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

Abstract

To provide a photosensitive surface treatment agent, a laminate, a transistor, a pattern formation method, and a transistor manufacturing method.SOLUTION: A photosensitive surface treatment agent comprises a compound represented by the formula (1) or a polymer compound induced from the formula (1). [In formula (1), R1 is a hydrogen atom or a C1-5 alkyl group, R2 and R3 independently represent a C1-3 alkyl group or a C1-13 fluoroalkyl group, R4 is a hydrogen atom or nitro group, n1 is 0 or 1, Y is a polymerizable group-containing group or a C1-20 linear or branched alkyl group].SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] In recent years, in the manufacture of microdevices such as semiconductor elements, integrated circuits, and devices for organic electroluminescence (EL) displays, a method has been proposed in which patterns with different surface properties are formed on a substrate and the differences in surface properties are utilized to create microdevices.

[0003] One example of a pattern formation method that utilizes differences in surface properties on a substrate is to form a region in which chemically active substituents are generated on a part of the substrate, which allows a metal material, organic material, or inorganic material to adhere to that part of the substrate.

[0004] Electroless plating is a technique for adhering a metal material to a substrate to form a metal film. For example, Patent Document 1 discloses a technique for forming fine wiring by electroless plating. Specifically, Patent Document 1 discloses 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 Application Laid-Open No. 2006-2201 Summary of the Invention

[0006] A first aspect of the present invention is a photosensitive surface treatment agent containing a compound represented by the following formula (1) or a polymer compound derived from the following formula (1).

[0007] [ka]

[0008] [In formula (1), R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 2 and R 3 are each independently an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 13 carbon atoms, and R 4 is a hydrogen atom or a nitro group, n1 is 0 or 1, and Y is a polymerizable group-containing group or a linear or branched alkyl group having 1 to 20 carbon atoms.]

[0009] Another aspect of the present invention is a transistor comprising a compound represented by the following formula (1) or a polymer compound derived from the following formula (1).

[0010] [ka]

[0011] [In formula (1), R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 2 and R 3 are each independently an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 13 carbon atoms, and R 4 is a hydrogen atom or a nitro group, n1 is 0 or 1, and Y is a polymerizable group-containing group or a linear or branched alkyl group having 1 to 20 carbon atoms.] [Brief explanation of the drawings]

[0012] [Figure 1] 1A to 1C are schematic diagrams for explaining a pattern forming method according to an embodiment of the present invention. [Figure 2] 5A to 5C are schematic diagrams for explaining a method for manufacturing a transistor according to the present embodiment. [Figure 3] 1A and 1B are a general photograph and an optical microscope photograph of a substrate plated using the photosensitive surface treatment agent of the present embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0013] <Photosensitive surface treatment agent> The photosensitive surface treatment agent of the present embodiment contains a compound represented by the following formula (1) or a polymer compound derived from a compound represented by the following formula (1).

[0014] [ka] [In formula (1), R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 2 and R 3 are each independently an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 13 carbon atoms, and R 4 is a hydrogen atom or a nitro group, n1 is 0 or 1, and Y is a polymerizable group-containing group or a linear or branched alkyl group having 1 to 20 carbon atoms.]

[0015] <Compound represented by formula (1)> When a photosensitive surface treatment agent containing the compound represented by formula (1) is applied to a substrate and irradiated with light, the nitrobenzyl group is eliminated, Y adheres to the substrate, and at the same time, thiol groups (-SH) are generated on the substrate surface. Metallic, organic, or inorganic materials can be attached to the areas where thiol groups have been generated.

[0016] According to the photosensitive surface treatment agent of the present embodiment, by disposing a metal material in a thiol generating site formed on the substrate surface, it is possible to form a metal pattern with a line width of 5 μm or less on the substrate surface without using a photoresist process, a development process, or an etching process.

[0017] (R 1 ) In formula (1), R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a tert-butyl group. Of these, a methyl group or an ethyl group is preferred, and a methyl group is more preferred.

[0018] (R 2 and R 3 ) R 2 and R 3 are each independently an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 13 carbon atoms. Examples of the alkyl group 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.

[0019] Examples of the fluoroalkyl group having 1 to 13 carbon atoms include methyl, ethyl, propyl, heptyl, nonyl, undecyl, and tridecyl groups in which some or all of the hydrogen atoms have been substituted with fluorine atoms. Preferred are those containing a perfluoroalkyl group having 4 to 10 carbon atoms, and more preferred are nonyl groups containing a perfluoroalkyl group having 6 carbon atoms.

[0020] (R 4 ) In formula (1), R 4 is a hydrogen atom or a nitro group.

[0021] (n1) In formula (1), n1 is 0 or 1.

[0022] (Y) In formula (1), Y is a polymerizable group-containing group or a linear or branched alkyl group having 1 to 20 carbon atoms. The term "polymerizable group" refers to a group that enables a compound having the polymerizable group to be polymerized by radical polymerization or the like, and refers to a group that contains a multiple bond between carbon atoms, such as an ethylenic double bond.

[0023] Examples of the polymerizable group include a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group.

[0024] The "polymerizable group-containing group" is a group containing a polymerizable group. The polymerizable group-containing group may be a group composed only of a polymerizable group, or may be a group composed of a polymerizable group and a group other than a polymerizable group.

[0025] Examples of Y include the following formula (Y1).

[0026] [ka] [In formula (Y1), Ya 01 represents an alkylene group having 1 to 10 carbon atoms, Ya 02 is a group in which two hydrogen atoms have been removed from an aromatic ring having 6 to 15 carbon atoms, Ra 01 represents a polymerizable group or a linear or branched alkyl group having 1 to 20 carbon atoms, and n2 and n3 each independently represent 0 or 1. * represents the bonding site to the sulfur element.]

[0027] (Ya 01 ) In formula (Y1), Ya 01 is an alkylene group having 1 to 10 carbon atoms. Ya 01 is preferably a linear or branched alkylene group. Examples of the linear alkylene group having 1 to 10 carbon atoms include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], and a pentamethylene group [-(CH2)5-].

[0028] Examples of branched alkylene groups having 1 to 10 carbon atoms include alkyl alkylene groups such as alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0029] (Ya 02 ) In formula (Y1), Ya 02 is a group in which two hydrogen atoms have been removed from an aromatic ring having 6 to 15 carbon atoms. Ya 02 Specific examples of the ring include groups in which two hydrogen atoms have been removed from a benzene ring, a fluorene ring, a naphthalene ring, or an anthracene ring.

[0030] (Ra 01 ) In formula (Y1), Ra 01 is a polymerizable group or a linear or branched alkyl group having 1 to 20 carbon atoms. The linear alkyl group is preferably a linear alkyl group having 3 to 18 carbon atoms, more preferably 5 to 15 carbon atoms, and even more preferably 6 to 12 carbon atoms.

[0031] Examples of the branched alkyl group include branched alkyl groups having 3 to 20 carbon atoms. The branched alkyl group preferably has 3 to 18 carbon atoms, and more preferably has 3 to 15 carbon atoms.

[0032] In formula (Y1), n2 and n3 each independently represent 0 or 1. * represents the bonding site to the sulfur element.

[0033] Examples of Y include the following formula (Y2).

[0034] [ka] [In formula (Y2), Ya 01 is an alkylene group having 1 to 10 carbon atoms, Ra 01 represents a polymerizable group or a linear or branched alkyl group having 1 to 20 carbon atoms, and * represents the bonding site with the sulfur element.]

[0035] Ya in formula (Y2) 01 , Ra 01 The explanation regarding is the same as above.

[0036] Examples of Y include the following formula (Y3).

[0037] [ka] [In formula (Y3), Ya 01 indicates an alkylene group having 1 to 10 carbon atoms, and * indicates the bonding site with the sulfur element.

[0038] Ya in formula (Y3) 01 The explanation regarding is the same as above.

[0039] Examples of Y include the following formula (Y3-2).

[0040] [ka] [In formula (Y3-2), Ya 01 indicates an alkylene group having 1 to 10 carbon atoms, and * indicates the bonding site with the sulfur element.

[0041] Ya in formula (Y3-2) 01 The explanation regarding is the same as above.

