Compound, photosensitive surface treatment agent, method for producing laminate, and method for producing transistor

Abstract

A compound represented by formula (1). [In formula (1), R represents an alkyl group having 1-5 carbon atoms, X represents a halogen element or an alkoxy group, n1 represents an integer of 0-5, and n2 represents an integer of 1 or more]

Description

Technical Field

[0001] This invention relates to a compound, a photosensitive surface treatment agent, a method for manufacturing a laminate, and a method for manufacturing a transistor. Background Technology

[0002] In recent years, in the fabrication of micro-devices such as semiconductor components, integrated circuits, and devices for organic electroluminescence (EL) displays, a method has been proposed to fabricate micro-devices by stacking metal materials, insulating layers, and semiconductor layers on a substrate.

[0003] In this method, the resulting microdevice has a structure in which a metal material and a semiconductor layer are stacked on a substrate with an insulating layer in between. From the viewpoint of obtaining excellent electrical characteristics and high reliability, it is particularly required that the substrate and the insulating layer be tightly bonded without peeling off for the resulting microdevice.

[0004] As a technique for achieving close contact between a substrate and the material laminated on the substrate, methods for modifying the surface of the substrate are known. Methods for modifying the substrate surface include pretreatment such as ultraviolet (UV) ozone cleaning or plasma treatment, and methods for applying modifiers such as silane coupling agents or hexamethyldisilazane.

[0005] For example, Patent Document 1 discloses oxygen plasma treatment, UV ozone treatment, UV irradiation, etc. as methods for surface modification.

[0006] [Existing technical documents]

[0007] [Patent Literature]

[0008] Patent Document 1: Japanese Patent Application Publication No. 2016-111360 Summary of the Invention

[0009] The first aspect of the present invention is a compound represented by the following formula (1).

[0010] [Chemistry 1]

[0011] [In formula (1), R is an alkyl group with 1 to 5 carbon atoms, X is a halogen element or alkoxy group, n1 is an integer from 0 to 5, and n2 is an integer greater than or equal to 1.]

[0012] The second aspect of the present invention is a photosensitive surface treatment agent comprising the compound represented by formula (1).

[0013] The third aspect of the present invention is a method for manufacturing a laminate, comprising: a step of forming a photosensitive primer layer comprising the photosensitive surface treatment agent of the second aspect on a substrate; a step of forming metal wiring on the photosensitive primer layer; and a step of forming an organic insulating layer on the photosensitive primer layer and the metal wiring.

[0014] The fourth aspect of the present invention is a method for manufacturing a transistor, comprising: a step of forming one or more electrodes selected from a source electrode, a drain electrode, or a gate electrode by means of the method for manufacturing a laminate of the third aspect.

[0015] The purpose of this invention is to provide a compound that can improve the adhesion between a substrate and an insulating layer stacked on the substrate, a photosensitive surface treatment agent, a method for manufacturing a laminate, and a method for manufacturing a transistor. Attached Figure Description

[0016] Figure 1 This is a diagram showing the general process of manufacturing the laminated body according to this embodiment.

[0017] Figure 2 This is a diagram illustrating an example of the general steps in the manufacturing process of a transistor.

[0018] Figure 3 This is a schematic cross-sectional view used to illustrate the bonding state of the laminated bodies in this embodiment. Detailed Implementation

[0019] <Compound>

[0020] One aspect of the present invention is a compound represented by the following formula (1).

[0021] [Chemistry 2]

[0022] [In formula (1), R is an alkyl group with 1 to 5 carbon atoms, X is a halogen atom or an alkoxy group, n1 is an integer from 0 to 5, and n2 is an integer greater than or equal to 1.]

[0023] The compound represented by formula (1) has a cinnamic acid ester group (cinnamic acid group) as a photodimerization reaction group. The carbon-carbon double bond in the cinnamic acid ester group can be crosslinked with the carbon-carbon double bond of another cinnamic acid ester group by light irradiation to form a four-membered ring.

[0024] The compound represented by formula (1) has absorption in i-rays (wavelength 365 nm) by having cinnamic acid ester groups. Therefore, the compound represented by formula (1) is a material that can efficiently form a cross-linked structure after photoreaction in i-rays.

[0025] When the compound represented by formula (1) is used as a material for the photosensitive primer described later, when manufacturing laminates or transistors, the adhesion between the substrate and the insulating layer can be improved.

[0026] (R)

[0027] In formula (1), R is an alkyl group having 1 to 5 carbon atoms, and R can be methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, wherein methyl or ethyl is preferred, and methyl is more preferred.

[0028] (n1)

[0029] In formula (1), n1 is an integer from 0 to 5, preferably from 0 to 3, more preferably from 0 to 2, and even more preferably from 0 or 1.

[0030] (X)

[0031] In formula (1), the halogen atom represented by X can be listed as: fluorine atom, chlorine atom, bromine atom or iodine atom, etc.

[0032] X is preferably an alkoxy group. Examples of alkoxy groups for X include -O-(CH3) and -O-(CH2)n(CH3).

