Compound, photosensitive surface treatment agent, laminate production method, and transistor production method

Abstract

This compound is 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

Compound, photosensitive surface treatment agent, laminate manufacturing method, and transistor manufacturing method

[0001] The present invention relates to a compound, a photosensitive surface treatment agent, a method for producing a laminate, and a method for producing a transistor.

[0002] BACKGROUND ART In recent years, in the manufacture of microdevices such as semiconductor elements, integrated circuits, and devices for organic EL displays, a method has been proposed in which a microdevice is produced by stacking a metal material, an insulating layer, and a semiconductor layer on a substrate.

[0003] In such a 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 interposed therebetween. From the viewpoint of obtaining excellent electrical properties and high reliability, the resulting microdevice is particularly required to have the substrate and the insulating layer adhere to each other without peeling off.

[0004] Known techniques for adhering a substrate to a material to be laminated thereon include modifying the surface of the substrate, such as pretreatments including UV ozone cleaning and plasma treatment, and coating the surface with a modifier such as a silane coupling agent or hexamethyldisilazane.

[0005] For example, Patent Document 1 discloses methods of modifying the surface, such as oxygen plasma treatment, UV ozone treatment, and UV irradiation.

[0006] JP 2016-111360 A

[0007] A first aspect of the present invention is a compound represented by the following formula (1):

[0008] [In formula (1), R is an alkyl group having 1 to 5 carbon atoms, X is a halogen element or an alkoxy group, n1 is an integer of 0 to 5, and n2 is an integer of 1 or more.]

[0009] A second aspect of the present invention is a photosensitive surface treatment agent containing a compound represented by the formula (1).

[0010] A third aspect of the present invention is a method for producing a laminate, comprising the steps of: forming a photosensitive primer layer containing the photosensitive surface treatment agent of the second aspect on a substrate; forming metal wiring on the photosensitive primer layer; and forming an organic insulating layer on the photosensitive primer layer and the metal wiring.

[0011] A fourth aspect of the present invention is 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 method for manufacturing a stack according to the third aspect.

[0012] An object of the present invention is to provide a compound capable of improving adhesion between a substrate and an insulating layer laminated on the substrate, a photosensitive surface treatment agent, a method for producing a laminate, and a method for producing a transistor.

[0013] 1A and 1B are diagrams showing an outline of steps in a method for manufacturing a laminate according to an embodiment of the present invention; FIG. 1C are diagrams showing an example of steps in a method for manufacturing a transistor; and FIG. 1D are schematic cross-sectional views for explaining a bonding state of the laminate according to an embodiment of the present invention.

[0014] <Compound> One aspect of the present invention is a compound represented by the following formula (1).

[0015] [In formula (1), R is an alkyl group having 1 to 5 carbon atoms, X is a halogen atom or an alkoxy group, n1 is an integer of 0 to 5, and n2 is an integer of 1 or more.]

[0016] The compound represented by formula (1) has a cinnamate group (cinnamic acid group) as a photodimerization reactive group. Upon irradiation with light, the carbon-carbon double bond in this cinnamate group can form a four-membered ring with the carbon-carbon double bond of another cinnamate group, thereby crosslinking.

[0017] The compound represented by formula (1) has a cinnamate group and thus has absorption at i-line (wavelength 365 nm), and therefore is a material that can efficiently form a crosslinked structure after a photoreaction with i-line.

[0018] When a laminate or a transistor is produced using the compound represented by formula (1) as a material for a photosensitive primer described below, the adhesion between the substrate and the insulating layer can be improved.

[0019] (R) In formula (1), R is an alkyl group having 1 to 5 carbon atoms, and examples of R include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a tert-butyl group. Among these, a methyl group or an ethyl group is preferred, and a methyl group is more preferred.

[0020] (n1) In formula (1), n1 represents an integer of 0 to 5, preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1.

[0021] (X) In formula (1), examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0022] X is preferably an alkoxy group. The alkoxy group of X is —O—(CH ３ ), —O—(CH ２ )n(CH ３ ) are listed.

[0023] (n2) In formula (1), n2 is an integer of 1 or more, and is preferably a natural number of 1 to 3.

[0024] A specific example of the compound represented by formula (1), compound (1)-A, is shown below.

