Polymer, cross-linked product thereof, and electronic device including the same

Abstract

To provide a polymer having solubility in solvents, printability at room temperature, photo-crosslinkability, superior adhesion to polyester, metal, and organic insulating films, and chemical resistance to acidic and alkaline resist cleaning fluids.SOLUTION: The present invention provides a polymer having some of the hydroxyl groups in polyvinyl alcohol substituted with cinnamoyl groups. The benzene rings of the cinnamoyl groups may be each independently substituted with hydrogen, fluorine, a cyano group, a nitro group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 fluoroalkyl group, or a C1-C6 cycloalkyl group.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polymer having solubility in a solvent, printability at room temperature, photocrosslinkability, excellent adhesiveness to polyester, metal, and organic insulating films, and further chemical resistance to acidic and alkaline resist cleaning liquids.

Background Art

[0002] Printed electronics refers to a technology for forming electronic devices and the like on a substrate by printing. In this technology, significant cost reduction can be achieved by enabling continuous printing in the same way as printing on paper. Therefore, a roll-to-roll method, which is a method of continuously pulling out and printing a flexible substrate wound in a roll shape and then winding it up, is suitable.

[0003] At this time, as the substrate to be used, in addition to thin-film glass capable of corresponding to the roll-to-roll method, the use of inexpensive polyethylene terephthalate (PET) is assumed in the future. There are several types of forms of electronic devices. When forming an electronic device on a substrate, for example, a process of sequentially forming an underlayer, a gate electrode, an organic insulating film layer, source / drain electrodes, a bank, an organic semiconductor film layer, and a protective layer on PET is performed. The above electrodes are formed by printing using gold ink, silver ink, or the like. The underlayer printed and formed on the substrate has a role of adhering the PET and the insulating film, and adhesiveness to the gate electrode is also required. Further, when forming the insulating film layer by a printing method, an organic solvent is used. Therefore, before forming the insulating layer, it is necessary to cure the underlayer to impart solvent resistance. At this time, in the continuous printing method, it is substantially impossible to heat, and a long curing time cannot be ensured. Therefore, a material for the underlayer that cures by short-time light irradiation is required.

[0004] When the substrate is glass, there is no restriction on the heating temperature, so polyvinylphenol (PVP) cross-linked bodies or polyparaphenylene have mainly been used as the underlayer. PVP requires thermal cross-linking, with the cross-linking temperature exceeding 100°C and the cross-linking time also being about 1 hour, so a continuous printing process cannot be applied. Also, since polyparaphenylene is also formed into a film by high-temperature vacuum evaporation, it cannot be continuously formed into a film and has the problem that it cannot be applied to the printing method. Furthermore, at the high temperature during the cross-linking temperature of PVP or the chemical vapor deposition polymerization of polyparaphenylene, when a plastic film is used as the substrate, the film has a fatal drawback of shrinking or deforming. That is, when using PVP or polyparaphenylene for the underlayer formed on the substrate, there is a fatal drawback that a continuous printing process cannot be applied.

[0005] Also, in the process of forming an electronic device on a substrate, there is a patterning step for forming an electrode circuit using a resist material. In this step, acid and alkali cleaning are performed for resist removal and etching after patterning, and depending on the element form, the underlayer comes into contact with these acidic and alkaline liquids.

[0006] Against such a background, there is a demand for a material that can be dissolved in a solvent, can be printed at room temperature, adheres to polyester, metal, and organic insulating films, and further has resistance to acidic and alkaline cleaning liquids.

[0007] Polymers obtained by partially esterifying polyvinyl alcohol for the purpose of paper surface treatment agents, medical materials, etc. and then cross-linking with a bifunctional isocyanate compound (Non-Patent Document 1), polymers cross-linked with dicarboxylic acids (Non-Patent Document 2), and polymers cross-linked with bifunctional acid anhydrides (Non-Patent Document 3) have been disclosed. Also, techniques for obtaining polyvinyl acetal by reacting polyvinyl alcohol with an aldehyde compound (Non-Patent Documents 4 and 5) have been disclosed, but none of these have photocrosslinkability.

[0008] A photocrosslinkable polymer obtained by reacting polyvinyl alcohol with cinnamoyl chloride and then reacting with an acid anhydride is disclosed (Patent Document 1), but these documents make no mention of the reaction with isocyanate and adhesiveness.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Non-Patent Documents

[0010]

Non-Patent Document 1

Non-Patent Document 2

Non-Patent Document 3

Non-Patent Document 4

Non-Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0011] The present invention has been made in view of the above problems, and an object thereof is to provide a polymer having solubility in a solvent, printability at room temperature, photocrosslinkability, excellent adhesiveness to a plastic substrate, metal, and organic insulating film, and further chemical resistance to acidic and alkaline resist cleaning liquids.