[0033] (n2)

[0034] In equation (1), n2 is an integer greater than or equal to 1, preferably a natural number between 1 and 3.

[0035] The following describes compound (1)-A as a specific example of the compound represented by formula (1).

[0036] [Chemistry 3]

[0037] Method for manufacturing the compound represented by formula (1)

[0038] The compound represented by formula (1) can be produced by reacting the compound represented by formula (1)-1 below with the compound represented by formula (1)-2 below.

[0039] The explanations of R, n1, X, and n2 in equations (1)-1 and (1)-2 below are the same as those of R, n1, X, and n2 in equation (1) above.

[0040] [Chemistry 4]

[0041] <Photosensitive Surface Treatment Agent>

[0042] In one embodiment of the invention, the photosensitive surface treatment agent comprises the compound represented by formula (1).

[0043] In one embodiment of the invention, the photosensitive surface treatment agent may also contain a solvent in addition to the compound represented by formula (1).

[0044] Solvents that may be included as photosensitive surface treatment agents include, for example, cyclopentanone, cycloheptanone, N-methyl-2-pyrrolidone (NMP) or cyclohexanone, among which cyclopentanone is preferred.

[0045] <Method for manufacturing laminates>

[0046] The method for manufacturing the laminate of this embodiment includes: a step of forming a photosensitive base coating containing the photosensitive surface treatment agent of this embodiment on a substrate; a step of forming metal wiring on the photosensitive base coating; and a step of forming an organic insulating layer on the photosensitive base coating and the metal wiring.

[0047] The following describes each process with reference to the diagram.

[0048] [Process of forming a photosensitive primer coating on a substrate]

[0049] like Figure 1 As shown in (a0), a photosensitive base coating 1 containing a photosensitive surface treatment agent is formed on the substrate 11. Methods for applying the photosensitive surface treatment agent include, for example, spin coating, dip coating, mold coating, spray coating, roll coating, and brush coating. Alternatively, coating can be performed using printing methods such as flexographic printing and screen printing.

[0050] In addition, in this process, a process may be applied to dry the solvent contained in the photosensitive surface treatment agent, for example, by means of heat or reduced pressure.

[0051] [The process of forming metal wiring on a photosensitive primer coating]

[0052] There are no particular limitations on the methods for forming metallic wiring on a photosensitive base coating; examples include vapor deposition, high-frequency sputtering, and electron beam sputtering. Alternatively, inks made by dissolving conductive nanoparticles in water or organic solvents can be used, employing methods such as spin coating, drop coating, dip coating, doctor blade coating, die coating, pad printing, roll coating, gravure printing, flexographic printing, screen printing, inkjet printing, and letterpress reverse printing.

[0053] From the viewpoint of forming finer metal wiring, it is preferable to use a photosensitive wiring forming material and form the metal wiring through an electroless plating process.

[0054] Photosensitive wiring forming materials are, for example, materials in which chemically active substituents can be formed in a portion of a substrate. Chemically active substituents are hydrophilic substituents capable of capturing and reducing the hydrophilic catalyst used in electroless plating of metallic materials. Examples include amino, hydroxyl, and thiol groups. Hereinafter, such chemically active substituents will sometimes be referred to as "active groups."

[0055] The following is an example of forming metallic wiring using photosensitive wiring forming materials through electroless plating.

[0056] like Figure 1 As shown in (a), a photosensitive wiring forming material 10a is coated on a photosensitive base coating 1.

[0057] The coating method for the photosensitive wiring forming material 10a can be, for example, spin coating, dip coating, mold coating, spray coating, roll coating, brush coating, etc. Alternatively, coating can be performed by printing methods such as flexographic printing and screen printing.

[0058] In addition, in this process, such as Figure 1 As shown in (a), the solvent may also be dried by means of heat or reduced pressure.

[0059] Therefore, as Figure 1 As shown in (b), a photosensitive wiring forming layer 10 is formed on the photosensitive base layer 1. Alternatively, a base film may be formed between the photosensitive base layer 1 and the photosensitive wiring forming material 10a. The base film can be formed, for example, by applying a coating solution prepared by dissolving a material in an organic solvent to form a four-membered ring with the carbon-carbon double bond of the cinnamic acid ester group of the compound represented by formula (A1) described later, and then crosslinking the coating solution.

[0060] Next, as Figure 1 As shown in (c), a photomask 13 with a prescribed pattern of exposure area is prepared. The exposure method is not limited to using a photomask; methods such as projection exposure using an optical system such as a lens or mirror, or maskless exposure using a spatial light modulation element, a laser beam, etc., can be employed. Furthermore, the photomask 13 may be configured to contact the photosensitive wiring forming layer 10, or it may be configured not to contact the photosensitive wiring forming layer 10.

[0061] Subsequently, as Figure 1 As shown in (c), UV light is irradiated onto the photosensitive wiring forming layer 10 through the photomask 13. Thus, the photosensitive wiring forming layer 10 is exposed in the exposure area of ​​the photomask 13.