[0025]

[0026] <<Method for Producing a Compound Represented by Formula (1)>> The compound represented by formula (1) can be produced by reacting a compound represented by the following formula (1)-1 with a compound represented by the following formula (1)-2. The explanations for R, n1, X, and n2 in the following formulas (1)-1 and (1)-2 are the same as the explanations for R, n1, X, and n2 in the above formula (1).

[0027]

[0028] <Photosensitive Surface Treatment Agent> 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 may contain a solvent in addition to the compound represented by the above formula (1).

[0029] Examples of the solvent that may be contained in the photosensitive surface treatment agent include cyclopentanone, cycloheptanone, N-methyl-2-pyrrolidone (NMP), and cyclohexanone, with cyclopentanone being preferred.

[0030] <Method for manufacturing laminate> The method for manufacturing a laminate of this embodiment includes the steps of forming a photosensitive primer layer containing the photosensitive surface treatment agent of this embodiment on a substrate, forming metal wiring on the photosensitive primer layer, and forming an organic insulating layer on the photosensitive primer layer and the metal wiring. Each step will be described below with reference to the drawings.

[0031] 1(a0), a photosensitive primer layer 1 containing a photosensitive surface treatment agent is formed on a substrate 11. Examples of methods that can be used to apply the photosensitive surface treatment agent include spin coating, dip coating, die coating, spray coating, roll coating, and brush coating. Alternatively, the agent may be applied by a printing method such as flexographic printing or screen printing.

[0032] In this step, a treatment may be added in which the solvent contained in the photosensitive surface treatment agent is dried by, for example, heat or reduced pressure.

[0033] [Step of forming metal wiring on photosensitive primer layer] The method for forming metal wiring on the photosensitive primer layer is not particularly limited, and examples thereof include vapor deposition, high-frequency sputtering, electron beam sputtering, etc. In addition, methods such as solution spin coating, drop casting, dip coating, doctor blade coating, die coating, pad printing, roll coating, gravure printing, flexographic printing, screen printing, inkjet printing, and letterpress reverse printing can also be used using an ink in which nanoparticles of a conductive material are dissolved in water or an organic solvent.

[0034] From the viewpoint of forming finer metal wiring, it is preferable to use a photosensitive wiring-forming material and form metal wiring by electroless plating. The photosensitive wiring-forming material is, for example, a material capable of forming a region in which a chemically active substituent is generated in a part of a substrate. The chemically active substituent is a hydrophilic substituent capable of capturing and reducing an electroless plating catalyst as a metal material. Specific examples include an amino group, a hydroxyl group, and a thiol group. Hereinafter, such a chemically active substituent may be referred to as an "active group."

[0035] An example of forming metal wiring by electroless plating using a photosensitive wiring-forming material will be described below. As shown in Fig. 1(a), a photosensitive wiring-forming material 10a is applied onto a photosensitive primer layer 1. Examples of methods that can be used to apply the photosensitive wiring-forming material 10a include spin coating, dip coating, die coating, spray coating, roll coating, and brush coating. Alternatively, the material may be applied by a printing method such as flexographic printing or screen printing.

[0036] 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.

[0037] 1(b), a photosensitive wiring-forming layer 10 is formed on the photosensitive primer layer 1. An undercoat film may be formed between the photosensitive primer layer 1 and the photosensitive wiring-forming material 10a. The undercoat film can be formed, for example, by using a coating liquid prepared by dissolving in an organic solvent a material capable of forming a four-membered ring with the carbon-carbon double bond of the cinnamate group of the compound represented by formula (A1) described below and crosslinking the material, and applying the coating liquid.

[0038] 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 a lens or mirror, or maskless exposure using a spatial light modulation element or a laser beam. The photomask 13 may be provided so as to be in contact with the photosensitive wiring formation layer 10, or may be provided so as not to be in contact with the photosensitive wiring formation layer 10.

[0039] 1C, the photosensitive wiring formation layer 10 is irradiated with UV light through the photomask 13. As a result, the photosensitive wiring formation layer 10 is exposed in the exposure region of the photomask 13.

[0040] As a result, as shown in FIG. 1(d), active group generated parts 14 are formed in the exposed parts, and active group non-generated parts 12 are formed in the unexposed parts.

