface, a fine metal pattern with a line width of, for example, 3 μm or less can be formed on the substrate surface without using a photoresist process, a development process, or an etching process.

[0030] One aspect of the present invention is a photosensitive surface treatment agent comprising a polymer compound represented by the following formula (P1).

[0031] [ka] (In formula (P1), R 1 Y is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms. 1 This is a linear or branched alkylene group having 1 to 4 carbon atoms, or a single bond, Y 2 R is a group obtained by removing two hydrogen atoms from an aromatic ring with 6 to 15 carbon atoms. 1 The terminal carbon atom of the alkyl group is Y1 It bonds with the carbon atoms that make up the alkylene group, R 1 and Y 1 They may form a ring. R 2 R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 3 and R 4 Each of these is independently an alkyl group having 1 to 3 carbon atoms, and R 5 (where n0 is a hydrogen atom or a methyl group, n0, n1, and n2 are each independent non-negative integers, and m is a natural number.)

[0032] In formula (P1), R 1 , R 2 , R 3 , R 4 , R 5 , Y 1 , Y 2 The explanations for n0, n1, and n2 are the same as above, and m is a natural number.

[0033] The polymer compound 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 represented by formula (P1).

[0034] [ka]

[0035] A polymer compound (P1)-A, in which a substituent represented by formula (1x) is attached to the end of the main chain of a polymer compound represented by formula (P1), is shown below as an example.

[0036] [ka]

[0037] Other specific examples of polymer compounds represented by formula (P1)-A are listed below.

[0038] [ka]

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] 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).

[0044] <Method for producing compounds> The compound represented by formula (M1) can be produced by the following method. In the following description of the manufacturing method, the explanation of each symbol in the formula is the same as described above.

[0045] The compound represented by formula (M1) can be produced by a step of synthesizing an active intermediate from an alcohol and reacting it with a primary or secondary amine. Examples of active intermediates include the active intermediate obtained by activating benzyl alcohol with carbonyl chloride as shown in reaction formula (R)-1 below (e.g., carboxylic acid chloride), the active intermediate obtained by activating benzyl alcohol with carbonylimidazole as shown in reaction formula (R)-2 below (e.g., oxycarbonylimidazole), and the active intermediate obtained by activating benzyl alcohol with carbonyloxysuccinimide as shown in reaction formula (R)-4 below (e.g., oxycarbonyloxysuccinimide). In reactions (R)-1, (R)-2, and (R)-4 below, R 1 A method for producing the compound represented by formula (M1) was shown using a secondary amine compound containing R 1 After forming a carbamate using a primary amine compound that does not contain R, R is placed on nitrogen according to the manufacturing method described later. 1 The compound represented by formula (M1) may be produced by introducing [a specific component].

[0046] [ka]

[0047] As a starting material for the above reaction (R)-1, for example, compound (R) of CAS No. 42855-00-5 2 (H), CAS No.363135-50-6(R 2 Examples of compounds containing Me include those containing Me. Compound (R) of CAS No. 42855-00-5 2 The synthesis method for H) is disclosed in Chemical Science (2016), 7(3), 1891-1895. Using the same method as disclosed in Chemical Science (2016), 7(3), 1891-1895, R 2 Compounds in which the alkyl group is the desired alkyl group can be produced.

[0048] [ka]

[0049] As a starting material for the above reaction (R)-2, for example, compound (R) of CAS No. 188305-03-5 2 (H), CAS No.2097130-00-0(R 2 Examples of compounds containing Me include those containing Me. Compound (R) of CAS No. 2097130-00-0 2 The synthesis method for Me is disclosed in Organic Letters (2017), 19(7), 1618-1621. Using the same method as disclosed in Organic Letters (2017), 19(7), 1618-1621, R 2 Compounds in which the alkyl group is the desired alkyl group can be produced.

[0050] [ka]

[0051] Furthermore, the compound represented by formula (M1) can be produced by reacting an activated intermediate, obtained by activating benzyl alcohol with formic acid chloride or carbonate, with an amino compound containing a terminal double bond to form a nitrobenzylcarbamate, and then reacting it with a metal catalyst or a trialkoxysilane such as trimethoxyhydrosilane.

