JP2017165887A - Composition for insulating film formation and gate insulating film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for insulating film formation which has excellent electric insulation properties having a high dielectric breakdown strength even at a curing temperature of lower than 200°C suitable for printing on a flexible film such as plastic, /good adhesion to a substrate, excellent solvent resistance and has high specific dielectric constant, and to provide an organic thin film transistor which has a gate insulating film using the composition for insulating film formation and excellent reliability.SOLUTION: There are provided a composition for insulating film formation which contains a compound (A) having 6 or more specific acryloyl groups, a metal oxide (B) and a solvent; and an insulating film obtained by the composition for insulating film formation.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a composition for forming an insulating film. Further, the present invention relates to a gate insulating film and an organic thin film transistor formed using the composition.

  Field effect transistors using inorganic materials such as polysilicon and amorphous silicon use chemical vapor deposition and oxidation in the process of forming a semiconductor layer, which requires large-scale equipment such as vacuum equipment and is complicated. Many processes are required. Further, since heating at 300 to 1000 ° C. is required in the crystallization process of the semiconductor layer, the substrate is required to have heat resistance.

  On the other hand, since an organic thin film transistor using an organic semiconductor can be manufactured at a lower temperature than an inorganic semiconductor, a flexible plastic substrate or film can be used as the substrate, and an element that is lightweight and hardly broken can be obtained. In addition, an element can be manufactured by applying a solution containing an organic material or forming a film using a printing method, and a large number of elements can be manufactured on a large-area substrate at a low cost.

In the bottom gate type which is one of the element structures of an organic thin film transistor, an organic semiconductor layer is formed so as to overlap with a gate insulating layer. Therefore, when manufacturing by coating or printing methods, the gate insulating layer has not only electrical insulation properties such as high dielectric breakdown strength and low leakage current density and adhesion to the substrate, but also resistance to solvents that dissolve organic semiconductors. Solvent property is required.
As such materials, various organic materials have been studied and developed. Polyvinyl alcohol (Patent Document 1), polyimide polymer (Patent Document 2), silicon polymer (Patent Document 3), acrylic polymer (Patent Document 4) Transistors using an organic material such as) as an insulating film have been proposed, but they do not show good semiconductor properties due to the presence of polar groups such as hydroxyl groups present on the surface of the insulating film, and are treated with a silane coupling agent or the like. An organic insulating film material that does not function unless it is used afterwards, requires a complicated process, and still exhibits satisfactory characteristics with a single layer without surface treatment has not been obtained.
Patent Document 5 discloses a silsesquioxane-based organic-inorganic hybrid material. It is said to have excellent electrical insulation and excellent solvent resistance. However, since the curable material has a long curing time and a high curing temperature, problems remain in productivity, such as inability to print and form in a short time, and limited substrates that can be used.

JP 2007-027524 A JP 2004-349319 A JP 2007-043055 A JP 2007-224293 A JP 2012-009796 A Japanese Unexamined Patent Publication No. 2005-026698

  The object of the present invention is to provide excellent electrical insulation having high dielectric breakdown strength even at a curing temperature of less than 200 ° C. suitable for printing on a flexible film such as plastic, good adhesion to a substrate, and excellent resistance to resistance. An object of the present invention is to provide a composition for forming an insulating film having a solvent property and a high relative dielectric constant, and a highly reliable organic thin film transistor comprising a gate insulating film using the composition for forming an insulating film.

  As a result of intensive studies to solve the above problems, the present inventors have found that the target can be achieved with the following composition for forming an insulating film and an insulating film using the composition, and the present invention has been completed.

That is, this invention relates to the composition for insulating film formation containing the compound (A) which has 6 or more of acryloyl groups represented by following General formula (1), a metal oxide (B), and a solvent.

［一般式（１）中、Ｒ_１は、下記いずれかの４価の有機残基を表す。

一般式（１）中、Ｒ_２は、下記いずれかの１価の有機残基を表す。

一般式（１）中、Ｒ_３は、１価の有機残基を示す。］ General formula (1)

[In General Formula (1), R ₁ represents any one of the following tetravalent organic residues.

In general formula (1), R ₂ represents any of the following monovalent organic residues.

In general formula (1), R ₃ represents a monovalent organic residue. ]

  Moreover, this invention relates to the said composition for insulating film formation which contains a polymerization initiator further.

  Moreover, this invention relates to the said composition for insulating film formation in which a polymerization initiator contains a thermal-polymerization initiator and a photoinitiator.