[0041] The UV light may be, for example, i-rays having a wavelength of 365 nm. The exposure dose and exposure time do not necessarily need to be such that complete deprotection proceeds, but may be such that some active groups are generated.

[0042] 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.

[0043] The active radical generating portion is capable of capturing and reducing the electroless plating catalyst described above, so that the electroless plating catalyst is captured only in the active radical generating portion, forming catalyst layer 15.

[0044] 1(f), electroless plating is performed to form a plating layer 16. The plating layer 16 may be made of nickel-phosphorus (NiP) or copper (Cu).

[0045] In one example of this process, the substrate 11 is immersed in an electroless plating bath to reduce metal ions on the catalyst surface, depositing a plating layer 16. At this time, because a catalyst layer 15 carrying a sufficient amount of catalyst is formed on the surface of the active group generating portion 14, the plating layer 16 can be selectively deposited only on the active group generating portion. This allows metal wiring to be formed on the photosensitive primer layer.

[0046] [Step of forming an organic insulating layer] An organic insulating layer is formed on the photosensitive primer layer and the metal wiring. From the viewpoint of improving adhesion between the substrate and the organic insulating layer, it is preferable to remove the active group non-generated portion 12 after forming the metal wiring and before forming the organic insulating layer.

[0047] A photosensitive organic insulating material is applied onto the photosensitive primer layer, and the photosensitive primer layer and the photosensitive organic insulating material are crosslinked to form an organic insulating layer. Specifically, as shown in Figure 1(g), an insulator layer 17 is formed by a known method so as to cover the plating layer 16 of the electroless plating pattern formed by the above-mentioned process and the active group non-generated portions 12 (or the portions that were the active group non-generated portions 12 if the active group non-generated portions 12 have been removed).

[0048] The insulator layer 17 is formed by, for example, using a coating liquid prepared by dissolving in an organic solvent a material capable of forming a four-membered ring with the carbon-carbon double bond of the cinnamate group of the compound represented by formula (A1) and crosslinking the four-membered ring with the carbon-carbon double bond of the cinnamate group of the compound represented by formula (A1). Details of such photosensitive organic insulating materials will be described later.

[0049] 3 shows a schematic cross-sectional view illustrating the bonding state of a laminate in which a photosensitive primer layer 1 is formed on a substrate 11 and an insulating layer 17 is further formed thereon. The carbon-carbon double bond of the cinnamate group of compound 1 contained in photosensitive primer layer 1 and the carbon-carbon double bond of the cinnamate group contained in the photosensitive organic insulating material form a four-membered ring. This improves the adhesion between substrate 11 and insulating layer 17.

[0050] By irradiating the coating with ultraviolet light through a mask having openings corresponding to the areas where the insulator layer 17 is to be formed, the insulator layer 17 can be formed into a desired pattern.

[0051] Through the above steps, a laminate in which a photosensitive primer layer, a metal material, and an insulating layer are laminated on a substrate can be formed.

[0052] <Method for Manufacturing Transistor> Furthermore, a method for manufacturing a transistor in which the plating layer 16 obtained in the above <Method for Manufacturing a Laminate> is used as a gate electrode will be described with reference to FIG.

[0053] As shown in FIG. 2(g1), a photosensitive wiring formation layer 10 is formed on an insulator layer 17 in the same manner as in the manufacturing method of the laminate described above, and an active radical generating section 14 is formed in the portion where the source electrode and the drain electrode are to be formed.

[0054] 2(g2), in the same manner as in the manufacturing method of the laminate described above, an electroless plating catalyst is supported on the active radical generating portion 14, a catalyst layer 15 is formed, 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.

[0055] As shown in FIG. 2(g3), a semiconductor layer 21 is formed between the plating layer 18 (source electrode) and the plating layer 19 (drain electrode).

[0056] The semiconductor layer 21 may be formed by dissolving an organic semiconductor material soluble in an organic solvent, such as TIPS pentacene (6,13-Bis(triisopropylsilylethylenyl)pentacene), in the organic solvent to prepare a solution, applying the solution between the plating layer 18 (source electrode) and the plating layer 19 (drain electrode), and drying the solution.

[0057] 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.