[0062] The result, such as Figure 1 As shown in (d), an active group generating section 14 is formed in the exposed section, and an active group non-generated section 12 is formed in the unexposed section.

[0063] UV light, for example, includes i-rays with a wavelength of 365 nm. Furthermore, the exposure amount or duration may not necessarily require complete deprotection; it can be sufficient to generate some active groups.

[0064] Next, as Figure 1 As shown in (e), an electroless plating catalyst is applied to the surface to form a catalyst layer 15. The electroless plating catalyst is a catalyst for reducing metal ions contained in the electroless plating solution, such as silver or palladium.

[0065] The active group generation section is capable of capturing and reducing the electroless plating catalyst. Therefore, the electroless plating catalyst is captured only on the active group generation section to form a catalyst layer 15.

[0066] like Figure 1 As shown in (f), an electroless plating process is performed to form a plating layer 16. In addition, nickel-phosphorus (NiP) or copper (Cu) can be used as materials for plating layer 16.

[0067] In one example of this process, the substrate 11 is immersed in an electroless plating bath, and metal ions are reduced on the catalyst surface to precipitate the plating layer 16. At this time, a catalyst layer 15 carrying a sufficient amount of catalyst is formed on the surface of the active group generation section 14, so the plating layer 16 can be selectively precipitated only on the active group generation section.

[0068] This allows metal wiring to be formed on a photosensitive base coating.

[0069] [Process for forming the organic insulating layer]

[0070] An organic insulating layer is formed on the photosensitive primer and the metal wiring.

[0071] From the viewpoint of improving the adhesion between the substrate and the organic insulating layer, it is preferable to remove the portion 12 where no active group is generated after the metal wiring is formed and before the organic insulating layer is formed.

[0072] A photosensitive organic insulating material is coated onto a photosensitive base layer, causing the photosensitive base layer and the photosensitive organic insulating material to cross-link and form an organic insulating layer.

[0073] Specifically, such as Figure 1 As shown in (g), the insulating layer 17 is formed by a known method in such a way that it covers the plating layer 16 of the electroless plating pattern formed by the process and the active base non-generated portion 12 (the portion of the active base non-generated portion 12 if the active base non-generated portion 12 is removed).

[0074] Insulating layer 17 is formed, for example, by coating a material prepared by dissolving a material that can form a four-membered ring with the carbon-carbon double bond of the cinnamic acid ester group of the compound represented by formula (A1) in an organic solvent, and then coating the coating solution. Details of this photosensitive organic insulating material are described later.

[0075] exist Figure 3 The diagram shows a cross-sectional view illustrating the bonding state of a laminate formed by forming a photosensitive base coating 1 on a substrate 11 and subsequently forming an insulating layer 17 thereon. The carbon-carbon double bonds of the cinnamic acid ester group in the photosensitive base coating 1 and the carbon-carbon double bonds of the cinnamic acid ester group in the photosensitive organic insulating material form a four-membered ring. This improves the adhesion between the substrate 11 and the insulating layer 17.

[0076] By irradiating the coating with ultraviolet light through a mask with openings corresponding to the area where the insulating layer 17 is formed, the insulating layer 17 can be formed into a desired pattern.

[0077] Through the above processes, a laminate consisting of a photosensitive base coating, a metal material, and an insulating layer can be formed on the substrate.

[0078] <Methods for Manufacturing Transistors>

[0079] Furthermore, using Figure 2 A method for manufacturing a transistor in which the plating layer 16 obtained by the above-described <method for forming a laminate> is described.

[0080] like Figure 2 As shown in (g1), a photosensitive wiring forming layer 10 is formed on the insulating layer 17 in the same manner as the manufacturing method of the laminate, and an active base generating portion 14 is formed in the portion where the active electrode and the drain electrode are formed.

[0081] like Figure 2 As shown in (g2), an electroless plating catalyst is supported on the active base generation section 14 in the same manner as the manufacturing method of the laminate, and after forming the catalyst layer 15, electroless plating is performed to form the plating layer 18 (source electrode) and the plating layer 19 (drain electrode). In addition, nickel-phosphorus (NiP) or copper (Cu) can be used as materials for plating layer 18 and plating layer 19, but they can also be formed from materials different from those used for plating layer 16 (gate electrode). Gold (Au) can also be deposited by performing different metals, such as electroless gold plating, on the surface of nickel-phosphorus (NiP) or copper (Cu).

[0082] like Figure 2 As shown in (g3), a semiconductor layer 21 is formed between the plating layer 18 (source electrode) and the plating layer 19 (drain electrode).

[0083] Semiconductor layer 21 can also be formed, for example, by preparing a solution of an organic semiconductor material soluble in an organic solvent such as TIPS (6,13-bis(triisopropylsilylethynyl)pentacene), dissolving the organic solvent in the organic solvent, coating it between plating layer 18 (source electrode) and plating layer 19 (drain electrode), and then drying it.