[0042] Examples of Y include the following formula (Y4).

[0043] [ka] [In formula (Y4), Ya 03 represents an alkylene group having 1 to 10 carbon atoms which may have an ether bond, Ya 02 is a group in which two hydrogen atoms have been removed from an aromatic ring having 6 to 15 carbon atoms, Ra 01 represents a polymerizable group or a linear or branched alkyl group having 1 to 20 carbon atoms, and * represents the bonding site with the sulfur element.]

[0044] Ya in formula (Y4) 02 , Ra 01 The explanation regarding is the same as above.

[0045] Ya in formula (Y4)03 represents an alkylene group having 1 to 10 carbon atoms which may have an ether bond (—O—). 03 is preferably an alkylene group having 1 to 10 carbon atoms or a group formed from a combination of an ether bond (—O—) and an alkylene group having 1 to 10 carbon atoms.

[0046] Examples of Y include the following formula (Y5).

[0047] [ka] [In formula (Y5), Ya 03 represents an alkylene group having 1 to 10 carbon atoms which may have an ether bond, Ya 02 indicates a group in which two hydrogen atoms have been removed from an aromatic ring having 6 to 15 carbon atoms, and * indicates the bonding site with the sulfur atom.

[0048] Ya in formula (Y5) 02 , Ya 03 The explanation regarding is the same as above.

[0049] Examples of Y include the following formula (Y5-2).

[0050] [ka] [In formula (Y5-2), Ya 03 represents an alkylene having 1 to 10 carbon atoms which may have an ether bond, Ya 02 indicates a group in which two hydrogen atoms have been removed from an aromatic ring having 6 to 15 carbon atoms, and * indicates the bonding site with the sulfur atom.

[0051] Ya in formula (Y5-2) 03 The explanation regarding is the same as above.

[0052] Specific examples of the compound represented by formula (1) are listed below.

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] <Polymer compound derived from compound represented by formula (1)> The polymer compound derived from the compound represented by formula (1) is a polymer compound in which the polymerizable group of the compound represented by formula (1) is converted into the main chain. The phrase "the polymerizable group is converted into a main chain" means that the multiple bond in the polymerizable group is cleaved to form a main chain. For example, in the case of a monomer having an ethylenic double bond, this means that the ethylenic double bond is cleaved and the single bond between carbon atoms forms a main chain.

[0059] The polymer compound derived from the compound represented by formula (1) is specifically represented by the following formula (1)-1.

[0060] [ka] [In formula (1)-1, R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 2 and R 3 are each independently an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 13 carbon atoms, and R 4 is a hydrogen atom or a nitro group, and Ya 01represents an alkylene group having 1 to 10 carbon atoms, Ya 02 represents a group in which two hydrogen atoms have been removed from an aromatic ring having 6 to 15 carbon atoms, n1, n2, and n3 each independently represent 0 or 1, and m represents a natural number.

[0061] In formula (1)-1, R 1 , R 2 , R 3 , R 4 , Ya 01 , Ya 02 , n1, n2, and n3 are the same as those described above, and m is a natural number.

[0062] The polymer compound derived from the compound represented by formula (1) preferably has a substituent represented by the following formula (1x) bonded to at least one end of the main chain: In the following formula (1x), * denotes the bonding site with the end of the main chain of the polymer compound derived from the compound represented by formula (1).

[0063] [ka]

[0064] Examples of polymer compounds in which a substituent represented by the above formula (1x) is bonded to the end of the main chain of a polymer compound represented by formula (1)-1 are shown below.

[0065] [ka]

[0066] Other specific examples of the polymer compound represented by formula (1)-1 are described below.

[0067] [ka]

[0068] The number average molecular weight of the polymer compound derived from the compound represented by formula (1) is preferably 300 to 100,000.

[0069] In one embodiment of the present invention, the photosensitive surface treatment agent comprises a compound represented by the above formula (1). In one embodiment of the present invention, the photosensitive surface treatment agent comprises a polymer compound represented by the above formula (1)-1.

[0070] In one embodiment of the present invention, the photosensitive surface treatment agent comprises a compound represented by the above formula (1) and a polymer compound represented by the above formula (1)-1.

[0071] In one embodiment of the present invention, the photosensitive surface treatment agent may contain a solvent, such as cyclopentanone, cycloheptanone, N-methyl-2-pyrrolidone (NMP), or cyclohexanone, with cyclopentanone being preferred.

[0072] <Method of manufacturing the compound> The compound represented by formula (1) can be produced by the following method. In the following description of the production method, the explanations of the symbols in the formulas are the same as those given above.

[0073] [Manufacturing method 1] The compound represented by formula (1) is produced by reacting an alcohol represented by the following formula (M1) with methacryloyl chloride or methacryloyl chloride.

[0074] [ka]

[0075] Specific example 1 of Production Example 1 is shown below.

[0076] [ka]

[0077] Specific example 2 of Production Example 1 is shown below.

[0078] [ka]

[0079] Specific example 3 of Production Example 1 is shown below.

[0080] [ka]

[0081] Specific example 4 of Production Example 1 is shown below.

[0082] [ka]

[0083] [Manufacturing method 2] An alcohol represented by the following formula (M2) is reacted with succinimidyl carbonate to obtain intermediate (M2)-1.

[0084] [ka]

[0085] The compound represented by formula (1)-A can be obtained by reacting intermediate (M2)-1 with 1-octanethiol. In this case, instead of 1-octanethiol, for example, 1-butanethiol (carbon number: 4), 1-hexanethiol (carbon number: 6), 1-hexadecanethiol (carbon number: 16), or 1-docosanethiol (carbon number: 22) can be used.

[0086] [ka]

[0087] [Manufacturing method 3] An alcohol compound represented by the following formula (M3) is reacted with triphenylphosphine and carbon tetrabromide to obtain intermediate (M3)-1. In this case, intermediate (M3)-1 may also be obtained by reacting an alcohol compound represented by the following formula (M3) with phosphorus tribromide.

[0088] [ka]

[0089] The compound represented by formula (1)-B can be obtained by reacting intermediate (M3)-1 with 1-octanethiol. In this case, instead of 1-octanethiol, for example, 1-butanethiol (carbon number: 4), 1-hexanethiol (carbon number: 6), 1-hexadecanethiol (carbon number: 16), or 1-docosanethiol (carbon number: 22) can be used.

[0090] [ka]

[0091] <Pattern formation method> The pattern formation method of this embodiment includes 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 a thiol-generating region in the exposed region, and disposing an electroless plating catalyst in the thiol-generating region and performing electroless plating. Each step will be described below with reference to the drawings.

[0092] As shown in FIG. 1(a), the photosensitive surface treatment agent 10a of the present embodiment is applied onto a substrate 11. Examples of the coating method that can be used include spin coating, dip coating, die coating, spray coating, roll coating, brush coating, etc. Coating may also be performed by a printing method such as flexographic printing or screen printing.

[0093] In this step, as shown in FIG. 1(a), a treatment for drying the solvent by, for example, heat or reduced pressure may be added.

[0094] As a result, a photosensitive surface treatment agent layer 10 is formed on the substrate 11 as shown in FIG. 1(b).

[0095] 1(c), a photomask 13 having an exposure area of ​​a predetermined pattern is prepared. The exposure method is not limited to a method using a photomask, and other methods can be used, such as projection exposure using an optical system such as lenses and mirrors, or maskless exposure using a spatial light modulator or laser beam. The photomask 13 may be provided so as to be in contact with the photosensitive surface treatment agent layer 10, or may be provided so as not to be in contact with the photosensitive surface treatment agent layer 10.

[0096] 1(c), the photosensitive surface treatment agent layer 10 is irradiated with UV light through a photomask 13. As a result, the photosensitive surface treatment agent layer 10 is exposed in the exposure region of the photomask 13.

[0097] As a result, as shown in FIG. 1(d), thiol-generated parts 14 are formed in the exposed parts, and thiol-ungenerated parts 12 are formed in the unexposed parts.

[0098] The UV light may be, for example, i-rays with a wavelength of 365 nm. The exposure dose and exposure time do not necessarily need to be such that complete deprotection proceeds, but are sufficient to generate some thiol groups.