[0058] When the semiconductor layer 21 is formed in this manner, the insulating polymer is concentrated below the semiconductor layer 21 (on the insulator layer 17 side). If polar groups such as amino groups are present at the interface between the organic semiconductor and the insulator layer, the transistor characteristics tend to deteriorate. However, by providing the organic semiconductor via the insulating polymer, the deterioration of the transistor characteristics can be suppressed. A transistor can be manufactured in this manner.

[0059] According to the above-described method, there is no need to provide a separate chemical resist or the like in the UV exposure process, and the process can be simplified using only a photomask. Naturally, therefore, the process of removing the resist layer is also not required. Furthermore, due to the catalytic reduction ability of the thiol group, the catalyst activation process that is usually required can be omitted, enabling high-resolution patterning while achieving significant cost reductions and time savings. Furthermore, since a dip coating method can be used, it can be used very well in roll-to-roll processes.

[0060] 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.

[0061] <Photosensitive Organic Insulating Material> As the photosensitive organic insulating material used in this embodiment, the following photosensitive organic insulating material 1 or photosensitive organic insulating material 2 can be used.

[0062] [Photosensitive Organic Insulating Material 1] Photosensitive organic insulating material 1 contains a chalcone compound and polyvinyl cinnamate (PVCi).

[0063] (Chalcone Compounds) Chalcone compounds are chalcone derivatives such as (unsubstituted) chalcone and substituted chalcone. Substituted chalcones include, for example, 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, and more preferably 1. The substitution position is preferably on the benzene ring on the alkene side of the unsaturated carbonyl, and more preferably at the ortho or para position. From the viewpoint of facilitating the photodimerization reaction and increasing i-line absorption, chalcones substituted with one alkoxy group having 1 to 5 carbon atoms at the para position of the benzene ring on the alkene side of the unsaturated carbonyl are preferred, and an alkoxy group having 1 to 3 carbon atoms is more preferred. Specific examples of chalcone compounds include chalcone and methoxychalcone. Chalcone and 4-methoxychalcone are more preferred. 2-Methoxychalcone and 4-methoxychalcone (hereinafter sometimes simply referred to as methoxychalcone) are even more preferred. The chalcone compounds according to this embodiment may be used singly or in combination of two or more.

[0064] (Polyvinyl cinnamate (PVCi)) Polyvinyl cinnamate is also called poly(vinyl cinnamate) and is available from, for example, Sigma-Aldrich Japan LLC.

[0065] (Solvent) The photosensitive organic insulating material 1 may further contain a solvent. Examples of the solvent 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 viewpoints of solubility and film-forming properties, the solvent contained is preferably an ester-based or ketone-based solvent, and among these, propylene glycol 1-monomethyl ether 2-acetate (PGMEA) and cyclopentanone are preferred.

[0066] (Other Components) Known antioxidants, light stabilizers, and ultraviolet absorbers may be added to improve weather resistance and light resistance. Known adhesion promoters may be added to improve adhesion. Known surface modifiers may be added to improve leveling properties, surface wettability, or hydrophobicity.

[0067] (Composition Ratio) Photosensitive organic insulating material 1 may contain the chalcone compound 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. In photosensitive organic insulating material 1, the total amount of chalcone compounds and polyvinyl cinnamate is preferably 10% by mass to 30% by mass, and more preferably 10% by mass to 15% by mass, relative to 100% by mass of the total composition. In photosensitive organic insulating material 1, the total amount of chalcone compounds is preferably 0.1% by mass to 15% by mass, and more preferably 0.1% by mass to 3% by mass, relative to 100% by mass of the total composition.

[0068] (i-Line Sensitivity of Photosensitive Organic Insulating Material 1) Photosensitive organic insulating material 1 contains a chalcone compound in addition to polyvinyl cinnamate, and therefore exhibits greater i-line absorption than a material containing only polyvinyl cinnamate. As a result, when using an i-line exposure machine with the same light intensity, the time required for photocuring is shortened. This significantly improves productivity. The i-line absorption intensity of photosensitive organic insulating material 1 can be adjusted by the type of chalcone compound, the content of the chalcone compound, etc. For example, when the chalcone compound is unsubstituted chalcone, it is preferably 10 to 50. Furthermore, when the chalcone compound is methoxychalcone, it is preferably 5 to 25.