Effects of the Invention

[0012] According to the present invention, it is possible to provide a polymer having solubility in a solvent, printability at room temperature, photocrosslinkability, excellent adhesiveness to a plastic substrate, metal, and organic insulating film, and further chemical resistance to acidic and alkaline resist cleaning liquids, and an electronic device using the polymer.

Brief Description of the Drawings

[0013]

Figure 1

Figure 2

Figure 3

Embodiments for Carrying Out the Invention

[0014] The present invention relates to a polymer containing repeating units of formula (1) and formula (3), an adhesive layer using the polymer, and an electronic device including the adhesive layer.

[0015]

Chemical formula

[0016] (In formula (1), R1 represents hydrogen or a methyl group, and R3, R4, and R5 each independently represent hydrogen, fluorine, a cyano group, a nitro group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 fluoroalkyl group, or a C1-C6 cycloalkyl group.)

[0017]

Chemical formula

[0018] The present invention will be described in detail below.

[0019] The present invention relates to a polymer characterized by containing repeating units of formula (1) and formula (3).

[0020]

Chem.

[0021] (In formula (1), R1 represents hydrogen or a methyl group, and R3, R4, and R5 each independently represent hydrogen, fluorine, a cyano group, a nitro group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 fluoroalkyl group, or a C1-C6 cycloalkyl group.)

[0022]

Chem.

[0023] In formula (1), R1 represents hydrogen or a methyl group, preferably hydrogen.

[0024] In formula (1), R3, R4, and R5 each independently represent hydrogen, fluorine, a cyano group, a nitro group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 fluoroalkyl group, or a C1-C6 cycloalkyl group.

[0025] The C1-C6 alkyl group for R3, R4, and R5 in formula (1) is not particularly limited, and examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, etc.

[0026] The C1-C6 alkoxy group for R3, R4, and R5 in formula (1) is not particularly limited, and examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, etc.

[0027] The C1-C6 fluoroalkyl group for R3, R4, and R5 in formula (1) is not particularly limited, and examples include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, etc.

[0028] In formula (1), the C1-C6 cycloalkyl groups in R3, R4 and R5 are not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclohexyl group and the like.

[0029] Among these, R3, R4 and R5 are preferably hydrogen.

[0030] Specific repeating units of formula (1) can include the following units.

[0031]

Chemical formula

[0032] The molecular weight of the repeating unit of formula (3) (also referred to as polyvinyl alcohol) used in the present invention is not limited at all, and is preferably 10,000 to 200,000. Further, it is preferable to use polyvinyl alcohol having a saponification degree of 90 mol% or more.

[0033] Specific polymers containing the repeating units of formula (1) and (3) can include the following polymers.

[0034]

Chemical formula

[0035] In the present invention, the molecular weight of the polymer containing the repeating units of formula (1) and formula (3) is not limited at all, and examples thereof include 5,000 to 500,000 (g / mol). From the viewpoints of the solution viscosity and mechanical strength of the polymer, it is preferably 10,000 to 200,000 (g / mol).

[0036] Since the polymer of the present invention is excellent in acid resistance, it preferably further contains the repeating unit of formula (2).

[0037]

Chemical formula

[0038] (In formula (2), R6 represents a phenyl group, a C7-C10 alkylphenyl group, a C7-C10 alkoxyphenyl group, a naphthyl group, a C7-C10 fluorophenyl group, a C7-C10 fluoroalkylphenyl group, a biphenyl group, an acetyl group, an adamantyl group, a C3-C6 alkyl group, or a C3-C6 cycloalkyl group.) Examples of the C7-C10 alkylphenyl group in R6 in formula (2) include a 4-methylphenyl group, a 3-methylphenyl group, a 4-ethylphenyl group, a 3-ethylphenyl group, a 4-n-propylphenyl group, a 3-n-propylphenyl group, a 4-isopropylphenyl group, a 3-isopropylphenyl group, a 4-n-butylphenyl group, a 3-n-butylphenyl group, a 4-sec-butylphenyl group, a 3-sec-butylphenyl group, a 4-isobutylphenyl group, a 3-isobutylphenyl group, and the like.

[0039] Examples of the C3-C6 alkyl group in R6 in formula (2) include an isopropyl group, an n-propyl group, an n-butyl group, a sec-butyl group, an n-pentyl group, an n-hexyl group, and the like. Examples of the C3-C6 cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.

[0040] Among these, a phenyl group is preferred as R6.

[0041] In the present invention, there is no particular limitation on the molecular weight of the polymer containing the repeating units of formula (1), formula (2), and formula (3), and examples thereof include 5,000 to 500,000 (g / mol). From the viewpoints of the solution viscosity and mechanical strength of the polymer, it is preferably 10,000 to 200,000 (g / mol).

[0042] In the present invention, specific examples of the polymer containing the repeating units of formula (1), formula (2), and formula (3) include the following polymers.