[0099] Next, as shown in Fig. 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 plating solution for electroless plating, and examples of such catalysts include silver and palladium.

[0100] Thiol groups are exposed on the surface of thiol generating section 14. Thiol groups are capable of capturing and reducing the electroless plating catalyst described above. Therefore, the electroless plating catalyst is captured only on thiol generating section 14, forming catalyst layer 15. Furthermore, electroless plating catalysts capable of supporting thiol groups can be used.

[0101] 1(f), electroless plating is performed to form a plating layer 16. Examples of materials for the plating layer 16 include nickel-phosphorus (NiP) and copper (Cu).

[0102] In this step, substrate 11 is immersed in an electroless plating bath to reduce metal ions on the catalyst surface and deposit plating layer 16. At this time, because catalyst layer 15 carrying a sufficient amount of catalyst is formed on the surface of thiol generating portion 14, plating layer 16 can be selectively deposited only on thiol generating portion 14.

[0103] Through the above steps, it is possible to form a wiring pattern on a predetermined substrate using the photosensitive surface treatment agent of the present embodiment.

[0104] <Transistor manufacturing method> Furthermore, a method for manufacturing a transistor in which the plating layer 16 obtained by the above-mentioned <pattern formation method> is used as a gate electrode will be described with reference to FIG.

[0105] As shown in FIG. 2( a), an insulator layer 17 is formed by a known method to cover the plating layer 16 and the thiol-free regions 12 of the electroless plating pattern formed by the pattern formation method described above. The insulator layer 17 may be formed by applying a coating solution prepared 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 insulator layer 17 can be formed into a desired pattern by irradiating the coating with UV light through a mask having openings corresponding to the regions where the insulator layer 17 is to be formed. Note that the thiol-free regions 12 may be removed, if necessary, before forming the insulator layer 17.

[0106] As shown in FIG. 2(b), a photosensitive surface treatment agent layer 10 is formed on an insulator layer 17 in the same manner as in the electroless plating pattern formation method described above, and a thiol generating section 14 is formed in the area where the source electrode and drain electrode are to be formed.

[0107] 2(c), in the same manner as in the pattern formation method described above, an electroless plating catalyst is supported on the thiol generator 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). Materials for the plating layers 18 and 19 include nickel-phosphorus (NiP) and copper (Cu), but they may be formed of a material different from that of the plating layer 16 (gate electrode). Alternatively, a different metal, such as gold (Au), may be deposited on the surface of nickel-phosphorus (NiP) or copper (Cu) by electroless gold plating.

[0108] As shown in FIG. 2(d), a semiconductor layer 21 is formed between the plating layer 18 (source electrode) and the plating layer 19 (drain electrode).

[0109] The semiconductor layer 21 may be formed by 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, applying the solution between the plating layer 18 (source electrode) and the plating layer 19 (drain electrode), and drying the solution.

[0110] 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, applying the solution containing the insulating polymer, and drying it.

[0111] When the semiconductor layer 21 is formed in this manner, the insulating polymer is concentrated below the semiconductor layer 21 (on the insulating layer 17 side). If a polar group such as a thiol group is present at the interface between the organic semiconductor and the insulating layer, the transistor characteristics tend to deteriorate, but by providing the organic semiconductor via the insulating polymer described above, the deterioration of the transistor characteristics can be suppressed. In this manner, a transistor can be manufactured.

[0112] The above method eliminates the need for a separate chemical resist during the UV exposure process, allowing for a simple process using only a photomask. Naturally, this eliminates the need for a resist layer removal step. Furthermore, the catalytic reduction ability of the thiol group eliminates the need for the catalyst activation step that is normally required, enabling high-resolution patterning while achieving significant cost and time savings. Furthermore, the ability to use a dip coating method makes it highly compatible with roll-to-roll processes.

[0113] The structure of the transistor is not particularly limited and can be appropriately selected depending on the purpose. For example, top-contact / bottom-gate type, top-contact / top-gate type, and bottom-contact / top-gate type transistors may be manufactured in the same manner.

[0114] <Laminate> This embodiment is a laminate containing the photosensitive surface treatment agent of the embodiment. The laminate of this embodiment is a laminate in which a substrate and a metal pattern are laminated, and contains a photosensitive surface treatment agent in the unexposed area where no pattern is formed.

[0115] <Transistor> This embodiment is a transistor including the photosensitive surface treatment agent of the embodiment. The laminate of this embodiment is a transistor having a laminate in which a substrate and a metal pattern are laminated, and contains a photosensitive surface treatment agent in the unexposed area where no pattern is formed. [Example]

[0116] 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.

[0117] Example 1: Synthesis of photosensitive thiol-generating monomer 2-((4,5-dimethoxy-2-nitrobenzyl)thio)ethan-1-ol (NBS-OH) represented by the following formula (M) was synthesized by the method described below.

[0118] [ka]

[0119] 1-(Bromomethyl)-4,5-dimethoxy-2-nitrobenzene (120.0 g, 435 mmol, 1.0 eq., Sigma-Aldrich) and acetonitrile (2.4 L, Fujifilm Wako Pure Chemical Industries) were placed in a 5 L four-neck flask under argon and stirred.

[0120] Cesium carbonate (170.0 g, 0.522 mmol, 1.2 eq., Fujifilm Wako Pure Chemical Industries) was added thereto, and then mercaptoethanol (40.8 g, 522 mmol, 1.2 eq., Tokyo Chemical Industry Co., Ltd.) was added dropwise over 15 minutes, followed by reaction in a bath at 50°C for 21 hours.

[0121] Water (2.4 L) was added, and the mixture was stirred for 10 minutes. The mixture was then concentrated under reduced pressure (40°C / 20 mmHg) to remove only the acetonitrile. The residue was transferred to a 15 L plastic container and extracted with ethyl acetate (4.8 L). The aqueous layer was further extracted with ethyl acetate (2.4 L). The combined ethyl acetate layers were washed three times with water (2.4 L) and then dried over anhydrous magnesium sulfate. After removing the desiccant, the mixture was concentrated under reduced pressure (40°C / 20 mmHg) to obtain a brown solid. The resulting crude product was purified using a silica gel column to obtain 92.4 g (78.3%) of NBS-OH.

[0122] The results of 1H-NMR (JEOL Ltd., 300 MHz) measurement are shown below. 1H-NMR (300MHz, CDCl3): δ2.11(1H,t),2.73(2H,t),3.76(2H,m),3.80(3H,s),3.99(3H,s),4.15(2H,s),6.94(1H,s),7.36(1H,s)

[0123] 2-((4,5-dimethoxy-2-nitrobenzyl)thio)ethyl methacrylate (NBS-MEMA) represented by the following formula (11) was synthesized by the method described below.

[0124] [ka]

[0125] NBS-OH and dry THF (400 mL, Fujifilm Wako Pure Chemical Industries, Ltd.) were dissolved in a 1 L four-neck flask under argon. Triethylamine (11.1 g, 110 mmol, 1.5 eq., Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the flask, and the mixture was cooled with ice water. Methacryloyl chloride (10.7 g, 102 mmol, 1.4 eq., Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise over 30 minutes, followed by stirring overnight (the ice bath was left on and the mixture was allowed to return to room temperature).

[0126] Ice water (400 g) was poured into the reactor, stirred for 5 minutes, and then transferred to a separatory funnel and extracted with ethyl acetate (800 mL). The ethyl acetate layer was then washed twice with 5% sodium bicarbonate water (400 mL) and three times with tap water (400 mL), and then dried over anhydrous sodium sulfate.

[0127] After removing the desiccant, the mixture was concentrated under reduced pressure (40°C / 20mmHg) to obtain 31g of a yellow solid. The obtained crude product was purified with a silica gel column to obtain 16.9g (67.6%) of NBS-MEMA.