  Further, the present invention provides the above composition for forming an insulating film, wherein the metal oxide (B) contains at least one element selected from the group consisting of titanium, zinc, zirconium, indium, tin, aluminum, silicon and phosphorus. About.

  Moreover, this invention relates to the said composition for insulating film formation whose metal oxide (B) is a titanium oxide or a barium titanate.

  Moreover, this invention relates to the said composition for insulating film formation whose D50 particle diameter of a metal oxide (B) is 0.005-0.200 micrometer.

  Moreover, this invention relates to the insulating film which is the hardened | cured material of the said composition for insulating film formation.

  The present invention also relates to a thin film transistor provided with the cured product of the composition for forming an insulating film as a gate insulating film.

The compound (A) has a high dispersibility with respect to the metal oxide (B) and functions as a dispersant having light or thermosetting properties because it contains a large number of acryloyl groups. Furthermore, the metal oxide (B) has a high dielectric constant, and by being uniformly dispersed by the compound (A), it has high curability and excellent electrical insulation, solvent resistance, adhesion, An insulating film having a high relative dielectric constant can be formed. Thereby, the cured film formed using the composition for insulating film formation of this invention can be used suitably for a gate insulating film and an organic thin-film transistor using the same. Furthermore, since the curing temperature is low, it is possible to print on various plastic films with low heat resistance, and it is also suitable for flexible gate insulating films for thin film transistors.
That is, according to the present invention, the curing temperature is low and can be printed on various plastic films, and the obtained cured film achieves excellent electrical insulation, solvent resistance, adhesion, and dielectric constant. A forming composition can be provided. In addition, a gate insulating film using the insulating film forming composition and a thin film organic transistor having good reliability can be provided.

  1 to 2 show structural examples of a thin film transistor using a gate insulating film of the present invention. 1 and 2, in the thin film transistor of the present invention, the gate electrode 2 is formed on the substrate 1, and the gate electrode 2 is covered with the gate insulating film 3 of the present invention.

In the example of FIG. 1, the source electrode 4 and the drain electrode 4 are provided on the gate insulating film 3, and the semiconductor layer 5 is formed so as to cover them. In the example of FIG. 2, the semiconductor layer 5 is formed on the gate insulating film 3, and the source electrode 4 and the drain electrode 4 are provided thereon.

<Insulating film forming composition>
The composition for forming an insulating film of the present invention contains a compound (A) having 6 or more acryloyl groups represented by the following general formula (1), a metal oxide (B), and a solvent. And Hereinafter, embodiments of the present invention will be described. In the present application, when “(meth) acryloyl”, “(meth) acrylic acid”, “(meth) acrylate”, “(meth) acryloyloxy”, and “(meth) allyl” are expressed, Unless otherwise stated, “acryloyl and / or methacryloyl”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, “acryloyloxy and / or methacryloyloxy”, and “allyl and / or methallyl”, respectively. ".

［一般式（１）中、Ｒ_１は、下記いずれかの４価の有機残基を表す。

一般式（１）中、Ｒ_２は、下記いずれかの１価の有機残基を表す。

一般式（１）中、Ｒ_３は、１価の有機残基を示す。］ [Compound (A) having 6 or more acryloyl groups represented by the general formula (1)]
General formula (1)

[In General Formula (1), R ₁ represents any one of the following tetravalent organic residues.

In general formula (1), R ₂ represents any of the following monovalent organic residues.

In general formula (1), R ₃ represents a monovalent organic residue. ]

In the general formula (1), R ₁ is a tetravalent organic residue, and includes a phenyl skeleton residue (x1-1), a biphenyl skeleton residue (x1-2), a fluorene skeleton residue (x1-3), Including butylene group residue (x1-4). Among these, a phenyl skeleton residue, a biphenyl skeleton residue, and a fluorene skeleton residue, which are organic residues containing an aromatic ring, are more preferable, and a biphenyl skeleton residue is particularly preferable.

In the general formula (1), examples of the organic residue represented by R ₃ include an organic residue containing an aromatic ring and an organic residue containing (meth) acryloyl. Among them, those having a biphenyl skeleton residue are preferable, and a monovalent organic residue represented by the following formula (3) is more preferable.