[0043]

Chemical formula

[0044] The polymer of the present invention can be applied and printed on a plastic substrate such as polyester and on a glass substrate using a solution dissolved in an organic solvent such as cyclohexanone and 2-methoxy-1-methylethyl acetate. There is no particular limitation on the coating or printing method. For example, spin coating, drop casting, dip coating, doctor blade coating, pad printing, squeegee coating, roll coating, rod bar coating, air knife coating, wire bar coating, flow coating, gravure printing, flexographic printing, screen printing, inkjet printing, relief reverse printing, etc. can be used for printing.

[0045] Examples of the plastic used as the substrate include polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, polycarbonate, polymethyl acrylate, polymethyl methacrylate, polyvinyl chloride, polyethylene, ethylene-vinyl acetate copolymer, polymethylpentene-1, polypropylene, cyclic polyolefin, fluorinated cyclic polyolefin, polystyrene, polyimide, polyvinyl phenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), poly(diisopropyl maleate), polyethersulfone, polyphenylene sulfide, polyphenylene ether, polyester elastomer, polyurethane elastomer, polyolefin elastomer, polyamide elastomer, styrene block copolymer, etc. Further, two or more of the above plastics can be laminated and used as the substrate.

[0046] The polymer of the present invention can be produced by a known method. The production process includes an esterification step of reacting the hydroxyl group of polyvinyl alcohol with a cinnamoyl compound having photocrosslinking properties by an esterification reaction to form a polymer having repeating units of formula (1) and formula (3), and preferably a urethanization step of reacting the hydroxyl group of polyvinyl alcohol with an isocyanate compound by a urethanization reaction to form a polymer having repeating units of formula (1), formula (2) and formula (3).

[0047] Examples of the aforementioned cinnamoyl compound include compounds represented by formula (4), and these can be used alone or in combination of multiple ones.

[0048]

Chemical formula

[0049] (In formula (4), R1 to R5 are the same as those defined in formula (1).) Specific examples of the cinnamoyl compound represented by formula (4) include, for example, the following.

[0050]

Chemical formula

[0051] The isocyanate compound used in the present invention is represented by formula (8).

[0052]

Chemical formula

[0053] (In formula (8), R6 is the same as those defined in formula (2).) Specific examples of the isocyanate compound include, for example, the following, and these can be used alone or in combination of multiple ones.

[0054]

Chemical formula

[0055] Hereinafter, the method for producing the polymer of the present invention will be described in detail.

[0056] The polymer containing the repeating units of formula (1) and formula (3) of the present invention is produced in an esterification step.

[0057] The polymer containing the repeating units of formula (1), (2) and formula (3) of the present invention is produced in two steps, an esterification step and a urethanization step. These two steps can be carried out in reverse order. That is, either a method of performing the urethanization step after the esterification step or a method of performing the esterification step after the urethanization step may be used. Further, the polymer may be isolated after the first step and the second step may be carried out, or the first step and the second step may be continuously carried out in the same reactor.

[0058] A continuous method of performing the urethanization step in the same reactor after the esterification step will be described.

[0059] In the first esterification step, polyvinyl alcohol and a cinnamoyl compound are reacted. Examples of this esterification step include a solution method in which polyvinyl alcohol is dissolved in an organic solvent and reacted, or a slurry method in which polyvinyl alcohol particles are dispersed in an organic solvent in which the resulting polymer is soluble and reacted. It is preferable to use the solution method with a shorter reaction time. At this time, examples of the organic solvent to be used include pyridine, cyclohexanone, 2-methoxy-1-methylethyl acetate, and 1-methyl-2-pyrrolidinone, and it is preferable to use 1-methyl-2-pyrrolidinone. Further, examples of the organic solvent that can be used in the slurry method include cyclohexanone and 2-methoxy-1-methylethyl acetate.

[0060] The reaction temperature in the esterification step is not limited as long as it is below the boiling point of the organic solvent used, for example, it is 15 to 120 °C. The addition amount of the cinnamoyl compound is appropriately changed according to the chemical composition of the target polymer, but it is 0.4 to 1.5 in molar ratio to the hydroxyl group in polyvinyl alcohol.

[0061] Next, the second-stage urethanization process will be described. An isocyanate compound represented by the formula (8) is added to the polymer solution obtained in the above esterification process. The reaction temperature is, for example, 15 to 120°C. The addition amount of the isocyanate compound is 0.7 to 1.5 with respect to the theoretical molar number of the hydroxyl groups remaining in the polyvinyl alcohol after the esterification process. The polymer solution obtained through these two processes is isolated and dried by a known method such as charging it into a poor solvent such as methanol or ion-exchanged water with stirring, thereby obtaining the target polymer.

[0062] Next, a method of performing the above two processes in two stages using another reactor will be described. In this method, the order of the esterification process and the urethanization process may be reversed. The solvents, raw materials, and reaction conditions in these two processes are the same as those in the above continuous method. The solvents, raw materials, and reaction conditions in these two processes are the same as those in the above continuous method.