[0128] The results of 1H-NMR (JEOL Ltd., 300 MHz) measurement are shown below. 1H-NMR (300MHz, CDCl3): δ1.94(2H,s),2.76(2H,t),3.95(3H,s),4.00(3H,s),4.16(2H,s),4.31(2H,t),5.59(1H,s),6.11(1H,s),7.27(1H,s), 7.66(1H,s)

[0129] Poly(2-((4,5-dimethoxy-2-nitrobenzyl)thio)ethyl methacrylate) (P-NBS-MEMA) represented by the following formula (12) was synthesized by the method described below.

[0130] [ka]

[0131] NBS-MEMA (15.0 g, 43.9 mmol, 1.0 eq.) and degassed DMF (30 ml, Fujifilm Wako Pure Chemical Industries, Ltd.) were dissolved in a 100 mL recovery flask under argon. AIBN (0.4 g, 2.2 mmol, 0.05 eq., Fujifilm Wako Pure Chemical Industries, Ltd.) was then added, and the bath temperature was raised to 65°C over 30 minutes and the mixture was heated and stirred at the same temperature for 24 hours.

[0132] The reaction mixture was allowed to cool, then added dropwise to methanol (600 mL) and stirred for 30 minutes. The precipitated solid was collected by filtration and washed three times with methanol (100 mL). The solid was redissolved in chloroform (150 mL) and then added dropwise to methanol (1.5 L) using a dropping funnel over 30 minutes.

[0133] After the addition was completed, the mixture was stirred for 15 minutes, filtered, washed three times with 100 mL of methanol, and dried under reduced pressure (60°C / <1 mmHg, 16 hours) to obtain 13.3 g of the desired P-NBS-MEMA.

[0134] The results of 1H-NMR (JEOL Ltd., 300 MHz) and GPC (Tosoh Corporation, HLC-8420GPC, Shodex KF-805L x 2) are shown below. 1H-NMR(300MHz,CDCl3):δ0.90-1.37(m),1.87-1.94(m),2.73(2H,m),3.90-4.10(10H,m),6.93(1H,s), 7.56(1H,s) GPC:MW:69770, Mn:32392, PDI:2.154

[0135] <Example 2> [Preparation of plated wiring] A surface treatment agent containing the polymer compound (P-NBS-MEMA) represented by formula (12) was used to form a film on a substrate, and plated wiring was produced.

[0136] Photosensitive surface treatment agent 1 was obtained by adding cyclopentanone to the polymer compound (P-NBS-MEMA) represented by formula (12) synthesized in Example 1 to adjust the concentration to 0.2 mass %.

[0137] Photosensitive surface treatment agent 1 was applied to a PEN substrate (Teonex Q65HA, manufactured by Teijin Limited) by spin coating (MS-A150, manufactured by Mikasa Co., Ltd.) at 1000 rpm. It was then dried at 100°C for 10 minutes to form a photosensitive surface treatment agent layer.

[0138] Next, the substrate on which the photosensitive surface treatment agent layer was formed on the entire surface was irradiated with 1000 mJ / cm of light with a wavelength of 365 nm through a photomask. 2 The photosensitive surface treatment agent layer was exposed to light, forming thiol-generated portions in the exposed areas and non-thiol-generated portions in the unexposed areas.

[0139] Next, the substrate was immersed in a catalyst colloid solution for electroless plating (Melplate Activator 7331, manufactured by Meltex) at room temperature for 10 minutes to attach a catalyst (Pd) to the thiol-generating area. After rinsing the surface with water, the substrate was immersed in an electroless plating solution (Melplate NI-867, manufactured by Meltex) at 73°C for 1 minute to deposit nickel phosphorus on the catalyst, producing fine plated wiring.

[0140] [Evaluation of plated wiring and solubility] FIG. 3 shows a photograph of the entire PEN substrate on which the plating wiring process was performed in the example, and an image taken with an optical microscope (Keyence Corporation, VHX-7000).

[0141] As can be seen from Figure 3, it was confirmed by visual and microscopic observation that high-definition, excellent plated wiring was formed without using resist, even in a low-temperature process below 100°C. Furthermore, no peeling or dissolution of any of the layers was observed.

[0142] Furthermore, the polymer compound (P-NBS-MEMA) represented by formula (12) synthesized in Example 1 was easily dissolved in cyclopentanone, and no change was observed over time.

[0143] From the above results, it was found that photosensitive surface treatment agent 1 can selectively pattern thiols at any desired position by light irradiation alone, and sufficient adhesion was obtained even after laminating a metal film using plating. This is expected to simplify management and reduce costs in the production and transportation of wiring formation films, as well as in the manufacturing process of electronic materials using such films.

[0144] Furthermore, it was found that high-resolution electroless plating wiring can be applied to smooth substrates without using resist, even in low-temperature processes. This allows for the elimination of processes such as surface preparation, resist development, and resist stripping, which require many chemicals, as well as the energy-intensive heating steps in PEB and other processes, which is expected to be beneficial in terms of both economics and environmental conservation. Furthermore, the use of light with a wavelength (365 nm) that places less strain on the substrate than DUV makes this technology ideal for processing on films, which is expected to be applied to roll-to-roll (RtoR) processes.

[0145] Furthermore, by using this embodiment, it is expected that transparent electrodes can be produced inexpensively. Considering the repeated use of these processes in the formation of multilayer wiring in electronic devices, the effects of a resist-free process are extremely significant. Furthermore, if the present invention can reduce the amount of chemical substances used and realize a device manufacturing process with fewer steps, it will not only improve mass productivity and economic efficiency, but also reduce the burden associated with developing and maintaining manufacturing equipment. Furthermore, the organic thin films produced by this invention function even at ultrathin films of about 2 to 10 nm, and have an extremely low environmental impact.

[0146] Example 3 (Synthesis of 4,5-dimethoxy-2-nitrobenzaldehyde) 3,4-Dimethoxybenzaldehyde (50.1 g, 301 mmol) was placed in a 500 mL recovery flask and dissolved in acetic acid (120 mL). Fuming nitric acid (57 mL, 930 mmol) was slowly added dropwise to the solution in an ice bath, and the mixture was stirred at 0° C. for 2 hours. The reaction solution was poured into cold water (800 mL), suction filtered, and washed successively with pure water and hexane. Recrystallization (ethanol) was carried out by slow cooling to obtain 35.2 g (166 mmol, 55%) of yellow crystals.

[0147] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 4.03 (3H, s), 4.04 (3H, s), 7.43 (1H, s), 7.62 (1H, s), 10.5 (1H, s).

[0148] [ka]

[0149] (Synthesis of 4,5-dimethoxy-2-nitrobenzyl alcohol) 4,5-Dimethoxy-2-nitrobenzaldehyde (14.1 g, 66.8 mmol) was placed in a 500 mL recovery flask and dissolved in tetrahydrofuran (200 mL) and methanol (100 mL). Sodium borohydride (3.79 g, 100 mmol) was added in small portions on an ice bath, and the mixture was stirred at 0°C for 30 minutes and then at room temperature for a further 90 minutes. After concentration, ethyl acetate (100 mL × 3), pure water (200 mL), and 2N hydrochloric acid (25 mL) were added for extraction, and the organic layer was washed with saturated brine (200 mL × 2), dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 13.8 g (64.7 mmol, 97%) of a yellow solid.

[0150] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 2.61 (1H, br s), 3.97 (3H, s), 4.01 (3H, s), 4.97 (2H, s), 7.18 (1H, s), 7.72 (1H, s).

[0151] [ka]

[0152] (Synthesis of (4,5-dimethoxy-2-nitrophenyl)methyl(2,5-dioxo-1-pyrrolidinyl)carbonate) 4,5-Dimethoxy-2-nitrobenzyl alcohol (1.00 g, 4.69 mmol) was placed in a 100 mL two-necked recovery flask and dissolved in dry acetonitrile (25 mL). Di(N-succinimidyl)carbonate (2.40 g, 9.37 mmol) and triethylamine (2.0 mL, 14.4 mmol) were added, and the mixture was stirred at room temperature under a nitrogen atmosphere for 18 hours. After concentration, the mixture was extracted with ethyl acetate (60 mL x 4), purified water (60 mL), and 2N hydrochloric acid (10 mL). The organic layer was washed with saturated brine (200 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated. The residue was purified by silica gel column chromatography (hexane:ethyl acetate = 1:2) to obtain 1.89 g (3.55 mmol, 76%) of a yellow powder.