[0052] The reaction equation (R)-5 below is an example of using a compound containing an allyl group as an amino compound containing a terminal double bond.

[0053] [ka]

[0054] The reaction equation (R)-6 below is an example of using a compound containing a vinyl group as an amino compound containing a terminal double bond.

[0055] [ka]

[0056] The compound represented by formula (M1) is formed by reacting an activated intermediate obtained by activating benzyl alcohol with formic acid chloride, carbonate, etc., with an aminosilane compound containing a primary amine to form a nitrobenzylcarbamate, followed by R 1 It can also be produced by reacting it with iodine or an alkyl compound containing a leaving group.

[0057] The following reaction equation (R)-7 is: 1 This also includes examples of reactions with compounds containing iodine.

[0058] [ka]

[0059] The following reaction equation (R)-8 is R 1 This is an example of a reaction with a compound containing a tosyloxy group. Note that the tosyloxy group is eliminated during the reaction.

[0060] [ka]

[0061] R 1 Carbamate compounds that do not contain can be produced by reacting benzyl alcohol with a compound containing an isocyanate. The following reaction formula (R)-10 is an example of reacting benzyl alcohol with an isocyanate compound containing a trialkoxysilyl group. R synthesized in this way 1 A carbamate compound that does not contain R is prepared by the above manufacturing method. 1 By introducing this, the compound represented by formula (M1) can be produced.

[0062] [ka]

[0063] <Method for producing polymer compounds> The compound represented by formula (P1) can be produced by the following method. In the following description of the manufacturing method, the explanation of each symbol in the formula is the same as described above.

[0064] The P1 precursor, which is a precursor of the polymer compound represented by formula (P1), is obtained by activating the benzyl alcohol shown in the reaction formula (PR)-1 below with carbonyl chloride, and R 1 It is produced by reacting it with an aminomethacrylate compound containing [the specified ingredient].

[0065] The P1 precursor, which is a precursor of the polymer compound represented by formula (P1), is obtained by activating benzyl alcohol with carbonyloxyimidazole as shown in the reaction formula (PR)-2 below, and R 1 It is produced by reacting it with an aminomethacrylate compound containing [the specified ingredient].

[0066] The P1 precursor, which is a precursor of the polymer compound represented by formula (P1), is obtained by activating benzyl alcohol with carbonyloxysuccinimide as shown in the reaction formula (PR)-4 below, and R 1 It is produced by reacting it with an aminomethacrylate compound containing [the specified ingredient].

[0067] The following reaction is R 1 A method for producing the compound represented by formula (P1) is shown using a secondary amine compound containing R. The method for producing the compound represented by formula (P1) is not limited to this, 1 After forming a carbamate using a primary amine compound that does not contain R, R is placed on nitrogen according to the manufacturing method described later. 1 The compound represented by formula (P1) may be produced by introducing [a specific component].

[0068] [ka]

[0069] 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 shown in the following reaction formula (PR)-5 with formyl chloride, carbonate, etc. with an amino alcohol compound to form nitrobenzyl carbamate, and then reacting with methacrylic acid.

[0070] 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 shown in the following reaction formula (PR)-6 with formyl chloride, carbonate, etc. with an amino alcohol compound to form nitrobenzyl carbamate, and then reacting with methacrylic acid chloride.

[0071]

Chemical formula

[0072] 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 with formyl chloride, carbonate, etc. as shown in the following reaction formula (PR)-7 with an amino compound containing a polymerizable functional group such as R 1 and a methacrylate.

[0073] When the stability of the polymerizable functional group is reduced due to nucleophilicity by an amino group as shown in the following reaction formula (PR)-8 for the P1 precursor, which is a precursor of the polymer compound represented by formula (P1), the production of the P1 precursor is stabilized by forming a salt of the amino group or introducing a protecting group and activating the amine in the reaction system.

[0074]

Chemical formula

[0075] R 1Carbamate compounds that do not contain can be produced by reacting benzyl alcohol with a compound containing an isocyanate. The following reaction formula (R)-11 is an example of reacting benzyl alcohol with an isocyanate compound containing a trialkoxysilyl group. R synthesized in this way 1 A carbamate compound that does not contain R is prepared by the above manufacturing method. 1 By introducing this, the compound represented by formula (M1) can be produced.