Formula (3)

[Method for Synthesizing Compound (A)]
The compound (A) in which R ₃ is a structure represented by the above formula (3) includes, for example, a tetracarboxylic dianhydride (x1) represented by the following general formula (2), pentaerythritol triacrylate, Compound (X) having a carboxyl group which is a reaction product with compound (x2) which is a hydroxyl group-containing polyfunctional monomer selected from pentaerythritol pentaacrylate, epoxy group-containing compound (Y), Can be obtained by reacting. When biphenyl glycidyl ether is used as the epoxy group-containing compound (Y), a compound (A) in which R ₃ is a structure represented by the above formula (3) can be obtained. Here, from the viewpoint of photocurability and hard coat properties, the compound (x2) needs to be pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

(Reaction of tetracarboxylic dianhydride (x1) represented by general formula (2) with hydroxyl group-containing polyfunctional monomer compound (x2))
General formula (2)

_{R 1} in the general formula (2) has the same meaning as _{R 1} in the general formula (1).

  Examples of the tetracarboxylic dianhydride (x1) represented by the general formula (2) include 1,2,4,5-benzenetetracarboxylic dianhydride and 3,3 ′, 4,4 ′ having a biphenyl skeleton. -Biphenyltetracarboxylic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride having a fluorene skeleton, or 9,9-bis [4- (3,4-dicarboxyphenoxy) ) Phenyl] fluorene dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride.

  Among these tetracarboxylic dianhydrides, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride has a biphenyl skeleton, and the biphenyl skeleton is efficiently incorporated in the molecule of the compound (A). This is particularly preferable because it can be introduced and can further have a hard coat property of the cured film and a good dispersibility of the metal oxide.

Specific commercial products of the compound (x2) pentaerythritol triacrylate and dipentaerythritol pentaacrylate include Biscoat # 300 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), KAYARAD PET30 (manufactured by Nippon Kayaku Co., Ltd.) , PETIA (manufactured by Daicel UCB), Aronix M305 (manufactured by Toagosei Co., Ltd.), NK ester A-TMM-3LMN (manufactured by Shin-Nakamura Chemical Co., Ltd.), light acrylate PE-3A (Kyoeisha Chemical Co., Ltd.) SR-444 (Sartomer Co., Ltd.), Light acrylate DPE-6A (Kyoeisha Chemical Co., Ltd.), KAYARAD DPHA (Nippon Kayaku Co., Ltd.), Aronix M402 (Toagosei Co., Ltd.) ) And the like.

In addition, the commercial item of a compound (x2) contains about 5 to 15 weight% of pentaerythritol diacrylate and dipentaerythritol tetraacrylate which each have two hydroxyl groups as subcomponents.
Therefore, in the reaction to obtain the compound (A), in addition to the compound (A), a reaction product derived from an auxiliary component, a resin having a high molecular weight such as the compound (A) is generated at the same time, and only the compound (A) cannot be calculated. There is. Therefore, the compound (A) may be described as “a reactant containing the compound (A)”.

  The reaction between the tetracarboxylic dianhydride (x1) and the compound (x2) is a reaction between two carboxylic anhydride groups possessed by the tetracarboxylic dianhydride and a hydroxyl group possessed by the compound (x2). As such, it is well known in the art. For example, the presence of a catalyst such as 1,8-diazabicyclo [5.4.0] -7-undecene in an organic solvent such as cyclohexanone and tetracarboxylic dianhydride (x1) and compound (x2). The reaction can be carried out at a temperature of 50 to 120 ° C. In this case, a polymerization inhibitor such as methylhydroquinone (2-METHYLHYDROQUINONE) can be added to the reaction system.

(Reaction of carboxyl group-containing compound (X) and epoxy group-containing compound (Y))
After the reaction, the compound (X) is added to the reaction mixture containing the compound (X) having a carboxyl group without purifying the compound, and the compound (Y) is reacted with the carboxyl group and the epoxy group. A) can be obtained. Examples of the epoxy group-containing compound (Y) include glycidyl (meth) acrylate, an epoxy group-containing (meth) acrylate such as (meth) acrylic acid (3,4-epoxycyclohexyl) methyl; o-phenylphenol glycidyl ether, Aromatic glycidyl such as p-phenylphenol glycidyl ether, monostyrenated phenol glycidyl ether, 4-cyano-4-hydroxybiphenyl glycidyl ether, 4,4′-biphenol monoglycidyl ether, 4,4′-biphenol diglycidyl ether Ether compounds and the like are preferable. Among these, biphenyl glycidyl ether represented by the following general formula (5) is particularly preferable from the viewpoint of dispersion stability.

General formula (5)

  The reaction between the carboxyl group-containing compound (X) and the epoxy group-containing compound (Y) represented by the general formula (4) is a reaction between a carboxyl group and an epoxy group, and as such is well known in the art. . For example, this reaction can be performed at a temperature of 50 to 120 ° C. in the presence of an amine catalyst such as dimethylbenzylamine.