[0153] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 2.86 (4H, s), 3.98 (3H, s), 4.07 (3H, s), 5.80 (2H, s), 7.05 (1H, s), 7.78 (1H, s).

[0154] [ka]

[0155] (Synthesis of S-octyl O-[(4,5-dimethoxy-2-nitrophenyl)methyl] carbonate) (4,5-dimethoxy-2-nitrophenyl)methyl(2,5-dioxo-1-pyrrolidinyl)carbonate (0.10 g, 0.28 mmol) was placed in a 10 mL two-necked test tube and dissolved in dry tetrahydrofuran (4 mL). 4-Dimethylaminopyridine (DMAP) (0.14 g, 1.14 mmol) and 1-octanethiol (0.19 mL, 1.12 mmol) were added, and the mixture was stirred at room temperature under a nitrogen atmosphere for 24 hours. After concentration, the mixture was extracted with ethyl acetate (50 mL x 3), purified water (50 mL), and 2N hydrochloric acid (3 mL). The organic layer was washed with saturated brine (200 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated. The residue was purified by silica gel column chromatography (hexane:ethyl acetate = 4:1) to obtain 0.06 g (0.15 mmol, 52%) of a yellow solid.

[0156] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 0.88 (3H, t, J = 6.9 Hz), 1.19-1.44 (10H, m), 1.66 (2H, quint, J = 7.5 Hz), 2.90 (2H, t, J = 7.4 Hz), 3.96 (3H, s), 3.99 (3H, s), 5.67 (2H, s), 7.01 (1H, s), 7.74 (1H, s).

[0157] [ka]

[0158] Example 4 (Synthesis of 4,5-dimethoxy-2-nitrobenzyl bromide) 4,5-Dimethoxy-2-nitrobenzyl alcohol (0.50 g, 2.34 mmol) was placed in a 30 mL two-necked recovery flask and dissolved in dry tetrahydrofuran (10 mL). Triphenylphosphine (0.927 g, 3.53 mmol) and carbon tetrabromide (1.16 g, 3.50 mmol) were added, and the mixture was stirred at room temperature for 1 hour under a nitrogen atmosphere. After filtration, the filtrate was concentrated and purified by silica gel column chromatography (hexane:ethyl acetate=3:1) to obtain 0.48 g (1.74 mmol, 74%) of a yellow powder.

[0159] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 3.97 (3H, s), 4.00 (3H, s), 4.88 (2H, s), 6.95 (1H, s), 7.68 (1H, s).

[0160] [ka]

[0161] (Synthesis of 4,5-dimethoxy-2-nitrobenzyl octyl sulfide) Dry acetonitrile (30 mL), potassium carbonate (0.57 g, 4.14 mmol), and 1-octanethiol (0.61 g, 4.14 mmol) were placed in a 100 mL two-necked flask and stirred at room temperature under a nitrogen atmosphere for 2 hours. 4,5-dimethoxy-2-nitrobenzyl bromide (0.80 g, 2.90 mmol) was added and the mixture was refluxed under a nitrogen atmosphere for 5 hours. After concentration, the mixture was extracted with chloroform (70 mL x 3), purified water (100 mL), and 2N hydrochloric acid (4 mL). The organic layer was washed with saturated brine (200 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated. The residue was purified by silica gel column chromatography (hexane:ethyl acetate = 6:1) to obtain 0.56 g (1.65 mmol, 56%) of a yellow powder.

[0162] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 0.88 (3H, t, J = 6.9 Hz), 1.19-1.40 (10H, m), 1.49-1.61 (2H, m), 2.49 (2H, t, J = 7.5 Hz), 3.94 (3H, s), 3.98 (3H, s), 4.10 (2H, s), 6.96 (1H, s), 7.62 (1H, s).

[0163] [ka]

[0164] <Example 5> (Synthesis of 1-(4,5-dimethoxy-2-nitrophenyl)ethanone) 3,4-Dimethoxyacetophenone (50.1 g, 278 mmol) was placed in a 500 mL recovery flask and dissolved in acetic acid (200 mL). Fuming nitric acid (47.6 mL, 1128 mmol) was slowly added dropwise in an ice bath, and the mixture was stirred at 0°C for 90 minutes. The reaction solution was poured into cold water (1500 mL), suction filtered, and washed successively with pure water and hexane. The product was recrystallized (from ethanol) by slow cooling to obtain 42.3 g (188 mmol, 68%) of yellow crystals.

[0165] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 2.51 (3H, s), 3.99 (3H, s), 4.02 (3H, s), 6.76 (1H, s), 7.62 (1H, s).

[0166] [ka]

[0167] (Synthesis of 1-(4,5-dimethoxy-2-nitrophenyl)ethanol) 1-(4,5-dimethoxy-2-nitrophenyl)ethanone (8.78 g, 39.0 mmol) was placed in a 300 mL recovery flask and dissolved in tetrahydrofuran (100 mL) and methanol (50 mL). Sodium borohydride (2.06 g, 58.5 mmol) was added in small portions on an ice bath, and the mixture was stirred at 0°C for 30 minutes and then at room temperature for a further 2 hours. After concentration, the mixture was extracted with dichloromethane (100 mL × 3), purified water (100 mL), and 2N hydrochloric acid (30 mL). The organic layer was washed with saturated brine (100 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 8.28 g (36.4 mmol, 96%) of a yellow solid.

[0168] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1H-NMR (CDCl3 / TMS, 400 MHz): δ 1.57 (3H, d, J = 6.3 Hz), 2.26 (1H, d, J = 3.7 Hz), 3.95 (3H, s), 4.01 (3H, s), 4.97 (1H, qd, J = 6.3, 3.7 Hz), 7.31 (1H, s), 7.58 (1H, s).

[0169] [ka]

[0170] (Synthesis of 1-(4,5-dimethoxy-2-nitrophenyl)ethyl (2,5-dioxo-1-pyrrolidinyl) carbonate) 1-(4,5-dimethoxy-2-nitrophenyl)ethanol (1.00 g, 4.43 mmol) was placed in a 100 mL two-necked recovery flask and dissolved in dry acetonitrile (15 mL). Di(N-succinimidyl)carbonate (1.71 g, 6.68 mmol) and triethylamine (1.8 mL, 13.0 mmol) were added, and the mixture was stirred at room temperature under a nitrogen atmosphere for 18 hours. After concentration, the mixture was extracted with chloroform (80 mL x 4), purified water (100 mL), and 2N hydrochloric acid (10 mL). The organic layer was washed with saturated brine (200 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated. The residue was purified by silica gel column chromatography (hexane:ethyl acetate = 1:1) to obtain 0.69 g (1.87 mmol, 43%) of a yellow powder.

[0171] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 1.77 (3H, d, J = 6.4 Hz), 2.80 (4H, s), 3.96 (3H, s), 4.07 (3H, s), 6.51 (1H, q, J = 6.4 Hz), 7.08 (1H, s), 7.65 (1H, s).

[0172] [ka]

[0173] (Synthesis of S-octyl O-[1-(4,5-dimethoxy-2-nitrophenyl)ethyl] carbonate) 1-(4,5-dimethoxy-2-nitrophenyl)ethyl(2,5-dioxo-1-pyrrolidinyl)carbonate (0.37 g, 1.00 mmol) was placed in a 20 mL two-necked recovery flask and dissolved in dry tetrahydrofuran (10 mL). 4-Dimethylaminopyridine (DMAP) (0.25 g, 4.01 mmol) and 1-octanethiol (0.68 mL, 3.92 mmol) were added, and the mixture was stirred at room temperature under a nitrogen atmosphere for 24 hours. After concentration, the mixture was extracted with chloroform (20 mL x 3), purified water (50 mL), and 2N hydrochloric acid (5 mL). The organic layer was washed with saturated brine (100 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated. The residue was purified by silica gel column chromatography (hexane:ethyl acetate = 8:1) to obtain 0.18 g (0.45 mmol, 45%) of a yellow solid.