[0076] [ka]

[0077] P1 is produced by reacting a P1 precursor containing polymerizable functional groups with various polymerization initiators, such as radical polymerization initiators and anionic polymerization initiators. Examples of this reaction are shown in the following reaction equations (PR)-9 to (PR)-11.

[0078] [ka]

[0079] The polymerization of P1 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.

[0080] 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.

[0081] 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 classical 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.

[0082] 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). Among these, 2,2'-azobisisobutyronitrile (AIBN) and 2,2'-azobis(2,4-dimethylvaleronitrile) (ADBN) are preferred, and 2,2'-azobisisobutyronitrile (AIBN) is particularly preferred.

[0083] The number-average molecular weight of the polymer compound synthesized in this manner is preferably between 300 and 100,000, more preferably between 1,000 and 90,000, and even more preferably between 2,000 and 40,000, from the viewpoint of reducing the risk of dissolution and peeling in plating baths and ensuring solubility during film formation, thus enabling 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 between 2,000 and 40,000. These can be measured by gel permeation chromatography (GPC).

[0084] In one embodiment of the present invention, the photosensitive surface treatment agent comprises a compound represented by the above formula (M1). In one embodiment of the present invention, the photosensitive surface treatment agent comprises a polymer compound represented by the above formula (P1).

[0085] In one embodiment of the present invention, the photosensitive surface treatment agent comprises a compound represented by formula (M1) and a polymer compound represented by formula (P1).

[0086] In one embodiment of the present invention, the photosensitive surface treatment agent may contain a solvent. By dissolving it in a common organic solvent such as an alcohol-based solvent, an ester-based solvent, a hydrocarbon-based aromatic solvent, an amine-based solvent, a ketone-based solvent, a glycol ether-based solvent, or an ether-based solvent, it can be used as a suitable surface treatment agent.

[0087] Examples of alcohol-based solvents include isopropyl alcohol (IPA) and n-butyl alcohol (n-butanol).

[0088] Examples of ester-based solvents include ethyl acetate (EAC), butyl acetate (NBAC), n-propyl acetate (NPAC), and 3-methoxy-3-methylbutyl acetate.

[0089] Examples of hydrocarbon aromatic solvents include toluene, xylene, benzene, ethylbenzene, and trimethylbenzene.

[0090] Examples of amine-based solvents include N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), and N,N-dimethylacetamide (DMAC).

[0091] 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.

[0092] 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).

[0093] 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.

[0094] 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.

[0095] 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.

[0096] In the case of a photosensitive surface treatment agent comprising the compound 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.

[0097] The concentration of the compound represented by formula (M1) or the polymer compound 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 economic efficiency, 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.

[0098] <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.

[0099] 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.

[0100] 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.

[0101] As a result, a photosensitive surface treatment layer 10 is formed on the substrate 11, as shown in Figure 1(b).

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] 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).

[0109] 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.

[0110] 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.

[0111] <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.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] 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).

[0116] 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).

[0117] 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.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] <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.

[0122] <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]

[0123] 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.

[0124] <Example 1> 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropanol was synthesized by the reaction shown below.

[0125] [ka]

[0126] In a 1 L round-bottom flask, 20.0 g (79.0 mmol, 1.0 eq) of 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropanone was added and dissolved in 200 mL of tetrahydrofuran (THF) and 100 mL of methanol. 4.48 g (118 mmol, 1.5 eq) of sodium tetraborohydride (NaBH4) was gradually added at 0°C (ice water), and the mixture was stirred at 0°C for 30 minutes, followed by stirring at room temperature for 2 hours. After concentration using an evaporator, the mixture was diluted with ethyl acetate (300 mL), washed with H2O (150 mL x 3), dried over anhydrous magnesium sulfate (MgSO4), filtered, concentrated, and vacuum-dried (water bath 60°C) to obtain 20.2 g (79.0 mmol, 100%) of the target product, a yellow viscous substance.