[0063] Since the polymer according to the present invention has a cinnamoyl group which is a photocrosslinkable group, it can also be made into a crosslinked product.

[0064] As a method of making a crosslinked product, photocrosslinking is preferable, and radiation or ultraviolet rays are preferably used for photocrosslinking. Examples of the radiation include ultraviolet rays having a wavelength of 245 to 350 nm. The irradiation amount of the radiation is appropriately changed according to the content of the photocrosslinkable group. For example, it is 50 to 4000 mJ / cm 2 . The environment for irradiating ultraviolet rays is not particularly limited, and it can be carried out in the air, in an inert gas such as nitrogen or argon, or under a certain amount of inert gas stream. If necessary, a photosensitizer can be added to the polymer solution to promote the photocrosslinking reaction. There is no limitation on the photosensitizer to be used. Examples thereof include benzophenone compounds, anthraquinone compounds, thioxanthone compounds, nitrophenyl compounds, etc., and benzophenone compounds are preferable. Further, two or more kinds of the sensitizers can be used in combination as necessary.

[0065] When crosslinking the polymer of the present invention with ultraviolet rays, heating may be performed if necessary. The temperature during heating is not particularly limited as long as the heat deformation of the plastic substrate to be printed and coated does not occur, and for example, conditions of 100 °C or lower can be mentioned.

[0066] Furthermore, in the polymer of the present invention, a compound containing a plurality of olefins such as ethylene and propylene in one molecule, a compound containing a plurality of acetylenes, butynes, etc. in one molecule, or a compound containing a plurality of cyclic olefins such as cyclopentene in one molecule may be blended as a crosslinking agent in order to increase the crosslinking density or shorten the crosslinking time. These compounds may be blended alone or in combination of two or more.

[0067] The polymer and crosslinked product of the present invention can contain various organic and inorganic polymers or oligomers, or a solid of organic and inorganic nanoparticles, or a liquid in which the nanoparticles are dispersed in an organic solvent, if necessary.

[0068] After crosslinking the polymer of the present invention with ultraviolet rays, by irradiating vacuum ultraviolet (VUV) light using a light-shielding mask, the surface tension of the portion irradiated with VUV can be changed. By this VUV treatment, a pattern having different surface tensions can be formed on the surface. The irradiation time of the VUV light varies depending on the structure of the polymer used for the insulating layer and the distance between the light source and the surface of the insulating layer. From the viewpoint of economy, 1 minute to 8 minutes is preferable, and more preferably 1 minute to 5 minutes.

[0069] By patterning, the non-cured portion can be easily removed with the above-mentioned organic solvent in which the present polymer dissolves.

[0070] The adhesive layer containing the polymer and / or crosslinked product of the present invention can be suitably used as an adhesive layer between different materials such as an insulating film layer or a metal electrode layer formed on a glass substrate or a plastic substrate when forming an electronic device or the like by printing.

[0071] Moreover, it can be an electronic device containing the above adhesive layer, particularly an organic transistor.

[0072] The organic transistor may have any of the element structures of the bottom gate-top contact type (A), bottom gate-bottom contact type (B), top gate-top contact type (C), and top gate-bottom contact type (D) shown in FIG. 1. In FIG. 2, 1 denotes an organic semiconductor layer, 2 denotes a substrate, 3 denotes a gate electrode, 4 denotes a gate insulating layer, 5 denotes a source electrode, and 6 denotes a drain electrode.

[0073] FIG. 2 shows an example of a bottom gate-top contact type element using the resin of the present invention as an adhesive layer. Here, 1 denotes an organic semiconductor layer, 2 denotes a substrate, 3 denotes a gate electrode, 4 denotes a gate insulating layer, 5 denotes a source electrode, 6 denotes a drain electrode, 7 denotes an adhesive layer, 8 denotes a bank, and 9 denotes a protective layer.

[0074] Examples of the gate electrode, source electrode, or drain electrode that can be used in the present invention include conductive materials such as gold, silver, aluminum, copper, titanium, platinum, chromium, polysilicon, silicide, indium tin oxide (ITO), and tin oxide. Further, a plurality of these conductive materials can be laminated and used.

[0075] The preferable performance of the organic transistor is as follows.

[0076] From the viewpoint of the practicality of the organic transistor element, the mobility of the organic transistor is preferably 0.20 cm 2 / Vs or more.

[0077] From the viewpoint of the practicality of the organic transistor element, the threshold voltage of the organic transistor is preferably -10.0 V or more and less than 0 V.

[0078] From the viewpoint of the practicality of the organic transistor element, the leakage current density of the organic transistor is preferably 10 -9 A / cm 2 or less.