[0069] [Photosensitive Organic Insulating Material 2] Photosensitive organic insulating material 2 contains a polymer having a chalcone skeleton.

[0070] (Polymer Having a Chalcone Skeleton) The chalcone skeleton contained in the polymer according to this embodiment is a structure derived from the various chalcone compounds contained in the photosensitive organic insulating material 1. The chalcone compounds according to this embodiment have the same meaning as the chalcone compounds according to the photosensitive organic insulating material 1, and preferred examples thereof are also the same. The chalcone skeleton contained in the polymer according to this embodiment is preferably a structure contained in a side chain linked to the main chain of the polymer. The main chain of the polymer according to this embodiment is preferably a vinyl polymer chain produced by a polymerization reaction of a monomer having an ethylenically unsaturated bond. The polymer having a chalcone skeleton according to this embodiment preferably has a vinyl polymer main chain and a side chain containing a chalcone skeleton.

[0071] The polymer having a chalcone skeleton according to this embodiment includes a vinyl polymer main chain and a side chain containing a chalcone skeleton, and may also include a side chain that does not contain a chalcone skeleton. The polymer having a chalcone skeleton according to this embodiment preferably includes a vinyl polymer main chain and a side chain containing a chalcone skeleton, and does not include any other side chains.

[0072] Specific examples of the polymer having a chalcone skeleton according to this embodiment include polymers represented by the following formulas (A1) to (A3).

[0073]

[0074]

[0075]

[0076] The weight-average molecular weight of the polymer having a chalcone skeleton according to 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. Gel permeation chromatography (GPC) can be used to measure the weight-average molecular weight.

[0077] In the polymer having a chalcone skeleton according to this embodiment, the content of the chalcone skeleton (a structure derived from a chalcone compound, for example, the structure of Compound 3 in the following scheme excluding the —OH group) is preferably 70% by mass to 97% by mass, and more preferably 50% by mass to 80% by mass, relative to 100% by mass of the polymer.

[0078] (Method for Producing a Polymer Having a Chalcone Skeleton) The method for producing a polymer having a chalcone skeleton according to this embodiment will be described in detail below using the polymer of formula (2) as an example. The method for producing a polymer according to this embodiment includes a step of synthesizing an ethylenically unsaturated compound having a chalcone skeleton and a polymerization step of polymerizing the ethylenically unsaturated compound to form a vinyl polymer main chain.

[0079] The ethylenically unsaturated compound having a chalcone skeleton can be produced by a known method in which a compound having a hydroxy group and a chalcone skeleton is reacted with an acid chloride having an ethylenically unsaturated group in a solvent. For example, as shown in Scheme 1 below, compound 3 is synthesized by the method described in Non-Patent Document 1. Compound 5 is synthesized by reacting the resulting phenol derivative compound 3 (or 4'-hydroxy-4-methoxychalcone manufactured by Biosynth) with compound 4.

[0080]

[0081] (Non-Patent Document 1: X. Yang et. al. with greater cytotoxic effects in leukemia cells, Bioorganic & Medicinal Chemistry Letters, Volume 19, Issue 15, (2009), Pages 4385-4388.

[0082] In the polymerization step of polymerizing an ethylenically unsaturated compound, for example, when the ethylenically unsaturated compound is radically copolymerized, the radical copolymerization can be performed using known methods such as solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, etc. The solvent used in the solution polymerization is not particularly limited as long as it dissolves the above-mentioned monomers and the polymer of the present invention, and examples thereof include toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, dimethylformamide, dimethyl sulfoxide, etc., and these solvents can also be used in combination.

[0083] The polymerization temperature is selected depending on the initiator used, but is not particularly limited. The initiator is not particularly limited, and examples include azo-based initiators such as azoisobutyronitrile; and peroxide-based initiators such as benzoyl peroxide and di(t-butyl) peroxide. A specific example is 2,2'-azobis(isobutyronitrile) (AIBN). The reaction time is not particularly limited and is set according to the half-life of the initiator used, but is preferably 4 to 30 hours from an economical standpoint.