[0127] Rf=0.50 (Hexane:ethyl acetate = 1:1), UV254, starting material Rf=0.57

[0128] 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)

[0129] Next, 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropyl N-succinimidyl carbonate was synthesized by the reaction shown below.

[0130] [ka]

[0131] In a 500 mL round-bottom flask, 20.2 g (79.0 mmol, 1.0 eq) of 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropanol was added and dissolved in 300 mL of anhydrous acetonitrile. 33 mL (238 mmol, 3.0 eq) of triethylamine and 30.3 g (118 mmol, 1.5 eq) of N,N'-disuccinimidyl carbonate (DSC) were added, and the mixture was stirred at room temperature for 20 hours under a nitrogen atmosphere. After concentration using an evaporator, the solution was diluted with chloroform (300 mL), washed sequentially with 0.5 N HCl (150 mL x 3) and sat. NaCl (150 mL), dried over anhydrous magnesium sulfate (MgSO4), filtered, concentrated, and vacuum-dried to obtain 31.8 g of a pale yellow powder. The solution was suspended in ethyl acetate (100 mL), filtered by suction, and vacuum-dried to obtain 20.1 g (53.1 mmol, 67%) of a pale yellowish-white powder. (After concentrating the filtrate, it was again suspended in ethyl acetate, filtered by suction, and vacuum-dried to obtain 6.62 g of a pale brown solid.)

[0132] Rf=0.35 (Hexane:ethyl acetate = 1:1), UV254 Note: Raw material Rf=0.50

[0133] 1 1H 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(3H,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)

[0134] Next, 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropyl N-methyl-N-(3-(trimethoxysilyl)propyl)carbamate was synthesized by the reaction shown below.

[0135] [ka]

[0136] To 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. The mixture was stirred at room temperature for 2 hours under a nitrogen atmosphere. Since the active carbonate of the starting material remained by TLC, 0.50 mL (2.52 mmol, 1.0 eq) of trimethoxy[3-(methylamino)propyl]silane was additionally added and stirred for 1 hour. Since the reaction was proceeding by TLC, the reaction solution was concentrated and vacuum dried to obtain 1.785 g of a pale yellow viscous solid as the crude yield. The pale yellow viscous solid was dissolved in chloroform and purified by silica gel column chromatography (φ = 4.0 cm, h = 15 cm, hexane:ethyl acetate:acetone:(MeO)4Si = 50:25:25:1). The purified product was concentrated and vacuum dried on a hot water bath (60 °C) to remove (MeO)4Si, and 1.089 g (2.29 mmol, 91%) of the target pale yellow viscous solid was obtained.

[0137] 1 1H-NMR (CDCl3) 400 MHz δ = 0.61 - 0.66 (m, 2H), 1.01 (d, 3H, J = 6.1 Hz), 1.05 (d, 3H, J = 6.9 Hz), 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 = 4.9 Hz), 6.89 (s, 1H), 7.62 (s, 1H)

[0138] 13 13C-NMR (CDCl3) 100 MHz δ = 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

[0139] Next, cyclohexyl(4,5-dimethoxy-2-nitrophenyl)methylmethyl(3-(trimethoxysilyl)propyl)carbamate was synthesized by the reaction shown below.

[0140] [ka]

[0141] 0.155 g (0.355 mmol, 1.0 eq) of cyclohexyl(4,5-dimethoxy-2-nitrophenyl)methyl(2,5-dioxopyrrolidine-1-yl) carbonate, 2 mL of anhydrous THF, and 85.0 μL (0.431 mmol, 1.2 eq) of trimethoxy[3-(methylamino)propyl]silane were added to a 10 mL two-necked test tube and stirred at room temperature under an N2 atmosphere for 3 hours. The disappearance of the starting materials was confirmed by TLC, and the reaction solution was concentrated and vacuum-dried to obtain 0.247 g of the crude product, a yellowish-brown viscosity. The solution was purified by silica gel column chromatography (hexane:ethyl acetate:acetone:tetramethoxysilane = 100:20:20:1, φ=2, h=15), concentrated, and vacuum-dried (water bath 60°C). After rinsing with hexane, the solution was concentrated and vacuum-dried to obtain 0.074 g (0.144 mmol, 41%) of the target product, a yellow solid.