[0079] In this organic transistor, the substrate that can be used is not particularly limited as long as it can ensure sufficient flatness for fabricating the device. For example, inorganic material substrates such as glass, quartz, aluminum oxide, highly doped silicon, silicon oxide, tantalum oxide, tantalum pentoxide, indium tin oxide, etc.; plastics; metals such as gold, copper, chromium, titanium, aluminum, etc.; ceramics; coated paper; surface-coated non-woven fabrics, etc. may be mentioned, and composite materials made of these materials or materials obtained by laminating these materials may also be used. Further, in order to adjust the surface tension, the surfaces of these materials can also be coated.

[0080] Also, in a BGTC (bottom gate-top contact) type device, electrodes are formed on the above-mentioned substrate or on the organic semiconductor layer. In this case, the method for forming the electrodes is not particularly limited, and examples include evaporation, high-frequency sputtering, electron beam sputtering, etc. Using an ink in which nanoparticles of the above-mentioned conductive material are dissolved in water or an organic solvent, solution spin coating, drop casting, dip coating, doctor blade, die coating, pad printing, roll coating, gravure printing, flexographic printing, screen printing, inkjet printing, relief reverse printing, etc. can also be adopted. Further, if necessary, a treatment for adsorbing fluoroalkylthiol, fluoroallylthiol, etc. on the electrodes may be performed.

[0081] There is no limitation on the organic semiconductor that can be used in the present invention, and both N-type and P-type organic semiconductors can be used, and it can also be used as a bipolar transistor combining N-type and P-type. For example, compounds of formulas (F-1) to (F-11) are exemplified.

[0082]

Chemical formula

[0083]

Chemical formula

[0084] [Chemistry]

[0085] [Chemistry]

[0086] [Chemistry]

[0087] [Chemistry]

[0088] [Chemistry]

[0089] [Chemistry]

[0090] [Chemistry]

[0091] [Chemistry]

[0092] [Chemistry]

[0093] In the present invention, as a method for forming an organic semiconductor layer, a method of dissolving an organic semiconductor in an organic solvent and then coating or printing is preferably used, and there are no restrictions as long as it is a method capable of forming a thin film of the organic semiconductor layer. When printing a solution in which an organic semiconductor is dissolved in an organic solvent, the solution concentration varies depending on the structure of the organic semiconductor and the solvent used, but from the viewpoint of forming a more uniform semiconductor layer and reducing the layer thickness, it is preferably 0.5 to 5% by weight. There are no restrictions on the organic solvent at this time as long as the organic semiconductor can be dissolved at a certain concentration for film formation. Examples include hexane, heptane, octane, decane, dodecane, tetradecane, decalin, indane, 1-methylnaphthalene, 2-ethylnaphthalene, 1,4-dimethylnaphthalene, dimethylnaphthalene isomer mixture, toluene, xylene, ethylbenzene, 1,2,4-trimethylbenzene, mesitylene, isopropylbenzene, pentylbenzene, hexylbenzene, tetralin, octylbenzene, cyclohexylbenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, trichlorobenzene, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, γ-butyrolactone, 1,3-butylene glycol, ethylene glycol, benzyl alcohol, glycerin, cyclohexanol acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, anisole, cyclohexanone, mesitylene, 3-methoxybutyl acetate, cyclohexanol acetate, dipropylene glycol diacetate, dipropylene glycol methyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 1,6-hexanediol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, ethyl acetate, phenyl acetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl-N-propyl ether, tetradecahydrophenanthrene, 1,2,3,4,5,6,7,8-octahydrophenanthrene, decahydro-2-naphthol, 1,2,3,4-Tetrahydro-1-naphthol, α-terpineol, isophorone triacetin, decahydro-2-naphthol, dipropylene glycol dimethyl ether, 2,6-dimethylanisole, 1,2-dimethylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, 1-benzothiophene, 3-methylbenzothiophene, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, dichloromethane, tetrahydrofuran, 1,2-dimethoxyethane, dioxane, cyclohexanone, acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, acetophenone, N,N-dimethylformamide, N-methyl-2-pyrrolidone, limonene and the like are exemplified. However, in order to obtain a crystal film with favorable properties, a solvent having a high dissolving power for the organic semiconductor and a boiling point of 100°C or higher is suitable, and xylene, isopropylbenzene, anisole, cyclohexanone, mesitylene, 1,2-dichlorobenzene, 3,4-dimethylanisole, pentylbenzene, tetralin, cyclohexylbenzene, decahydro-2-naphthol are preferred. Further, a mixed solvent in which two or more of the above-mentioned solvents are mixed at an appropriate ratio can also be used.,

[0094] Various organic and inorganic polymers or oligomers, or organic and inorganic nanoparticles can be added to the organic semiconductor layer as needed, either as solids or as a dispersion in which the nanoparticles are dispersed in water or an organic solvent, and a protective film can be formed by coating a polymer solution on the above-mentioned polymer dielectric layer. Further, various moisture-proof coatings, light-resistant coatings, etc. can be performed on this protective film as needed.

Examples

[0095] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0096] < 1 1H-NMR measurement> Measurement was carried out using JNM-ECZ400S FT-NMR (manufactured by JEOL Ltd.) with dimethyl sulfoxide-d6 or deuterated chloroform as the deuterated solvent.