[0174] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 0.87 (3H, t, J = 6.9 Hz), 1.27-1.39 (10H, m), 1.43-1.62 (2H, m), 1.65 (3H, d, J = 6.4 Hz), 2.74-2.87 (2H, m), 3.94 (3H, s), 3.99 (3H, s), 6.58 (1H, q, J = 6.4 Hz), 7.02 (1H, s), 7.61 (1H, s).

[0175] [ka]

[0176] Example 6 (Synthesis of 1-(4,5-dimethoxy-2-nitrophenyl)ethyl bromide) 1-(4,5-dimethoxy-2-nitrophenyl)ethanol (10.1 g, 44.4 mmol) was placed in a 200 mL two-necked recovery flask and dissolved in dry dichloromethane (300 mL). Under a nitrogen atmosphere and an ice bath, phosphorus tribromide (15.2 g, 56.2 mmol) dissolved in dry dichloromethane (50 mL) was slowly added dropwise, and the mixture was stirred at 0°C for 1 hour. The organic layer was collected by adding purified water (150 mL), and the aqueous layer was extracted with methylene chloride (100 mL × 2). The combined organic layer was washed with saturated brine (150 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated. The residue was purified by silica gel column chromatography (hexane:ethyl acetate = 4:1) to obtain 8.94 g (30.8 mmol, 70%) of a yellow viscous liquid.

[0177] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 2.07 (3H, d, J = 6.9 Hz), 3.95 (3H, s), 4.02 (3H, s), 6.04 (1H, q, J = 6.9 Hz) 7.28 (1H, s), 7.46 (1H, s).

[0178] [ka]

[0179] (Synthesis of 1-(4,5-dimethoxy-2-nitrophenyl)ethyl octyl sulfide) Dry acetonitrile (30 mL), potassium carbonate (0.52 g, 4.07 mmol), and 1-octanethiol (0.71 mL, 4.07 mmol) were placed in a 100 mL two-necked flask and stirred at room temperature under a nitrogen atmosphere for 2 hours. 1-(4,5-dimethoxy-2-nitrophenyl)ethyl bromide (0.84 g, 2.91 mmol) was added and the mixture was refluxed under a nitrogen atmosphere for 4 hours. After concentration, the mixture was extracted with chloroform (70 mL x 3), purified water (100 mL), and 2N hydrochloric acid (4 mL). The organic layer was washed with saturated brine (200 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated. The residue was purified by silica gel column chromatography (hexane:ethyl acetate = 8:1) to obtain 0.58 g (1.65 mmol, 57%) of a yellow powder.

[0180] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 0.87 (3H, t, J = 6.9 Hz), 1.14-1.37 (10H, m), 1.39-1.51 (2H, m), 1.57 (3H, d, J = 7.0 Hz), 2.21-2.32 (1H, m), 2.32-2.43 (1H, m), 3.94 (3H, s), 3.99 (3H, s), 4.85 (1H, q, J = 7.0 Hz), 7.35 (1H, s), 7.41 (1H, s).

[0181] [ka]

[0182] Example 7 (Synthesis of 1-(3,4-dimethoxyphenyl)-2-methyl-1-propanone) 1,2-Dimethoxybenzene (64.8 mL, 508 mmol) and isobutyric anhydride (93.0 mL, 576 mmol) were placed in a 500 mL recovery flask, and iodine (7.72 g, 30.4 mmol) was added. The mixture was stirred at room temperature for 2.5 hours. After washing with saturated aqueous sodium thiosulfate (50 mL), the mixture was extracted with ethyl acetate (100 mL x 3) and purified water (150 mL). The organic layer was washed with saturated brine (100 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated to yield 73.1 g (351 mmol, 69%) of a brown viscous liquid.

[0183] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 1.22 (6H, d, J = 6.9 Hz), 3.56 (1H, sept, J = 6.9 Hz), 3.94 (3H, s), 3.95 (3H, s), 6.90 (1H, d, J = 8.5 Hz), 7.55 (1H, d, J = 2.0 Hz), 7.60 (1H, dd, J = 8.5, 2.0 Hz).

[0184] [ka]

[0185] (Synthesis of 1-(4,5-dimethoxy-2-nitrophenyl)-2-methyl-1-propanone) 1-(3,4-dimethoxyphenyl)-2-methyl-1-propanone (13.6 g, 65.1 mmol) was placed in a 200 mL recovery flask and dissolved in acetic acid (32.5 mL). Fuming nitric acid (10.8 mL, 260 mmol) was slowly added dropwise to the solution in an ice bath, and the mixture was stirred at 0°C for 2 hours. The reaction solution was poured into cold water (800 mL), suction filtered, and washed successively with pure water and hexane. Recrystallization (ethanol) was carried out by slow cooling to obtain 9.56 g (37.8 mmol, 58%) of yellow crystals.

[0186] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 1.22 (6H, d, J = 7.0 Hz), 2.91 (1H, sept, J = 7.0 Hz), 3.98 (3H, s), 3.99 (3H, s), 6.69 (1H, s), 7.66 (1H, s).

[0187] [ka]

[0188] (Synthesis of 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropanol) 1-(4,5-dimethoxy-2-nitrophenyl)-2-methyl-1-propanone (10.2 g, 40.4 mmol) was placed in a 300 mL recovery flask and dissolved in tetrahydrofuran (80 mL) and methanol (40 mL). Sodium borohydride (2.32 g, 61.3 mmol) was added in small portions on an ice bath, and the mixture was stirred at 0°C for 30 minutes and then at room temperature for a further 2 hours. After concentration, the mixture was extracted with dichloromethane (100 mL × 3), purified water (100 mL), and 2N hydrochloric acid (35 mL). The organic layer was washed with saturated brine (150 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 10.2 g (40.0 mmol, 99%) of a yellow solid.

[0189] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 0.96 (6H, d, J = 6.8 Hz), 1.97-2.11 (1H, m), 2.18 (1H, br s), 3.95 (3H, s), 3.99 (3H, s), 5.27 (1H, br d, J =3.6 Hz), 7.21 (1H, s), 7.57 (1H, s).

[0190] [ka]

[0191] (Synthesis of 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropyl(2,5-dioxo-1-pyrrolidinyl)carbonate) 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropanol (4.3 g, 16.8 mmol) was placed in a 50 mL two-necked recovery flask and dissolved in dry acetonitrile (30 mL). Di(N-succinimidyl)carbonate (8.92 g, 34.8 mmol) and triethylamine (4.7 mL, 33.9 mmol) were added, and the mixture was stirred at room temperature under a nitrogen atmosphere for 18 hours. After concentration, the mixture was extracted with chloroform (50 mL x 4), purified water (50 mL), and 2N hydrochloric acid (10 mL). The organic layer was washed with saturated brine (200 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated. The residue was purified by silica gel column chromatography (hexane:ethyl acetate = 2:1) to obtain 0.52 g (4.24 mmol, 64%) of a yellow powder.

[0192] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 1.04 (3H, d, J = 6.9 Hz), 1.10 (3H, d, J = 6.9 Hz), 2.23-2.31 (1H, m), 2.79 (4H, s), 3.95 (3H, s), 4.06 (3H, s), 6.41 (1H, d, J = 5.0 Hz), 6.97 (1H, s), 7.67 (1H, s).

[0193] [ka]

[0194] (Synthesis of S-octyl O-(1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropyl)carbonate) 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropyl (2,5-dioxo-1-pyrrolidinyl) carbonate (98.5 mg, 0.25 mmol) was placed in a 10 mL two-necked test tube and dissolved in dry tetrahydrofuran (2 mL). 4-Dimethylaminopyridine (DMAP) (64.3 mg, 0.53 mmol) and 1-octanethiol (0.087 mL, 0.50 mmol) were added, and the mixture was stirred at room temperature under a nitrogen atmosphere for 24 hours. After concentration, the mixture was extracted with ethyl acetate (60 mL x 3), purified water (60 mL), and 2N hydrochloric acid (2 mL). The organic layer was washed with saturated brine (100 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated. The residue was purified by silica gel column chromatography (hexane:ethyl acetate = 4:1) to obtain 43.6 mg (0.10 mmol, 41%) of a yellow solid.