[0142] 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)

[0143] 13C-NMR(CDCl3)100MHz δ=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

[0144] 2-((tert-butoxycarbonyl)(methyl)amino)ethyl methacrylate (Boc-NMe-AEMA) was synthesized by the reaction shown below.

[0145] [ka]

[0146] Under 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 charged into a 500 mL four-necked flask and cooled with ice. To this reaction mixture, a mixed solution of 13.42 g (128.4 mmol, 1.5 eq.) of methacryloyl chloride and 75 ml of dichloromethane was added dropwise over 5 minutes at an internal temperature of 20°C or less.

[0147] The reaction solution changed from colorless and transparent to a pale red suspension as the reaction mixture was added dropwise. After removing the ice bath and stirring at room temperature for 1 hour, the disappearance of the starting materials was confirmed by TLC (ethyl acetate / heptane = 1 / 1, ninhydrin) and GC. The reaction was quenched by adding 90 mL (90 mmol, 1.05 eq.) of 1 M NaOH aqueous solution to the reaction solution.

[0148] The organic layer was removed, concentrated under reduced pressure at 40°C, and then diluted with 300 mL of heptane. The heptane solution was washed three times with 90 mL of 1 M NaOH aqueous solution and once with 30 g of 20% saline solution. The organic layer was dehydrated with sodium sulfate and concentrated under reduced pressure at 40°C to obtain 21.7 g of crude reddish-orange oil.

[0149] This crude compound was mixed with a crude compound (Boc-NMe-AE-OH, 5g) obtained separately in a synthesis study using the same method, and diluted with 100mL of heptane. The diluted solution was charged onto 150g of silica gel and subjected to column purification (elution: heptane only → ethyl acetate / heptane = 1 / 5). After adding 30mg of MEHQ (equivalent to 1000ppm) to the fraction of the target product, the target product was obtained as a slightly yellowish oil by vacuum concentration.

[0150] Yield: 30.93g, yield: 97.1%

[0151] 1 H-NMR(CDCl3)400MHz δ=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)

[0152] 2-(methylamino)ethyl methacrylate trifluoroacetate (Boc-NMe-AEMA-TFAsalt) was synthesized by the reaction shown below.

[0153] [ka]

[0154] Under 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 charged into a 300 mL round-bottom flask at room temperature and stirred. The reaction solution became slightly more yellowish after the addition of trifluoroacetic acid.

[0155] After stirring overnight at room temperature, the disappearance of the starting materials was confirmed by TLC (methanol / dichloromethane = 1 / 10, ninhydrin) and NMR. 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 diluted solution was charged onto 300 g of silica gel and purified by column (development: dichloromethane only → methanol / dichloromethane = 1 / 2). 30 mg of MEHQ (equivalent to 1000 ppm) was added to the fraction of the target product, and the solution was concentrated under reduced pressure to obtain the target product as a slightly yellowish oil.

[0156] Yield 28.16g, yield 88.8%

[0157] 1 H-NMR(CDCl3)400MHz δ=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)

[0158] 2-(((1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropoxy)carbonyl)(methyl)amino)ethyl methacrylate (NMe-iPrNBC-AEMA) was synthesized by the reaction shown below.

[0159] [ka]

[0160] Under an argon atmosphere, 8 g (20.18 mmol) of iPrNBC-OSu, 288 ml of THF, and 3.5 ml (25.23 mmol, 1.25 eq) of TEA were charged into a 500 ml four-necked flask to form a turbid, pale yellow solution. A 20 wt% methanol solution of 29.85 g of Boc-NMe-AEMA-TFAsalt was added dropwise. The turbidity of the solution gradually increased with each addition. The mixture was stirred at room temperature, and after 3.5 hours, the disappearance of the starting materials was confirmed by TLC, indicating the end of the reaction. Distilled water (280 ml) and ethyl acetate (280 ml) were added to the reaction mixture, and the mixture was stirred to separate the organic layer. The aqueous layer was extracted with ethyl acetate, and all the separated organic layers were combined. The organic layers were washed twice with 5% NaCl aq. The organic layers were dehydrated with sodium sulfate to remove solid components, and then concentrated under reduced pressure at 30°C. The residue was diluted with ethyl acetate, and after filtering out the insoluble solid components, the solution was concentrated to obtain a yellow liquid (10.2 g). This was diluted with ethyl acetate (20 ml) and packed into a silica gel column (160 g). The solution was purified by eluting with a heptane / ethyl acetate gradient of 3 / 1 → 1 / 1 → 1 / 2. When the crude solution was developed with heptane / ethyl acetate = 3 / 1, a faint spot was observed just above the target product (Rf = 0.22), so the column elution was performed using a heptane / ethyl acetate gradient. The fraction of the target product was concentrated to obtain a yellow liquid (5.20 g). The obtained yellow liquid was diluted with ethyl acetate, MEHQ (0.52 mg, 100 ppm) was added, and the solution was stored under refrigeration.