[0097] <Chemical composition of the polymer> Measured using dimethyl sulfoxide-d6 1 The chemical composition of the polymer was determined from the H-NMR chart according to the following formula. Vinyl cinnamate (mole fraction) = 4 / (6A + 1) Vinyl alcohol (mole fraction) = (6A - 3) / (6A + 1) Here, A = S1 / S2, where S1 represents the integrated value of the peaks at δ0.9 to δ5.6 ppm and S2 represents the integrated value of the peaks at δ6.7 to δ8.2 ppm. Among the chemical composition of the polymer, the amount of vinyl cinnamate units was determined by the above calculation. The content of vinyl carbamate units was determined by the following formula in the case of, for example, phenyl vinyl carbamate units (denoted as Y). Y = (2 / B - 3 - 7X) / 5 B = S3 / S4 Here, X is the mole fraction of the above vinyl cinnamate units. Here, S3 represents the integrated value of the peaks at δ0.9 to δ2.9 ppm and S4 represents the integrated value of the peaks at δ0.9 to δ8.4 ppm.

[0098] <UV irradiation> A UV mask aligner, UPE-1605MA, manufactured by USIO LITING Co., Ltd. was used.

[0099] 3500 ppm of 4,4'-bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a sensitizer to the polymer solution, spin-coated to form a film, baked at 100 °C, and then irradiated with ultraviolet light for crosslinking.

[0100] <Solvent resistance (remaining film ratio)> On a 30 × 30 mm 2 glass (Eagle XG manufactured by Corning Inc.), the polymer solution was spin-coated to form a film using MS-A100 manufactured by Mikasa Co., Ltd. using a spin coater, baked at 100 °C for 5 minutes and dried thoroughly, and then 3000 mJ / cm 2The polymer film was photocrosslinked by irradiating it with ultraviolet rays. The thickness of this film was measured using a Bruker Dektak XT stylus profiler and designated as T0. Next, the glass plate coated with this photocrosslinked polymer film was immersed in cyclohexanone of the polymer for 1 minute, taken out, dried at 100 °C for 5 minutes using a hot plate, and the film thickness after drying was measured and designated as T1. Using these film thickness measurement values, the remaining film ratio (R) was calculated by the following formula R = T1 / T0 × 100 (%) The higher the remaining film ratio, the higher the degree of crosslinking of the polymer, indicating excellent solvent resistance. On the other hand, when the remaining film ratio R is 0, it indicates that the polymer film is completely dissolved and has poor solvent resistance.

[0101] <Adhesion> As a cross-cut tape peeling test, after cross-cutting (25 grids of 2 mm × 2 mm size), a tape peeling test was performed, and the peeling rate was expressed as the number of peeled / the number of grids.

[0102] The peeling test was performed on the following laminated structures. The uppermost surface of the following laminate was cross-cut using a cutter knife, and a peeling test was performed using cellophane tape.

[0103] I Glass / Polymer of the present invention (uppermost surface) II Glass / Polyimide double-sided tape / PET / Polymer of the present invention (uppermost surface) III Glass / Polyvinyl carbazole / Polymer of the present invention (uppermost surface) IV Glass / Metal film / Polymer of the present invention (uppermost surface) V Glass / Polymer of the present invention / Metal film For the PET film, polyethylene terephthalate with an untreated surface (thickness 100 μm, manufactured by Teijin DuPont) was used, and for the polyimide double-sided tape, the one manufactured by Nitto Denko was used. The thickness of the polymer of the present invention and the insulating film poly(4'-vinyl carbazole) obtained in Reference Example 1 described later was 500 to 700 nm, and a film was formed by spin coating. The metal (gold, silver, aluminum) layer was formed by vacuum evaporation using a small vacuum evaporation apparatus VTR-350M / ERH manufactured by ULVAC Kiko Co., Ltd., and its thickness was 25 nm.

[0104] (Reference Example 1) Insulating Film As the insulating film, poly(4'-vinylchalcone) containing 93 mol% of chalcone groups and 7 mol% of styrene units synthesized using the method described in Japanese Patent No. 6953986 was used.