[0084] Alternatively, the semiconductor layer 21 can also be formed by adding one or more insulating polymers such as polystyrene (PS) or polymethyl methacrylate (PMMA) to the solution, coating the solution containing the insulating polymer, and drying it.

[0085] When the semiconductor layer 21 is formed in this manner, an insulating polymer is concentrated 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 performance to degrade. However, by employing a structure in which the organic semiconductor is disposed with the insulating polymer in between, the degradation of transistor performance can be suppressed. A transistor can be manufactured in the manner described above.

[0086] According to the method described above, the UV exposure process does not require the addition of chemical resists, making it a simple process utilizing only a photomask. Therefore, the process of removing the resist layer is also unnecessary. Furthermore, the reduction capability of the thiol-based catalyst eliminates the need for the normally required catalyst activation process, resulting in significant cost reduction, time shortening, and the ability to achieve highly precise patterning. Additionally, the dip coating method can be used, making it highly suitable for roll-to-roll processes.

[0087] Furthermore, there are no particular restrictions on the structure of the transistor, and it can be selected appropriately according to the purpose. For example, top-contact-bottom-gate, top-contact-top-gate, and bottom-contact-top-gate transistors can also be manufactured in the same way.

[0088] Photosensitive Organic Insulating Materials

[0089] The photosensitive organic insulating material used in this embodiment may be either photosensitive organic insulating material 1 or photosensitive organic insulating material 2.

[0090] [Photosensitive organic insulating material 1]

[0091] Photosensitive organic insulating material 1 contains chalcone compounds and polyvinylcinnamate (PVCi).

[0092] (Chalcones)

[0093] Chalcone compounds are chalcones (unsubstituted), substituted chalcones, and other chalcone derivatives. Examples of substituted chalcones include chalcones having one or more substituents selected from the group consisting of alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, and polyoxyalkoxy groups. The number of substituents is preferably 1 to 3, more preferably 1. The substitution position is preferably on the benzene ring on the olefin side of the unsaturated carbonyl group, more preferably via ortho or para substitution. From the viewpoint of facilitating photodimerization and increasing i-ray absorption, chalcones with an alkoxy group having 1 to 5 carbon atoms at the para position of the benzene ring on the olefin side of the unsaturated carbonyl group are preferred, more preferably alkoxy groups having 1 to 3 carbon atoms.

[0094] Specific examples of chalcone compounds include chalcone, methoxychalcone, etc. More preferably, chalcone or 4-methoxychalcone. Even more preferably, 2-methoxychalcone or 4-methoxychalcone (hereafter sometimes simply referred to as methoxychalcone).

[0095] Chalcone compounds of this embodiment can be used alone or in combination of two or more.

[0096] (Polyvinyl cinnamate (PVCi))

[0097] Polyvinyl cinnamate is also known as poly(vinyl cinnamate). For example, it is available from Sigma-Aldrich Japan Ltd.

[0098] (solvent)

[0099] The photosensitive organic insulating material 1 may also include a solvent. Examples of solvents include: alcohol-based solvents, ester-based solvents, hydrocarbon-based aromatic solvents, amide-based solvents, ketone-based solvents, glycol ether-based solvents, and ether-based solvents. From the viewpoint of solubility and film-forming properties, ester-based and ketone-based solvents are preferred, particularly propylene glycol 1-monomethyl ether 2-acetate (PGMEA) and cyclopentanone.

[0100] (Other ingredients)

[0101] To improve weather resistance and lightfastness, known antioxidants, light stabilizers, and UV absorbers may be added. To improve adhesion, known adhesion promoters may be added. To improve leveling, surface wettability, or hydrophobicity, known surface modifiers may be added.

[0102] (Composition ratio)

[0103] The photosensitive organic insulating material 1 may contain the chalcone compounds and polyvinyl cinnamate in the following mass ratio: Total mass of chalcone compounds: The ratio of the total mass of chalcone compounds to the mass of polyvinyl cinnamate is 0.01 to 1, preferably 0.01 to 0.3, more preferably 0.03 to 0.3, and even more preferably 0.05 to 0.1.

[0104] In the photosensitive organic insulating material 1, the total amount of chalcone compounds and polyvinyl cinnamate is preferably 10% to 30% by mass, more preferably 10% to 15% by mass, relative to 100% by mass of the total composition.

[0105] In the photosensitive organic insulating material 1, the total amount of chalcone compounds is preferably 0.1% to 15% by mass, more preferably 0.1% to 3% by mass, relative to 100% by mass of the total composition.

[0106] (I-ray sensitivity of photosensitive organic insulating material 1)

[0107] The photosensitive organic insulating material 1 contains chalcone compounds in addition to polyvinyl cinnamate, thus exhibiting greater absorption in i-rays compared to the case containing only polyvinyl cinnamate. Consequently, the photocuring time required is shorter when using an i-ray exposure machine with the same light intensity, leading to a significant improvement in productivity.