[0161] Yield 5.20g, yield 60.7%

[0162] 1 H-NMR(CDCl3)400MHz δ=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)

[0163] 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.

[0164] [ka]

[0165] In a 50 mL round-bottom flask, 2.45 g (5.77 mmol, 1.00 eq.) of NMe-iPrNBC-AEMA and 4 mL of DMF (degassed for 30 minutes) were added under argon and dissolved (yellow solution). 47.5 mg (0.289 mmol, 0.05 eq.) of azobisisobutyronitrile AIBN was then added, followed by heating to 65°C over 30 minutes, and stirring at the same temperature for 36 hours. Completion of the reaction was confirmed by NMR spectroscopy. After cooling, the reaction solution was added dropwise to 60 mL of methanol using a Pasteur pipette and stirred for 20 minutes.

[0166] The obtained slurry solution was centrifuged (10,000 rpm, 10 min), the supernatant was removed, methanol (40 mL) was added, and after stirring by hand, it was centrifuged again (10,000 rpm, 10 min). After repeating the same procedure once more, the obtained solid was dissolved in chloroform. This was added dropwise to methanol (60 mL) using a Pasteur choke and stirred for 20 minutes. The obtained slurry solution was centrifuged (10,000 rpm, 10 min), the supernatant was removed, methanol (40 mL) was added, and after stirring by hand, it was centrifuged again (10,000 rpm, 10 min). After repeating the same procedure once more, the obtained solid was dried under reduced pressure (60°C / <1 mmHg, 16 h) to obtain 1.89 g of the target P-NMe-iPrNBC-AEMA.

[0167] 1H-NMR(CDCl3)400MHz δ=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) GPC number average molecular weight Mn=9041

[0168] The polymer (P1)-A11 shown below was synthesized.

[0169] [ka]

[0170] <Rating> [Manufacturing of plated wiring 1] A surface treatment agent containing a polymer compound represented by formula (P1)-A11 was used to form a film on a substrate, and plated wiring was manufactured.

[0171] Cyclopentanone was added to the polymer compound represented by formula (P1)-A11 synthesized in Example 1, and the concentration was adjusted to 0.2% by mass to obtain photosensitive surface treatment agent 1.

[0172] Photosensitive surface treatment agent 1 was applied to a polyimide substrate (UBE Corporation, product name UPILEX) by spin coating (Mikasa Corporation, MS-A150, 1000 rpm). The photosensitive surface treatment agent layer was then formed by drying at 100°C for 20 minutes.

[0173] Next, a photosensitive surface treatment layer was deposited over the entire substrate, and 365 nm light at a rate of 2000 mJ / cm² was applied to it via a photomask. 2 The photosensitive surface treatment layer was exposed to light, forming amino group generation areas in the exposed areas and amino group non-generation areas in the unexposed areas.

[0174] Next, the material was immersed in a colloidal catalyst solution for electroless plating (Melplate Activator 7331, manufactured by Meltex Corporation) at room temperature for 3 minutes to deposit the catalyst (Pd) onto the amine generating area. After washing the surface with water, it was immersed in an electroless plating solution (Melplate NI-867, manufactured by Meltex Corporation) at 73°C for 1 minute to deposit nickel-phosphorus onto the catalyst and create a fine plated wiring.

[0175] [Manufacturing of plated wiring 2] The plated wiring was manufactured in the same manner as described in [Manufacturing 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).