[0084] For example, as shown in Scheme 2 below, the compound 5 obtained above is polymerized to synthesize compound 6. The synthesis reaction conditions will be described in detail in the Examples. The evaluation results of compound 6 will also be described in the Examples.

[0085]

[0086] In the polymerization step, the ethylenically unsaturated monomers used as raw materials for the polymerization reaction may contain an ethylenically unsaturated compound not having a chalcone skeleton, in addition to an ethylenically unsaturated compound having a chalcone skeleton, such as Compound 5 in Scheme 2. When an ethylenically unsaturated compound not having a chalcone skeleton is contained, the side chains of the resulting polymer will contain side chains not having a chalcone skeleton in addition to side chains having a chalcone skeleton. In this case, the total mass of the ethylenically unsaturated compounds not having a chalcone skeleton is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, and even more preferably 0 part by mass, relative to 100 parts by mass of the total mass of the ethylenically unsaturated compounds having a chalcone skeleton.

[0087] (Solvent) The photosensitive organic insulating material 2 may further contain a solvent. Examples of the solvent include alcohol-based, ester-based, and ketone-based solvents. Among these, propylene glycol 1-monomethyl ether 2-acetate (PGMEA) and cyclopentanone are preferred. Furthermore, the solvent used in the polymerization reaction may be used as is as part of the solvent for the composition.

[0088] (Other Components) Known antioxidants, light stabilizers, and ultraviolet absorbers may be added to improve weather resistance and light resistance. Known adhesion promoters may be added to improve adhesion. Known surface modifiers may be added to improve leveling properties, surface wettability, or hydrophobicity.

[0089] (Composition ratio) The polymer having a chalcone skeleton is preferably 50% by mass to 100% by mass, more preferably 75% by mass to 100% by mass, based on 100% by mass of the components (solid content) excluding the solvent of the photosensitive organic insulating material 2. 100% by mass is even more preferable. The chalcone compound and polyvinyl cinnamate may be contained in the following mass ratios. In the photosensitive organic insulating material 2, the total amount of the polymer having a chalcone skeleton is preferably 10% by mass to 30% by mass, more preferably 10% by mass to 15% by mass, based on 100% by mass of the total amount of the composition.

[0090] (i-Line Sensitivity of the Composition) Because the photosensitive organic insulating material 2 contains a polymer having a chalcone skeleton, it exhibits greater i-line absorption than conventional materials containing only polyvinyl cinnamate. As a result, the time required for photocuring is shorter when using an i-line exposure machine with the same light intensity. This significantly improves productivity. The i-line absorption intensity of the photosensitive organic insulating material 2 can be adjusted by the type of chalcone compound relative to the chalcone skeleton, the content of the chalcone skeleton in the polymer, and other factors. For example, when the chalcone compound is methoxychalcone, i.e., when there is a polymer having a methoxychalcone skeleton, the content is preferably 50 to 90 parts by mass. High i-line absorption reduces deep curability, resulting in poor photocuring in thick films and poor edge patternability. The content can be adjusted as desired to achieve excellent photocurability at a desired film thickness.

[0091] Photosensitive organic insulating material 1 and photosensitive organic insulating material 2 have photocrosslinking groups that are photodimerization reactive, and radiation is preferably used for the photocrosslinking. Examples of radiation include ultraviolet and visible light with wavelengths of 245 to 450 nm. From the viewpoint of maximizing the effects of the present invention, radiation near i-line is preferred, and an i-line monochromatic light source is more preferred. The radiation dose can be appropriately changed depending on the composition of the polymer, but is, for example, 100 to 300 mJ / cm. ２ In order to prevent a decrease in the degree of crosslinking and improve economic efficiency by shortening the process time, the dose is preferably 50 to 200 mJ / cm ２ The environment for irradiating with ultraviolet light or visible light is not particularly limited, and irradiation can be carried out in the air, in an inert gas, or in a constant flow of inert gas.

[0092] Furthermore, the photosensitive organic insulating material 1 and the photosensitive organic insulating material 2 can be photocrosslinked efficiently in a short time. In order to achieve photocrosslinking efficiently in a shorter time, for example, when using i-rays, it is preferable to set the light irradiation time to 2 minutes or less. Note that, since this is suitable for controlling the crosslinking time, it is even more preferable to set the light irradiation time to 1 minute or less when using i-rays, for example.