[0108] The absorption intensity of the photosensitive organic insulating material 1 in i-rays can be adjusted by the type and content of the chalcone compound. For example, when the chalcone compound is an unsubstituted chalcone, an intensity of 10 to 50 is preferred. Furthermore, when the chalcone compound is a methoxychalcone, an intensity of 5 to 25 is preferred.

[0109] [Photosensitive organic insulating material 2]

[0110] Photosensitive organic insulating material 2 contains a polymer with a chalcone backbone.

[0111] (Polymers with a chalcone backbone)

[0112] The chalcone backbone of the polymer described in this embodiment refers to the structure derived from various chalcone compounds contained in the photosensitive organic insulating material 1. The chalcone compounds in this embodiment have the same meaning as those in the photosensitive organic insulating material 1, and their preferred examples are also the same. The chalcone backbone of the polymer described in this embodiment is preferably a structure contained in the side chains linked to the main chain of the polymer.

[0113] The main chain of the polymer in this embodiment is preferably a vinyl polymer chain generated by the polymerization reaction of monomers having ethylene unsaturated bonds.

[0114] The polymer with a chalcone backbone in this embodiment is preferably a vinyl polymer backbone and a side chain containing a chalcone backbone.

[0115] The polymer with a chalcone backbone in this embodiment may contain side chains that do not contain a chalcone backbone, in addition to a vinyl polymer backbone and side chains containing a chalcone backbone. Preferably, the polymer with a chalcone backbone in this embodiment contains no other side chains besides a vinyl polymer backbone and side chains containing a chalcone backbone.

[0116] Specific examples of polymers having a chalcone skeleton in this embodiment include polymers represented by the following formulas (A1) to (A3).

[0117] [Chemistry 5]

[0118] [Chemistry 6]

[0119] [Chemistry 7]

[0120] The weight-average molecular weight of the polymer with the chalcone backbone in this embodiment is preferably 5,000 to 100,000, more preferably 10,000 to 80,000, and even more preferably 20,000 to 50,000.

[0121] The weight-average molecular weight can be determined using gel permeation chromatography (GPC).

[0122] In the polymer having a chalcone skeleton in this embodiment, the content of the chalcone skeleton (a structure derived from chalcone compounds, such as the structure obtained by removing the -OH group of compound 3 in the process described below) is preferably 70% to 97% by mass, more preferably 50% to 80% by mass, relative to 100% by mass of the polymer.

[0123] (Method for manufacturing polymers with a chalcone backbone)

[0124] The method for manufacturing the polymer having a chalcone skeleton according to this embodiment will be described in detail below using the polymer of formula (2) as an example.

[0125] The method for manufacturing the polymer in this embodiment includes: a step of synthesizing an ethylene unsaturated compound having a chalcone backbone, and a polymerization step of polymerizing the ethylene unsaturated compound to form a vinyl polymer backbone.

[0126] The ethylene-unsaturated compound having a chalcone skeleton can be produced by a known method of reacting a compound having hydroxyl groups and a chalcone skeleton with an acyl chloride having ethylene-unsaturated groups in a solvent. For example, compound 3 is synthesized by the method described in Non-Patent Document 1, as shown in the following process 1. A method for synthesizing compound 5 is illustrated by reacting compound 3, a obtained phenol derivative (or, 4'-hydroxy-4-methoxychalcone produced using Biosynth), with compound 4.

[0127] [Chemistry 8]

[0128] (Non-patent literature 1: X. Yang et al., Synthesis of a series of novel dihydroartemisinin derivatives containing a substituted chalcone with greater cytotoxic effects in leukemia cells, Bioorganic & Medicinal Chemistry Letters, Vol. 19, No. 15, (2009), pp. 4385-4388.)

[0129] In the polymerization process of polymerizing unsaturated ethylene compounds, for example, when the unsaturated ethylene compounds are subjected to free radical copolymerization, the free radical copolymerization can be carried out using known methods such as solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization.

[0130] There are no limitations on the solvents used in solution polymerization as long as they are capable of dissolving the monomers and the polymers of the present invention. Examples of solvents include toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, dimethylformamide, and dimethyl sulfoxide. These solvents can also be used in combination.

[0131] The polymerization temperature depends on the initiator used, but there are no particular limitations. Initiators are not particularly limited; examples include azo initiators such as azoisobutyronitrile, and peroxide initiators such as benzoyl peroxide and di(tert-butyl peroxide). As a specific example, 2,2'-azobis(isobutyronitrile) (AIBN) can be cited. The reaction time is not limited and is set according to the half-life of the initiator used, but from an economic point of view, 4 to 30 hours is preferred.

[0132] For example, as shown in process 2 below, the obtained compound 5 is polymerized to synthesize compound 6.

[0133] The conditions for the synthesis reaction are described in detail in the examples. Additionally, the evaluation results for compound 6 are also described in the examples.