[0105] (Example 1) Polymer 1 In a nitrogen box, 12 g of polyvinyl alcohol (manufactured by Tokyo Chemical Industry, degree of polymerization 1700, molecular weight 75,000 g / mol), 100 mL of dehydrated 1-methyl-2-pyrrolidinone (manufactured by Fujifilm Wako Pure Chemical Corporation), and a magnetic stirrer were charged into a 500 mL two-necked flask, and dissolved with stirring at 100 °C under a nitrogen seal. A solution prepared by dissolving 38 g of cinnamoyl chloride (manufactured by Tokyo Chemical Industry) in 60 mL of dehydrated 1-methyl-2-pyrrolidinone was added dropwise to this solution with stirring. Then, the temperature was slowly lowered to room temperature and reacted for 27 hours. The reaction solution was poured into 3 L of methanol to precipitate the polymer, and Polymer A was isolated by filtration. After dissolving the obtained Polymer A in 400 mL of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Corporation), it was poured into 4 L of ion-exchanged water to precipitate the polymer, and then filtered. The filtrate was washed with 400 mL of methanol with stirring, filtered again, and vacuum dried at 60 °C to obtain 36 g of Polymer A. The esterification rate of the obtained Polymer A was 1 70 mol% as determined by 1H-NMR. A film containing Polymer A was formed by spin-coating a PGMEA solution (concentration 9 wt%) of the obtained Polymer A on a glass plate, and irradiated with ultraviolet light of 3500 mJ / cm 2 to obtain a film containing a crosslinked product of Polymer A. The residual film ratio in the immersion test of the obtained film containing the crosslinked product of Polymer A in propylene glycol methyl ether acetate (hereinafter referred to as PGMEA, manufactured by Fujifilm Wako Pure Chemical Corporation) was 99%.

[0106] [Chemical Formula]

[0107] 36 g of this polymer A was dissolved in 300 mL of 1-methyl-2-pyrrolidinone at room temperature, and then 13 g of phenyl isocyanate (manufactured by Tokyo Chemical Industry) was added with stirring. After the addition, the mixture was reacted at room temperature for 27 hours, then poured into 3 L of methanol to precipitate Polymer 1. After filtration, it was dissolved again in 350 mL of tetrahydrofuran at room temperature, then poured into 4 L of methanol to precipitate the polymer, filtered, and dried in vacuo at 60 °C to obtain 44 g of Polymer 1. The composition of the obtained Polymer 1 was vinyl cinnamate unit:phenyl vinyl carbamate:vinyl alcohol unit = 70 / 28 / 2 (mol%). The 1 1H-NMR chart of the obtained polymer is shown in Figure 3. A PGMEA solution (concentration 9 wt%) of the obtained polymer was spin-coated on a glass plate to form a film containing Polymer 1, and irradiated with ultraviolet light of 3500 mJ / cm 2 to obtain a film containing a crosslinked product of Polymer 1. The residual film ratio in the immersion test of the obtained film containing the crosslinked product of Polymer 1 in PGMEA was 100%.

[0108] [Chemical formula]

[0109] (Example 2) Polymer 2 In a nitrogen box, a 500 mL two-necked flask was charged with 10 g of polyvinyl alcohol powder, 150 mL of dehydrated 1-methyl-2-pyrrolidinone, and a magnetic stir bar, and dissolved with stirring at 100 °C under a nitrogen seal. After cooling the obtained solution to room temperature, a solution prepared by dissolving 34 g of cinnamoyl chloride in 40 mL of dehydrated 1-methyl-2-pyrrolidinone was slowly added with stirring, and reacted at room temperature for 19 hours. 9.1 mL of phenyl isocyanate was added to this reaction solution. After the addition, the mixture was reacted at room temperature for 28 hours, then poured into 4 L of methanol to precipitate Polymer 2. After filtration, it was dried in vacuo at 60 °C to obtain 30 g of Polymer 2. The composition of the obtained Polymer 2 was vinyl cinnamate unit:phenyl vinyl carbamate:vinyl alcohol unit = 61 / 24 / 15 (mol%). A PGMEA solution (concentration 9 wt%) of the obtained Polymer 2 was spin-coated on a glass plate to form a film containing Polymer 2, and irradiated with ultraviolet light of 3500 mJ / cm 2A film containing a crosslinked polymer 2 was obtained by irradiating with ultraviolet rays. The remaining film ratio in the immersion test of the obtained film containing the crosslinked polymer 2 in PGMEA was 99%.

[0110] [Chemical formula]

[0111] (Example 3) Polymer 3 In a 500 mL two-necked flask in a nitrogen box, 10 g of polyvinyl alcohol powder, 190 mL of dehydrated 1-methyl-2-pyrrolidinone, and a magnetic stir bar were charged, and it was dissolved with stirring at 100 °C under a nitrogen seal. After cooling the obtained solution to room temperature, a solution prepared by dissolving 31 g of cinnamoyl chloride in 100 mL of 1-methyl-2-pyrrolidinone was added with stirring, and the reaction was carried out at room temperature for 27 hours. It was poured into 3 L of ion-exchanged water to precipitate polymer B, and polymer B was isolated by filtration. After dissolving the obtained polymer B in 400 mL of tetrahydrofuran, it was again poured into 4 L of methanol to precipitate the polymer. After filtration, it was vacuum-dried at 60 °C to obtain 40 g of polymer B. The esterification rate of the obtained polymer B was 1 73 mol% by 1H-NMR. A film containing polymer B was formed by spin-coating a PGMEA solution (concentration 9 wt%) of the obtained polymer B on a glass plate, and it was irradiated with ultraviolet rays of 3500 mJ / cm 2 to obtain a film containing a crosslinked polymer B. The remaining film ratio in the immersion test of the obtained film containing the crosslinked polymer B in PGMEA was 99%.