[0093] 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.

[0094] <Synthesis of Compound Represented by Formula (1)> (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. Hereinafter, "(E)-4-(3-(4-methoxyphenyl)acryloyl)phenyl(3-(trimethoxysilyl)propyl)carbamate (MC-SC)" will be referred to as Compound 1.

[0095]

[0096] In a 300 mL flask, 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 THF (tetrahydrofuran) were added and dissolved under an inert atmosphere (argon atmosphere). 0.24 mL (0.406 mmol, 0.01 eq.) of dibutyltin dilaurate was added thereto, and then 10.0 g (48.7 mmol, 1.20 eq.) of (3-isocyanatopropyl)trimethoxysilane was slowly added dropwise over 20 minutes. The mixture was then heated to 70°C, and the internal temperature was increased to 66°C over 1 hour.

[0097] After 12 hours, the presence of unreacted raw materials was confirmed by NMR, so (3-isocyanatepropyl)trimethoxysilane (0.3 eq. = 2.50 g) and 0.24 mL (0.406 mmol, 0.01 eq.) of dibutyltin dilaurate were added and the mixture was heated again. After 22 hours, the reaction solution was concentrated under reduced pressure (40°C / 20 mmHg) to obtain a crude product.

[0098] The crude product was purified by silica gel column chromatography (eluent: chloroform / methanol = 20 / 1), and the target fraction was concentrated and then redissolved in chloroform (18 mL) and added dropwise to n-heptane (400 mL) using a Pasteur pipette. After stirring for 30 minutes, the precipitated solid was collected by filtration, washed three times with n-heptane (100 mL), and dried under reduced pressure (40 °C / < 1 mmHg) for 12 hours to obtain 9.45 g (50.8%) of the target MC-SC.

[0099] The results of 1H-NMR (400 MHz) and ESI-MS measurements are shown below. 1H-NMR (400 MHz, CDCl ３ ): 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) ESI-MS:C ２３ H ２９ NO ７ Si+H ＋ (M+H) +Calculated m / z = 460, measured m / z = 460

[0100] <Synthesis of 4'-hydroxy-4-methoxychalcone> 4'-hydroxy-4-methoxychalcone, a compound corresponding to Compound 3 in Scheme 1 above and having a hydroxy group and a methoxychalcone skeleton, was synthesized by the following method. Under an argon atmosphere, 4-hydroxyacetophenone (390 g, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), p-anisaldehyde (390 g, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and methanol (5.5 L, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed in a 20 L four-neck flask. Next, 50% aqueous NaOH solution (2.7 L) was added dropwise over 60 minutes while maintaining the internal temperature at 15°C or below in an ice bath. The ice bath was then 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 solution was poured into it. Next, 1 N aqueous HCl solution (approximately 35 L) was poured in portions. When the internal temperature was about to exceed 30°C, ice was added to maintain the temperature at approximately 25°C. The pH was adjusted to about 4, and the precipitated solid was separated by suction filtration, washed with a mixed solution of methanol and distilled water (2 / 1, 3 L), and the resulting solid was dried under reduced pressure at 50°C for 24 hours to obtain 544.6 g of a pale yellow solid. Recrystallization was carried out using ethanol to obtain 520.8 g of the target pale yellow solid, 4'-hydroxy-4-methoxychalcone (yield 71%).

[0101] The 1H-NMR measurement results for 4'-hydroxy-4-methoxychalcone are shown below: 1H-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)

[0102] Synthesis of (E)-4-(3-(4-methoxyphenyl)acryloyl)phenyl methacrylate (E)-4-(3-(4-methoxyphenyl)acryloyl)phenyl methacrylate, an ethylenically unsaturated compound having a methoxychalcone skeleton, corresponding to Compound 5 in Scheme 1 above, was synthesized by the following method. 4'-Hydroxy-4-methoxychalcone (30.0 g) and dry THF were added to a 2 L four-neck flask under an argon atmosphere and dissolved. Triethylamine (FUJIFILM Wako Pure Chemical Industries, Ltd., 15.5 g) was added thereto, and the mixture was cooled with ice water. After that, methacryloyl chloride (FUJIFILM Wako Pure Chemical Industries, Ltd., 14.8 g) was added dropwise, followed by stirring overnight. Water (600 mL) was poured into a reactor, transferred to a separatory funnel, and extracted with ethyl acetate (FUJIFILM Wako Pure Chemical Industries, Ltd., 1.2 L). Next, the ethyl acetate layer was washed twice with 5% aqueous sodium bicarbonate (600 mL) and three times with water (600 mL), and then dried over 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 product, and the mixture was suspended and stirred for 30 minutes, then filtered to obtain a white solid. This was dried under reduced pressure (40°C / <1 mmHg) to obtain 30.1 g (79.2%) of the target product, (E)-4-(3-(4-methoxyphenyl)acryloyl)phenyl methacrylate.