[0134] [Chemistry 9]

[0135] In the polymerization step, the ethylene unsaturated monomers used as raw materials for the polymerization reaction may include, in addition to ethylene unsaturated compounds with a chalcone skeleton such as compound 5 from step 2, ethylene unsaturated compounds without a chalcone skeleton. When ethylene unsaturated compounds without a chalcone skeleton are included, the side chains of the obtained polymer include both side chains with and without a chalcone skeleton. In this case, the total mass of ethylene unsaturated compounds without a chalcone skeleton is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, and even more preferably 0 parts by mass, relative to 100 parts by mass of the total mass of the ethylene unsaturated compounds with a chalcone skeleton.

[0136] (solvent)

[0137] The photosensitive organic insulating material 2 may also include a solvent. Examples of solvents include alcohol-based, ester-based, and ketone-based solvents. Among these, propylene glycol 1-monomethyl ether 2-acetate (PGMEA) and cyclopentanone are preferred. Alternatively, the solvent used in the polymerization reaction may be used directly as part of the solvent of the composition.

[0138] (Other ingredients)

[0139] To improve weather resistance and lightfastness, known antioxidants, light stabilizers, and UV absorbers may be added. To improve adhesion, known adhesion promoters may be added. To improve leveling, surface wettability, or hydrophobicity, known surface modifiers may be added.

[0140] (Composition ratio)

[0141] Of the 100% by mass of the component (solid component) obtained by removing the solvent from the photosensitive organic insulating material 2, preferably 50% to 100% by mass of the polymer having a chalcone backbone, more preferably 75% to 100% by mass, and even more preferably 100% by mass. Chalcone compounds and polyvinyl cinnamate may be included in the following mass ratios.

[0142] In the photosensitive organic insulating material 2, the total amount of the polymer having the chalcone backbone is preferably 10% to 30% by mass, more preferably 10% to 15% by mass, relative to 100% by mass of the total composition.

[0143] (I-ray sensitivity of the composition)

[0144] The photosensitive organic insulating material 2 contains a polymer with a chalcone backbone, thus exhibiting greater absorption in I-rays compared to existing technologies that only contain polyvinyl cinnamate. As a result, the time required for photocuring is shortened when using an I-ray exposure machine with the same light intensity. Productivity can be significantly improved.

[0145] The absorption intensity of the photosensitive organic insulating material 2 in i-rays can be adjusted by the type of chalcone compound relative to the chalcone backbone and the content of the chalcone backbone in the polymer. For example, when the chalcone compound is methoxychalcone, i.e., when it is a polymer having a methoxychalcone backbone, 50 to 90 parts by mass are preferred. When the i-ray absorption is high, the deep curing property decreases, resulting in photocuring of thick films or a decrease in end-drawing properties. In order to obtain excellent photocuring property with the desired film thickness, the content can be adjusted arbitrarily.

[0146] Photosensitive organic insulating material 1 and photosensitive organic insulating material 2 include photocrosslinking groups with photodimerization reactivity, wherein radiation is preferably used in the photocrosslinking. Examples of radiation include ultraviolet light with wavelengths of 245 nm to 450 nm and visible light. From the viewpoint of maximizing the effects of the invention, radiation near i-rays is preferred, and more preferably an i-ray monochromatic light source. The radiation dose is appropriately varied depending on the composition of the polymer, for example, 100 mJ / cm². 2 ~300 mJ / cm 2To prevent a decrease in crosslinking degree and to improve economic efficiency due to shorter process time, a value of 50 mJ / cm is preferred. 2 ~200 mJ / cm 2 There are no special restrictions on the environment when irradiating with ultraviolet or visible light; it can be carried out in the atmosphere, in an inert gas, or under a certain amount of inert gas flow.

[0147] Furthermore, both the photosensitive organic insulating material 1 and the photosensitive organic insulating material 2 can efficiently perform photocrosslinking within a short time. To achieve efficient photocrosslinking even in a shorter time, it is preferable, for example, to set the light irradiation time to within 2 minutes when using i-rays. Moreover, for better control of the crosslinking time, it is even more preferable, for example, to set the light irradiation time to within 1 minute when using i-rays.

[0148] [Example]

[0149] The present invention will be described in more detail below through embodiments, but the present invention is not limited to the following embodiments.

[0150] <Synthesis of the compound represented by formula (1)>

[0151] The (E)-4-(3-(4-methoxyphenyl)acryloyl)phenyl(3-(trimethoxysilyl)propyl)carbamate (MC-SC) represented by the following formula (1) was synthesized by the method described below.

[0152] From now on, “(E)-4-(3-(4-methoxyphenyl)acryloyl)phenyl(3-(trimethoxysilyl)propyl)carbamate (MC-SC)” will be recorded as compound 1.

[0153] [Chemistry 10]

[0154] In a 300 mL flask under inert (argon) conditions, 10.3 g (40.6 mmol, 1.00 eq.) of (2E)-1-(4-hydroxyphenyl)-3-(4-methoxyphenyl)-2-propen-1-one and 200 mL of anhydrous tetrahydrofuran (THF) were added and dissolved. Then, 0.24 mL (0.406 mmol, 0.01 eq.) of dibutyltin dilaurate was added, followed by the slow dropwise addition of 10.0 g (48.7 mmol, 1.20 eq.) of (3-isocyanate propyl)trimethoxysilane over 20 minutes. The mixture was then heated to 70 °C and gradually increased to an internal temperature of 66 °C over 1 hour.