[0112] [Chemical formula]

[0113] After dissolving 10 g of this polymer B in 100 mL of 1-methyl-2-pyrrolidinone at room temperature, 3 g of phenyl isocyanate was added with stirring. After the addition, the mixture was reacted at room temperature for 20 hours, then poured into 3 L of methanol to precipitate the polymer. After filtration, it was dried in vacuo at 60 °C to obtain 18 g of polymer 3. The composition of the obtained polymer 3 was vinyl cinnamate unit:phenyl vinyl carbamate:vinyl alcohol unit = 73 / 25 / 2 (mol%). A PGMEA solution (concentration 9 wt%) of the obtained polymer 3 was spin-coated on a glass plate to form a film containing polymer 3, and irradiated with ultraviolet rays of 3500 mJ / cm 2 to obtain a film containing a crosslinked product of polymer 3. The residual film ratio in the PGMEA immersion test of the obtained film containing the crosslinked product of polymer 3 was 99%.

[0114] [Chemical formula]

[0115] (Examples 4 to 7) 2 g of polymer A obtained in the esterification step of Example 1 and 18 g of NMP were charged into a 50 mL two-necked flask, and 3,5-bis(trifluoromethyl)phenyl isocyanate (I1), p-methoxyphenyl isocyanate (I2), p-tolyl isocyanate (I3), 1-naphthyl isocyanate (I4) (all manufactured by Tokyo Chemical Industry) were added in an amount 1.5 times the number of moles of the hydroxyl groups in the polymer. The reaction was carried out under the same conditions as in the urethanization step of Example 1 to obtain polymers 4 to 7. The yields and chemical compositions of the obtained polymers are shown in Table 1.

[0116] [Table 1]

[0117] (Examples 8 to 14) Table 2 shows the results of the cross-cut tape peeling test of the polymers obtained in Examples 1 to 7 against glass, PET, metal vapor deposition films (gold, silver, aluminum), and insulating films. As the insulating film, poly(4'-vinyl chalcone) described in Reference Example 1 was used. Polymers 1 to 7 showed excellent adhesiveness to glass, PET, metal thin films, and insulating films.

[0118]

Table 2

[0119] (Comparative Examples 1 to 2) The crosslinked PVP film and the crosslinked polyvinyl cinnamate film were formed in a glass plate shape, and the cross-cut tape peeling test was performed in the same manner as in the examples. The results are shown in Table 2. Peeling was observed in the gold thin film for the crosslinked PVP film, and there was a problem that the PET film was thermally deformed when forming a film on the PET film and thermally crosslinking. In addition, peeling was observed in the PET film and metal thin films (gold, silver, aluminum) for the crosslinked poly(vinyl cinnamate) film, and the adhesiveness was poor.

[0120] Note that the crosslinked film of PVP was obtained by mixing Solution 1, a 20 wt% solution in which 8 g of poly(vinylphenol) manufactured by Sigma-Aldrich was dissolved in 32 g of PGMEA, and Solution 2, a 10 wt% solution in which 4 g of a methylated solution of poly(melamine formaldehyde) (manufactured by Sigma-Aldrich) was dissolved in 36 g of PGMEA, at a volume ratio of 1:2, spin-coating on a glass plate, and then heat-treating at 90 °C for 10 minutes and at 150 °C for 1 hour. The crosslinked film of polyvinyl cinnamate (manufactured by Sigma-Aldrich) was obtained by spin-coating a 10 wt% PGMEA solution of polyvinyl cinnamate in a glass shape and irradiating with ultraviolet light at 3500 mJ / cm 2 irradiation.

Claims

1. A polymer characterized by containing repeating units of formula (1) and formula (3). 【Chemical Formula 1】 (In formula (1), R １ represents hydrogen or a methyl group, and R ３ , R ４ and R ５ each independently represent hydrogen, fluorine, a cyano group, a nitro group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 fluoroalkyl group, or a C1-C6 cycloalkyl group.) [Chemical 2]

2. The polymer according to claim 1, further containing a repeating unit of formula (2). 【Chemical 3】 (In formula (2), R ６ represents a phenyl group, a C7-C10 alkylphenyl group, a C7-C10 alkoxyphenyl group, a naphthyl group, a C7-C10 fluorophenyl group, a C7-C10 fluoroalkylphenyl group, a biphenyl group, an acetyl group, an adamantyl group, a C3-C6 alkyl group, or a C3-C6 cycloalkyl group.)

3. A crosslinked product composed of the polymer according to claim 1 or 2.

4. An adhesive layer comprising the polymer according to claim 1 and / or the crosslinked product according to claim 2.

5. An electronic device comprising the adhesive layer according to claim 4.

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