[0176] [Evaluation of plated wiring] Figures 3A to 3D show overall photographs of the polyimide substrate and quartz substrate that underwent plating and wiring treatment in the examples, as well as optical microscope (KEYENCE Corporation, VHX-7000) images, respectively. Figure 3A shows the overall resolution chart drawn on a polyimide substrate and a quartz substrate. Figure 3B is an optical microscope image of a high-resolution chart drawn on a quartz substrate. Figure 3C shows optical microscope images with L / S = 3 / 3 to 10 / 10 μm drawn on a quartz substrate. Figure 3D shows optical microscope images of L / S = 1 / 1 to 8 / 8 μm drawn on a quartz substrate.

[0177] From Figures 3A to 3D, it was confirmed by visual inspection and microscopy that using a surface treatment agent containing the polymer compound represented by formula (P1)-A11 allows for the formation of high-resolution, high-quality plated wiring.

[0178] <Photolysis rate constant k(s) using model compound -1 ) Evaluation > The following compounds (1) to (7) 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. 2The light was irradiated for 5, 10, 15, 20, 25, and 30 seconds, and HPLC measurements were performed respectively.

[0179] [Chemical formula] [[ID=,6]]

[0180] [Chemical formula] <00,00887> From the HPLC measurement, the peak area of the raw material obtained (S0: the area before light irradiation, S t ) : the area after light irradiation for t seconds) was substituted into the following formula to obtain the photodegradation rate constant k (s<00,00108) ). The results are shown in Table 1. <00008,89>

[0182] [Mathematical formula]

[0183] [[ID =36]] [Table 1]

[0184] In the compounds (1) to (7), it was confirmed that the photodegradation rate of the compounds (2) to (7) was improved compared to the compound (1). The compound (1) is a model compound in which the group corresponding to R 1 in the compound represented by the formula (M1) is a hydrogen atom. From the above results, when R 1 is a linear or branched alkyl group having 1 to 4 carbon atoms, it was confirmed that the photodegradation rate of the nitrobenzyl group desorption was improved compared to the compound in which the group corresponding to R 1 is a hydrogen atom.

[0185] Compound (2) is a model compound of the polymer compound represented by formula (P1)-A11. Compounds (3) to (7) had photodegradation rate constants equivalent to those of compound (2). Therefore, it can be reasonably inferred that the same effects as those obtained when using the polymer compound represented by formula (P1)-A11 will be obtained when using the compounds (M1)-1 to (M1)-6 or the polymer compounds (P1)-A2 to (P1)-A6 exemplified above. [Explanation of symbols]

[0186] 11: Substrate, 10a: Photosensitive surface treatment agent, 10: Photosensitive surface treatment agent layer, 13: Photomask, 14: Amine generation area, 12: Amine non-generation area, 15: Catalyst layer, 16: Plating layer, 17: Insulator layer, 18: Plating layer (source electrode), 19: Plating layer (drain electrode), 21: Semiconductor layer

Claims

1. A photosensitive surface treatment agent comprising a compound represented by the following formula (M1). 【Chemistry 1】 (In formula (M1), R １ Y 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 is Y １ It bonds with the carbon atoms that make up the alkylene group, R １ and Y １ They may form a ring. R ２ is an isopropyl group or a cyclohexyl group, and R ３ and R ４ are each independently an alkyl group having 1 to 3 carbon atoms, n0 is an integer of 0 or more, and X is a halogen atom or an alkoxy group.)

2. A photosensitive surface treatment agent comprising a polymer compound represented by the following formula (P1)-A11. 【Chemistry 2】 (In formula (P1)-A11, the methyl group bonded to N can be substituted with a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms. m is a natural number.)

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

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

5. The photosensitive surface treatment agent according to claim 2 or 3, wherein at least one terminal of the polymer compound is a substituent represented by the following general formula (1x). 【Transformation 3】

6. A step of applying the photosensitive surface treatment agent according to claim 1 or 2 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.

7. A step of applying the photosensitive surface treatment agent according to claim 1 or 2 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.

8. A step of applying the photosensitive surface treatment agent according to claim 1 or 2 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.

9. 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 8.

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