[0103] The results of 1H-NMR measurement of (E)-4-(3-(4-methoxyphenyl)acryloyl)phenyl methacrylate are shown below. 1H-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)

[0104] <Synthesis of Poly(4-Methoxychalcone)> Poly(4-Methoxychalcone), a compound represented by the above formula (2), corresponding to compound 6 in Scheme 2 above, and a polymer having a methoxychalcone skeleton, was synthesized by the following method. Poly(4-Methoxychalcone) will be referred to as "PMC" hereinafter. PMC was synthesized by polymerizing the E)-4-(3-(4-methoxyphenyl)acryloyl)phenyl methacrylate obtained above, as shown in Scheme 2 above. To a 3-L four-neck flask, under an argon atmosphere, were added (E)-4-(3-(4-methoxyphenyl)acryloyl)phenyl methacrylate and degassed DMF, and the mixture was stirred. AIBN (3.82 g, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was then added, and the mixture was heated to 60°C and heated with stirring for 21 hours. After cooling, the mixture was added dropwise to methanol (30 L), stirred for 60 minutes, 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.

[0105] The results of 1H-NMR measurement of PMC are shown below. 1H-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). The weight-average molecular weight, chalcone skeleton content, solid content, etc. of the obtained PMC were evaluated, and the results are shown below. The evaluation method is as described above. Weight-average molecular weight: 44,131 Chalcone skeleton content: 74 parts by mass Polymethoxychalcone was obtained by the above method. Hereinafter, polymethoxychalcone will be referred to as "PMC."

[0106] <Production of Photosensitive Surface Treatment Agent> Compound 1 and PMC were mixed in the blending ratio shown in Table 1 below to obtain photosensitive surface treatment agents 1 to 3.

[0107]

[0108] [Evaluation of Adhesion] Photosensitive surface treatment agents 1 to 3 were applied to each of the substrates listed in Table 2 below, and the substrates were formed using a spin coater at a rotation speed of 1,000 rpm and heated at 150°C for 10 minutes to form organic insulating layers. The formed insulating film was scored in a grid pattern at intervals of 2 mm vertically and horizontally, and a tape peel test (100-mask loss-cut method: in accordance with JIS 5600) was performed using tape. The results were evaluated using the following classifications of 0 to 5, with classification 0 or lower being evaluated as having "high adhesion."

[0109]

[0110] In Table 2, PEN means polyethylene naphthalate.

[0111]

[0112] 1: Photosensitive primer layer, 10: Photosensitive wiring-forming layer, 10a: Photosensitive wiring-forming material, 11: Substrate, 12: Active group non-generated portion, 13: Photomask, 14: Active group generated portion, 15: Catalyst layer, 17: Insulator layer, 21: Semiconductor layer

Claims

1. A compound represented by the following formula (1): [In formula (1), R is an alkyl group having 1 to 5 carbon atoms, X is a halogen element or an alkoxy group, n1 is an integer of 0 to 5, and n2 is an integer of 1 or more.] 2. A photosensitive surface treatment agent comprising the compound according to claim 1.

3. A method for manufacturing a laminate, comprising the steps of: forming a photosensitive primer layer containing the photosensitive surface treatment agent according to claim 2 on a substrate; forming metal wiring on the photosensitive primer layer; and forming an organic insulating layer on the photosensitive primer layer and the metal wiring.

4. A method for manufacturing a transistor, comprising the step of forming at least one of a source electrode, a drain electrode, and a gate electrode by the method for manufacturing a laminate according to claim 3.

Images