[0155] Twelve hours later, to confirm the presence of unreacted reactants by nuclear magnetic resonance (NMR), (3-isocyanate propyl)trimethoxysilane (0.3 eq. = 2.50 g) and dibutyltin dilaurate (0.24 mL, 0.406 mmol, 0.01 eq.) were added, followed by reheating. After 22 hours, the reaction solution was concentrated under reduced pressure (40 °C / 20 mmHg) to obtain the crude product.

[0156] The crude product was purified by silica gel column chromatography (eluent: chloroform / methanol = 20 / 1). The fraction of the target compound was concentrated and redissolved in chloroform (18 mL), then added dropwise to n-heptane (400 mL) using a Pasteur pipette. After stirring for 30 minutes, the precipitated solid was filtered off, washed three times with n-heptane (100 mL), and dried under reduced pressure for 12 hours (40℃ / <1 mmHg) to obtain 9.45 g (50.8%) of the target MC-SC.

[0157] The following shows 1 Results of H-NMR (400 MHz) and electrospray ionization mass spectrometry (ESI-MS).

[0158] 1 H-NMR(400 MHz, CDCl3): δ0.71(2H,t),1.73(2H,tt),3.29(2H,m),3.60(9H,s),3.86(3H,s),5.38 (1H,t),6.94(2H,d),7.26(2H,d),7.39(1H,d),7.60(1H,d),7.78(1H,d),8.03(2H,d)

[0159] ESI-MS: C 23 H 29 NO7Si+H + (M+H) + The calculated value m / z = 460, and the measured value m / z = 460.

[0160] <Synthesis of 4'-hydroxy-4-methoxychalcone>

[0161] The following method was used to synthesize a compound equivalent to compound 3 in process 1, namely 4'-hydroxy-4-methoxychalcone, which has a hydroxyl and methoxychalcone skeleton.

[0162] In an argon atmosphere, 390 g of 4-hydroxyacetophenone (manufactured by Fujifilm and Kojin Chemical Co., Ltd.), 390 g of p-anisaldehyde (manufactured by Fujifilm and Kojin Chemical Co., Ltd.), and 5.5 L of methanol (manufactured by Fujifilm and Kojin Chemical Co., Ltd.) were mixed in a 20 L four-necked flask. Then, 2.7 L of a 50% NaOH aqueous solution was added dropwise over 60 minutes while maintaining an internal temperature below 15°C in an ice bath. Afterward, the ice bath was removed, and the mixture was stirred at room temperature for 95 hours. 5.4 L of distilled water was placed in a 90 L container, and the reaction mixture was then added. Subsequently, approximately 35 L of a 1 N HCl aqueous solution was added in small increments. Ice was added to maintain an internal temperature of approximately 25°C, as the internal temperature was to be kept above 30°C. The pH was adjusted to approximately 4, and the precipitated solid was separated by suction filtration. The solid was washed with a 2 / 1, 3 L mixture of methanol and distilled water. The obtained solid was then dried under reduced pressure at 50°C for 24 hours, yielding 544.6 g of a pale yellow solid. Recrystallization with ethanol yielded 520.8 g of the target compound, 4'-hydroxy-4-methoxychalcone (yield 71%).

[0163] The following shows 4'-hydroxy-4-methoxychalcone 1 Results of H-NMR measurements.

[0164] 1 H- NMR(CDCl3)3.86(3H,s),5.52(1H,s),6.93(4H,m),7.41(1H,m),7.60(2H,m),7.81(1H,m),8.01(2H,m)

[0165] Synthesis of (E)-4-(3-(4-methoxyphenyl)acryloyl)phenyl methacrylate

[0166] The following method was used to synthesize an ethylene-unsaturated compound, namely (E)-4-(3-(4-methoxyphenyl)acryloyl)phenyl methacrylate, which is equivalent to compound 5 in process 1 and has a methoxychalcone skeleton.

[0167] In a 2 L four-necked flask, 30.0 g of 4'-hydroxy-4-methoxychalcone and dry THF were added and dissolved under argon atmosphere. Triethylamine (15.5 g, manufactured by Fujifilm and Hikari Pure Chemical Industries, Ltd.) was added, and the mixture was cooled with ice water. Methacrylamide (14.8 g, manufactured by Fujifilm and Hikari Pure Chemical Industries, Ltd.) was added dropwise, and the mixture was stirred overnight. Water (600 mL) was added to the reactor, and the mixture was transferred to a separatory funnel for extraction with 1.2 L of ethyl acetate (manufactured by Fujifilm and Hikari Pure Chemical Industries, Ltd.). The ethyl acetate layer was then washed twice with 600 mL of 5% sodium bicarbonate solution, three times with water (600 mL), and dried with anhydrous sodium sulfate. After removing the desiccant, the mixture was concentrated under reduced pressure (40 °C / 20 mmHg) to obtain a pale yellow solid. Ethanol (600 mL) was added to the obtained crude solid, and the mixture was suspended and stirred for 30 minutes. The mixture was then filtered to obtain a white solid. The synthesis of (E)-4-(3-(4-methoxyphenyl)acryloyl)phenyl methacrylate as the target compound was obtained by drying under reduced pressure (40 °C / <1 mmHg).