  These reactions may be carried out without solvent or in a solvent inert to the reaction. Examples of such solvents include hydrocarbon solvents such as n-hexane, benzene and toluene; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; diethyl ether, tetrahydrofuran or Ether solvents such as dioxane; Halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, or parkrene; acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazo Examples include polar solvents such as lysinone. Two or more of these solvents may be used in combination.

  The number of acryloyl groups in the compound (A) needs to be 6 or more. In the present invention, a compound having less than 6 acryloyl groups can be used in combination, but when the compound (A) is not included, the hardness of the resulting cured film is lowered.

[Metal oxide (B)]
The metal oxide preferably has a D50 particle size of 0.005 to 0.200 μm. The D50 particle size of the metal oxide can be measured using, for example, “Nanotrack UPA” manufactured by Nikkiso Co., Ltd. using a dynamic light scattering method. In the case of a composition for forming an insulating film having a D50 particle diameter of less than 0.005 μm, the cohesive force between the fine particles is very large, so that the dispersibility at the primary particle level with high transparency tends to be lowered. On the other hand, when the D50 particle diameter exceeds 0.200 μm, since the particle diameter is large, scattering tends to occur with respect to light such as visible light, and turbidity tends to occur in the cured film.
The metal oxide (B) particles have various shapes such as a spherical shape, a needle shape, and a scale shape. Among them, a scale shape is most preferable from the viewpoint of dielectric constant.

  The metal oxide (B) preferably contains at least one element selected from the group consisting of titanium, zinc, zirconium, aluminum, silicon, phosphorus, and fluorine. In particular, a metal oxide containing any one element of titanium, zinc, zirconium, aluminum, silicon, and phosphorus is more preferable. Specific examples include titanium oxide, zinc oxide, zirconium oxide, silicon oxide, aluminum oxide, and barium titanate. Among them, titanium oxide, zirconium oxide, and barium titanate, which have a high relative dielectric constant, are used. Titanium oxide or barium titanate is particularly preferable. These metal oxides may be treated with organic or inorganic materials on the surface. These metal oxides may be used in combination of two or more.

As a commercial product of metal oxide,
Ishihara Sangyo Co., Ltd .: TTO-55 (A) (titanium oxide), TTO-55 (B) (titanium oxide), TTO-55 (C) (titanium oxide), TTO-55 (D) (titanium oxide) , TTO-55 (S) (titanium oxide), TTO-55 (N) (titanium oxide), TTO-51 (A) (titanium oxide), TTO-51 (C) (titanium oxide), TTO-S-1 (Titanium oxide), TTO-S-2 (titanium oxide), TTO-S-3 (titanium oxide), TTO-S-4 (titanium oxide), TTO-F-1 (iron-containing titanium oxide), TTO-F -2 (iron-containing titanium oxide), TTO-F-3 (iron-containing titanium oxide), TTO-F-11 (iron-containing titanium oxide), ST-01 (titanium oxide), ST-21 (titanium oxide), ST -30L (titanium oxide), ST-31 (titanium oxide),
Made by CI Kasei Co., Ltd .: Nanotech TiO2, Nanotech SiO2, Nanotech Al2O3, Nanotech ZnO,
Hakusuitec Co., Ltd .: PazetCK (aluminum-doped zinc oxide),
Sakai Chemical Industry Co., Ltd .: FINEX-25 (zinc oxide), FINEX-25LP (zinc oxide), FINEX-50 (zinc oxide), FINEX-50LP (zinc oxide), FINEX-75 (zinc oxide), NANOFINE- 50A (zinc oxide), NANOFINE-50SD (zinc oxide), EZ-1 (zinc oxide), STR-60C (titanium oxide), STR-60C-LP (titanium oxide), STR-100C (titanium oxide), STR- 100C-LP (titanium oxide), STR-100A-LP (titanium oxide), STR-100W (titanium oxide), KZM-20 (barium titanate)
Sumitomo Osaka Cement Co., Ltd .: OZC-3YC (zirconium oxide), OZC-3YD (zirconium oxide), OZC-3YFA (zirconium oxide), OZC-8YC (zirconium oxide), OZC-0S100 (zirconium oxide),
NIPPON Denko Co., Ltd .: PCS (zirconium oxide), PCS-60 (zirconium oxide), PCS-90 (zirconium oxide), T-01 (zirconium oxide),
Made by Teika Co., Ltd .: MT-100S (titanium oxide), MT-100HD (titanium oxide), MT-100SA (titanium oxide), MT-500HD (titanium oxide), MT-500SA (titanium oxide), MT-600SA ( Titanium oxide), MT-700HD (titanium oxide), MZ-303S (zinc oxide), MZY-303S (zinc oxide), MZ-303M (zinc oxide), MZ-505S (zinc oxide), MZY-505S (zinc oxide) ), MZ-505M (zinc oxide),
Made by Nippon Aerosil Co., Ltd .: Aluminum Oxide C (aluminum oxide), AEROSIL130 (silicon oxide), AEROSIL200 (silicon oxide), AEROSIL200V (silicon oxide), AEROSIL200CF (silicon oxide), AEROSIL200FA (silicon oxide), AEROSIL300 (silicon oxide) , AEROSIL300CF (silicon oxide), AEROSIL380 (silicon oxide), AEROSILR972 (silicon oxide), AEROSILR974 (silicon oxide), AEROSILR976 (silicon oxide), AEROSILR202 (silicon oxide), AEROSILR805 (silicon oxide), AEROSILR812 (ILO), 8ER (Silicon oxide), AEROSILMO 50 (silicon oxide), AEROSILTT600 (silicon oxide), AEROSILMOX80 (silicon oxide / aluminum oxide), AEROSILMOX170 (silicon oxide / aluminum oxide), AEROSILCOX84 (silicon oxide / aluminum oxide),
Etc.