[0195] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 0.87 (3H, t, J = 6.6 Hz), 1.00 (3H, d, J = 6.9 Hz), 1.02 (3H, d, J = 6.9 Hz), 1.18-1.39 (10H, m), 1.53-1.63 (2H, m), 2.12-2.24 (1H, m), 2.74-2.86 (2H, m), 3.95 (3H, s), 3.97 (3H, s), 6.47 (1H, d, J = 5.5 Hz), 6.92 (1H, s), 7.63 (1H, s).

[0196] [ka]

[0197] Example 8 (Synthesis of 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropyl bromide) 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropanol (3.17 g, 12.4 mmol) was placed in a 500 mL two-necked recovery flask and dissolved in dry benzene (250 mL). Pyridine (0.5 mL, 6.20 mmol) was added, and phosphorus tribromide (1.80 mL, 19.0 mmol) dissolved in dry benzene (100 mL) was slowly added dropwise under a nitrogen atmosphere in an ice bath, followed by stirring at 0°C for 2 hours. After adding purified water (10 mL) and concentrating, ethyl acetate (100 mL × 3) and purified water (150 mL) were added for extraction. The organic layer was washed with saturated brine (150 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated. Purification was performed by silica gel column chromatography (hexane:ethyl acetate = 5:1) to obtain 2.05 g (6.44 mmol, 52%) of a yellow viscous liquid.

[0198] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 0.94 (3H, d, J = 6.8 Hz), 1.22 (3H, d, J = 6.6 Hz), 2.23-2.35 (1H, m), 3.95 (3H, s), 3.99 (3H, s), 5.73 (1H, d, J = 8.0 Hz) , 7.22 (1H, s), 7.45 (1H, s).

[0199] [ka]

[0200] (Synthesis of 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropyl octyl sulfide) Dry acetonitrile (10 mL), potassium carbonate (73.0 mg, 0.53 mmol), and 1-octanethiol (0.10 mL, 0.58 mmol) were placed in a 50 mL two-necked flask and stirred at room temperature under a nitrogen atmosphere for 2 hours. 1-(4,5-dimethoxy-2-nitrophenyl)-2-methylpropyl bromide (0.11 g, 0.35 mmol) was added and the mixture was refluxed under a nitrogen atmosphere for 4 hours. After concentration, the mixture was extracted with chloroform (30 mL x 3), purified water (100 mL), and 2N hydrochloric acid (2 mL). The organic layer was washed with saturated brine (100 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated. The residue was purified by silica gel column chromatography (hexane:ethyl acetate = 8:1) to yield 12.5 mg (0.03 mmol, 9%) of a yellow powder.

[0201] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 0.87 (3H, t, J = 6.7 Hz), 0.89 (3H, d, J = 6.6 Hz), 1.11 (3H, d, J = 6.7 Hz), 1.14-1.36 (10H, m), 1.39-1.50 (2H, m), 1.94-2.07 (1H, m), 2.16-2.26 (1H, m), 2.29-2.40 (1H, m), 3.94 (3H, s), 3.98 (3H, s), 4.60 (1H, d, J = 8.1 Hz), 7.32 (1H, s), 7.38 (1H, s).

[0202] [ka]

[0203] Example 9 (Synthesis of 1-(3,4-dimethoxyphenyl)-2,2-dimethyl-1-propanone) 1,2-Dimethoxybenzene (27.7 mL, 217 mmol) and pivalic anhydride (44.0 mL, 217 mmol) were placed in a 200 mL recovery flask, and iodine (3.30 g, 13.0 mmol) was added. The mixture was stirred at room temperature for 20 hours. After washing with saturated aqueous sodium thiosulfate (100 mL), the mixture was extracted with ethyl acetate (100 mL x 3) and purified water (150 mL). The organic layer was washed with saturated brine (150 mL x 2), dried over anhydrous magnesium sulfate, filtered, and concentrated to yield 31.5 g (142 mmol, 65%) of a brown viscous liquid.

[0204] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 1.39 (9H, s), 3.92 (3H, s), 3.94 (3H, s), 6.85 (1H, d, J = 8.6 Hz), 7.42 (1H, d, J = 2.0 Hz), 7.55 (1H, dd, J = 8.6, 2.0 Hz).

[0205] [ka]

[0206] (Synthesis of 1-(4,5-dimethoxy-2-nitrophenyl)-2,2-dimethyl-1-propanone) 1-(3,4-dimethoxyphenyl)-2,2-dimethyl-1-propanone (16.3 g, 73.3 mmol) was placed in a 200 mL recovery flask and dissolved in acetic acid (25 mL). Fuming nitric acid (45 mL, 1067 mmol) was slowly added dropwise in an ice bath, and the mixture was stirred at 0°C for 2 hours. The reaction solution was poured into cold water (1500 mL), suction filtered, and washed successively with pure water and hexane. The mixture was recrystallized (ethanol) by slow cooling to obtain 5.64 g (21.1 mmol, 29%) of yellow crystals.

[0207] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 1.26 (9H, s), 3.98 (3H, s), 3.99 (3H, s), 6.59 (1H, s), 7.70 (1H, s).

[0208] [ka]

[0209] (Synthesis of 1-(4,5-dimethoxy-2-nitrophenyl)-2,2-dimethylpropanol) 1-(4,5-dimethoxy-2-nitrophenyl)-2,2-dimethyl-1-propanone (5.64 g, 21.1 mmol) was placed in a 300 mL recovery flask and dissolved in tetrahydrofuran (140 mL) and methanol (84 mL). Sodium borohydride (2.00 g, 52.8 mmol) was added in small portions on an ice bath, and the mixture was stirred at 0°C for 30 minutes and then at room temperature for a further 2 hours. After concentration, ethyl acetate (100 mL × 4), purified water (150 mL), and 2N hydrochloric acid (35 mL) were added for extraction, and the organic layer was washed with saturated brine (150 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 5.58 g (20.7 mmol, 98%) of a yellow solid.

[0210] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 0.90 (9H, s), 2.05 (1H, d, J = 3.6 Hz), 3.94 (3H, s), 3.97 (3H, s), 5.63 (1H, d, J =3.3 Hz), 7.24 (1H, s), 7.45 (1H, s).

[0211] [ka]

[0212] (Synthesis of 1-(4,5-dimethoxy-2-nitrophenyl)-2,2-dimethylpropyl(2,5-dioxo-1-pyrrolidinyl)carbonate) 1-(4,5-dimethoxy-2-nitrophenyl)-2,2-dimethylpropanol (1.00 g, 3.72 mmol) was placed in a 100 mL two-necked recovery flask and dissolved in dry acetonitrile (15 mL). Di(N-succinimidyl)carbonate (1.44 g, 5.63 mmol) and triethylamine (1.56 mL, 11.5 mmol) were added, and the mixture was stirred at room temperature under a nitrogen atmosphere for 18 hours. After concentration, the mixture was extracted with chloroform (80 mL x 4), purified water (100 mL), and 2N hydrochloric acid (10 mL). The organic layer was washed with saturated brine (200 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated. The residue was purified by silica gel column chromatography (hexane:ethyl acetate = 1:1) to obtain 0.65 g (1.59 mmol, 43%) of a yellow powder.

[0213] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 1.02 (9H, s), 2.79 (4H, s), 3.95 (3H, s), 4.04 (3H, s), 6.71 (1H, s), 6.98 (1H, s), 7.60 (1H, s).

[0214] [ka]

[0215] (Synthesis of S-octyl O-(1-(4,5-dimethoxy-2-nitrophenyl)-2,2-dimethylpropyl)carbonate) 1-(4,5-dimethoxy-2-nitrophenyl)-2,2-dimethylpropyl(2,5-dioxo-1-pyrrolidinyl)carbonate (0.31 g, 0.73 mmol) was placed in a 20 mL two-necked recovery flask and dissolved in dry tetrahydrofuran (10 mL). 4-Dimethylaminopyridine (DMAP) (0.37 mg, 2.92 mmol) and 1-octanethiol (0.51 mL, 2.92 mmol) were added, and the mixture was stirred at room temperature under a nitrogen atmosphere for 20 hours. After concentration, the mixture was extracted with chloroform (10 mL x 3), purified water (30 mL), and 2N hydrochloric acid (6 mL). The organic layer was washed with saturated brine (50 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated. The residue was purified by silica gel column chromatography (hexane:ethyl acetate = 8:1) to obtain 0.18 g (0.41 mmol, 56%) of a yellow solid.