[0168] The following shows (E)-4-(3-(4-methoxyphenyl)acryloyl)phenyl methacrylate. 1 Results of H-NMR measurements.

[0169] 1 H-NMR(CDCl3)2.09(3H,s),3.87(3H,s),5.81(1H,m),6.39(1H,m),6.93(2H,d),7.26(2H,d),7.38(1H,m),7.63(2H,d),7.78(1H,m),8.08(2H,d)

[0170] <Synthesis of Poly(4-Methoxychalcone)>

[0171] The polymer, poly(4-methoxychalcone), which is equivalent to compound 6 of process 2 and has a methoxychalcone backbone, is synthesized by the following method. Poly(4-methoxychalcone) will be referred to as "PMC" below.

[0172] PMC is synthesized by polymerizing the (E)-4-(3-(4-methoxyphenyl)acryloyl)phenyl methacrylate obtained in the process described in step 2.

[0173] In a 3 L four-necked flask, (E)-4-(3-(4-methoxyphenyl)acryloyl)phenyl methacrylate and degassed dimethylformamide (DMF) were added under argon atmosphere and stirred. AIBN (manufactured by Fujifilm and Hikari Pure Chemical Industries, Ltd., 3.82 g) was added, and the mixture was heated to 60 °C and stirred for 21 hours. After cooling, the mixture was added dropwise to methanol (30 L). After stirring for 60 minutes, the mixture was filtered under reduced pressure, washed three times with methanol (2 L), and the resulting solid was dried under reduced pressure (50 °C / <1 mmHg) to obtain 135 g of the target PMC.

[0174] The following shows PMC's 1 Results of H-NMR measurements.

[0175] 1 H-NMR(CDCl3)1.57(3H,br),1.94(1H,br),3.75(3H,br),6.83(2H,br),7.31(6H,m,br),7.96(2H,br)

[0176] For the obtained PMC, the weight-average molecular weight, chalcone skeleton content, and solids composition were evaluated, and the results are shown below. The evaluation method is as described.

[0177] Weight average molecular weight: 44131

[0178] Chalcon skeleton content: 74 parts by weight

[0179] Polymethoxychalcone was obtained by the method described above. Polymethoxychalcone will henceforth be referred to as "PMC".

[0180] <Manufacturing of Photosensitive Surface Treatment Agents>

[0181] Compound 1 and PMC were mixed according to the mixing ratio shown in Table 1 below to obtain photosensitive surface treatment agent 1 to photosensitive surface treatment agent 3.

[0182] [Table 1]

[0183] [Evaluation of close contact]

[0184] Photosensitive surface treatment agent 1 to photosensitive surface treatment agent 3 are coated on each of the substrates listed in Table 2 below. The coating is formed by spin coating at 1000 rpm and heated at 150°C for 10 minutes, thereby forming an organic insulating layer.

[0185] On the formed insulating film, cuts are made in a grid pattern with a longitudinal and transverse interval of 2 mm, and a tape peel test is performed using tape (100 mask low scalar method: according to Japanese Industrial Standards (JIS) 5600).

[0186] The results are evaluated using the following classification from 0 to 5, with those classified below 0 being evaluated as "high close contact".

[0187] [Table 2]

[0188] In Table 2, PEN refers to polyethylene naphthalate.

[0189] [Table 3]

[0190] Explanation of icon numbers

[0191] 1: Photosensitive base coating

[0192] 10: Photosensitive wiring forming layer

[0193] 10a: Photosensitive wiring forming material

[0194] 11: Substrate

[0195] 12: Part where active groups are not generated

[0196] 13: Photomask

[0197] 14: Active group generation section

[0198] 15: Catalyst layer

[0199] 17: Insulating layer

[0200] 21: Semiconductor layer

Claims

1. A compound represented by the following formula (1), [Chemistry 1] [In formula (1), R is an alkyl group with 1 to 5 carbon atoms, X is a halogen element or alkoxy group, n1 is an integer from 0 to 5, and n2 is an integer greater than 1].

2. A photosensitive surface treatment agent comprising the compound according to claim 1.

3. A method for manufacturing a laminate, comprising: The process of forming a photosensitive undercoat containing the photosensitive surface treatment agent according to claim 2 on a substrate; The process of forming metal wiring on the photosensitive base coating; as well as The process of forming an organic insulating layer on the photosensitive base coating and the metal wiring.

4. A method for manufacturing a transistor, comprising: forming one or more electrodes selected from a source electrode, a drain electrode, or a gate electrode by means of the method for manufacturing a laminate according to claim 3.

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