[0216] The measurement results of 1H-NMR (JEOL Ltd., 400 MHz) and the reaction formula are shown below. 1 H-NMR (CDCl3 / TMS, 400 MHz): δ 0.87 (3H, t, J = 6.8 Hz), 0.97 (9H, s), 1.17-1.39 (10H, m), 1.52-1.63 (2H, m), 2.73-2.88 (2H, m), 3.94 (3H, s), 3.95 (3H, s), 6.77 (1H, s), 6.92 (1H, s), 7.57 (1H, s).

[0217] [ka]

[0218] Each of the compounds produced in Examples 3 to 9 was dissolved in acetonitrile to prepare a 0.1 mM solution. The solution was irradiated with an ultra-high pressure mercury lamp at a wavelength of 365 nm and an illuminance of 25 mW / cm through a 365 nm bandpass filter and a water filter. 2 The sample was irradiated with light for 0, 5, 10, 15, 20, 25 and 30 seconds, and then subjected to HPLC measurement.

[0219] The peak area of ​​the raw material obtained by HPLC measurement (S0: area before light irradiation, S t : area after t seconds of light irradiation) into the following equation, and calculate the photolysis rate constant k(s -1 The results are shown in Table 1.

[0220]

number

[0221] [Table 1]

[0222] It was confirmed that the compounds produced in Examples 3 to 9 all had photodecomposition rate constants exceeding 0, indicating that they were photodecomposed. All of the compounds produced in Examples 3 to 9 generate thiols when irradiated with light, and therefore, it is possible to selectively pattern thiols at any desired position, as in Example 2.

[0223] It was confirmed that the photolysis rate of the compounds of Examples 3 to 9 was improved when a substituent R was introduced into the benzyl position compared to the unsubstituted (R=H) compound. When compared at the same R, sulfides photodecomposed faster than thiocarbonates. It was found that sulfides with a methyl group (Me) at the benzyl position were the fastest. [Explanation of symbols]

[0224] 11: substrate, 10a: photosensitive surface treatment agent, 10: photosensitive surface treatment agent layer, 13: photomask, 14: thiol-generating portion, 12: thiol-ungenerated 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 (1) or a polymer compound derived from the following formula (1): 【Chemical 1】 [In formula (1), R １ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ２ and R ３ are each independently an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 13 carbon atoms, and R ４ represents a hydrogen atom or a nitro group, n1 represents 0 or 1, and Y represents a polymerizable group-containing group or a linear or branched alkyl group having 1 to 20 carbon atoms.

2. The photosensitive surface treatment agent according to claim 1 , wherein Y is represented by the following formula (Y1): 【Chemistry 2】 [In formula (Y1), Ya ０１ represents an alkylene group having 1 to 10 carbon atoms, ０２ represents a group in which two hydrogen atoms have been removed from an aromatic ring having 6 to 15 carbon atoms, Ra ０１ represents a polymerizable group or a linear or branched alkyl group having 1 to 20 carbon atoms, and n2 and n3 each independently represent 0 or 1. * represents the bonding site with the sulfur element.]

3. The photosensitive surface treatment agent according to claim 1 or 2, wherein Y is represented by the following formula (Y2): 【Chemistry 3】 [In formula (Y2), Ya ０１ represents an alkylene group having 1 to 10 carbon atoms, Ra ０１ represents a polymerizable group or a linear or branched alkyl group having 1 to 20 carbon atoms, and * represents the bonding site with the sulfur element.

4. The photosensitive surface treatment agent according to any one of claims 1 to 3, wherein Y is represented by the following formula (Y3): 【Chemistry 4】 [In formula (Y3), Ya ０１ indicates an alkylene group having 1 to 10 carbon atoms, and * indicates the bonding site with the sulfur element.

5. The photosensitive surface treatment agent according to any one of claims 1 to 4, wherein Y is represented by the following formula (Y3-2): 【Chemistry 5】 [In formula (Y3-2), Ya ０１ indicates an alkylene group having 1 to 10 carbon atoms, and * indicates the bonding site with the sulfur element.

6. The photosensitive surface treatment agent according to any one of claims 1 to 5, wherein Y is represented by the following formula (Y4): 【Chemistry 6】 [In formula (Y4), Ya ０１ represents an alkylene group having 1 to 10 carbon atoms which may have an ether bond, Ya ０２ represents a group in which two hydrogen atoms have been removed from an aromatic ring having 6 to 15 carbon atoms, Ra ０１ represents a polymerizable group or a linear or branched alkyl group having 1 to 20 carbon atoms, and * represents the bonding site with the sulfur element.

7. The photosensitive surface treatment agent according to any one of claims 1 to 6, wherein Y is represented by the following formula (Y5): 【Chemistry 7】 [In formula (Y5), Ya ０１ represents an alkylene group having 1 to 10 carbon atoms which may have an ether bond, Ya ０２ indicates a group in which two hydrogen atoms have been removed from an aromatic ring having 6 to 15 carbon atoms, and * indicates the bonding site with the sulfur element.

8. The photosensitive surface treatment agent according to any one of claims 1 to 7, wherein Y is represented by the following formula (Y5-2): 【Chemistry 8】 [In formula (Y5-2), Ya ０１ represents an alkylene group having 1 to 10 carbon atoms which may have an ether bond, and * represents the bonding site with the sulfur element.

9. The photosensitive surface treatment agent according to any one of claims 1 to 8, wherein the polymer compound derived from the compound represented by formula (1) is a polymer compound represented by the following formula (1)-1: 【Chemistry 9】 [In formula (1)-1, R １ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ２ and R ３ are each independently an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 13 carbon atoms, and R ４ is a hydrogen atom or a nitro group, and Ya ０１ represents an alkylene group having 1 to 10 carbon atoms, ０２ represents a group in which two hydrogen atoms have been removed from an aromatic ring having 6 to 15 carbon atoms, n1, n2, and n3 each independently represent 0 or 1, and m represents a natural number.

10. 10. The photosensitive surface treatment agent according to claim 9, wherein the polymer compound derived from the compound represented by formula (1) has a substituent represented by the following formula (1x) bonded to at least one terminal of the main chain: 【Chemistry 10】 [* indicates the bonding site with the terminal of the main chain of the polymer compound derived from the compound represented by formula (1)]

11. 11. The photosensitive surface treatment agent according to claim 1, wherein the polymer compound derived from formula (1) has a number average molecular weight of 300 to 100,000.

12. The photosensitive surface treatment agent according to any one of claims 1 to 11, which comprises cyclopentanone.

13. A laminate comprising the photosensitive surface treatment agent according to any one of claims 1 to 12.

14. A transistor comprising the photosensitive surface treatment agent according to any one of claims 1 to 12.

15. A step of applying the photosensitive surface treatment agent according to any one of claims 1 to 12 onto a substrate to form a photosensitive resin film; irradiating the photosensitive resin film with light of a predetermined pattern; and performing electroless plating on at least a portion of the region irradiated with the predetermined pattern light.

16. A step of applying the photosensitive surface treatment agent according to any one of claims 1 to 12 onto a substrate to form a photosensitive resin film; irradiating the photosensitive resin film with light of a predetermined pattern; and a step of placing an electroless plating catalyst in at least a portion of the region irradiated with the predetermined patterned light and performing electroless plating.

17. A step of applying the photosensitive surface treatment agent according to any one of claims 1 to 12 onto a substrate to form a photosensitive resin film; a step of irradiating the photosensitive resin film with light of a predetermined pattern to form a thiol generation region in an exposed region; and a step of placing an electroless plating catalyst in the thiol-generating region and performing electroless plating.

18. A method for manufacturing a transistor, comprising the step of forming at least one electrode selected from a source electrode, a drain electrode, and a gate electrode by the pattern formation method according to any one of claims 15 to 17.

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