  The compounding of the metal oxide (B) and the compound (A) in the composition for forming an insulating film is not particularly limited, but the reaction product containing the compound (A) is 10 weights with respect to 100 parts by weight of the metal oxide (B). The amount is preferably from 50 parts by weight to 50 parts by weight, and more preferably from 10 parts by weight to 35 parts by weight. When it is in the above range, the dispersibility and the film forming property are particularly excellent.

  When adding a solvent, it is preferable to perform a curing treatment after volatilizing the solvent. The solvent is not particularly limited, and various known organic solvents can be used. Specifically, for example, cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, acetylacetone, toluene, xylene, n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy-1-butanol , 3-methoxy-2-butanol, ethylene glycol monomethyl ether, ethylene glycol mono n-butyl ether, 2-ethoxyethanol, 1-methoxy-2-propanol, diacetone alcohol, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethylene Glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, 2-ethoxyethyl acetate, butyl acetate , Isoamyl acetate, dimethyl adipate, dimethyl succinate, dimethyl glutarate, tetrahydrofuran, and methyl pyrrolidone. These organic solvents may be used in combination of two or more.

  Among them, the hydroxyl group-containing solvent has good wettability with respect to metal oxides having highly hydrophilic particle surface properties. Therefore, when it is contained in the solvent composition, the dispersibility of the metal oxide and the formation of the insulating film thereof are included. This is preferable because it is very effective in improving the aging stability of the composition for use and also improves the leveling property of the coating process. The hydroxyl group-containing solvent content in the total solvent composition is preferably 10 to 100% by weight. Specifically, as the hydroxyl group-containing solvent, n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy-1-butanol, 3-methoxy-2-butanol, ethylene glycol Examples thereof include monomethyl ether, ethylene glycol mono n-butyl ether, 2-ethoxyethanol, 1-methoxy-2-propanol, diacetone alcohol, ethyl lactate, butyl lactate, and propylene glycol monomethyl ether. In particular, 3-methoxy-1-butanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, and ethylene glycol mono n-butyl ether are preferable because the dispersibility and dispersion stability of the metal oxide become better.

  Even if the composition for forming a gate insulating film of the present invention is prepared by simply mixing the compound (A) and the metal oxide powder, the intended effect can be obtained sufficiently. However, it can be mixed mechanically with a kneader, roll, attritor, super mill, dry pulverizer, etc., or a solution containing the compound (A) is added to a suspension system using a metal oxide powder and an organic solvent to oxidize the metal. Even better results can be obtained if the reaction is carried out in an intimate mixed system such as deposition of the compound (A) on the surface of the object.

  The insulating film forming composition is preferably a metal oxide dispersion in which metal oxide powder is uniformly dispersed. The metal oxide dispersion can be preferably produced by using the compound (A) and dispersing the metal oxide (B) in the presence of an organic solvent. As the degree of dispersion, the dispersion particle diameter D50 is preferably less than 200 nm, more preferably less than 150 nm, when measured with “Nanotrack UPA” manufactured by Nikkiso Co., Ltd. using a dynamic light scattering method.

  For the dispersion or dissolution of the compound (A), metal oxide (B), or composition for forming an insulating film in a non-aqueous vehicle such as an organic solvent, and mixing thereof, a paint conditioner (manufactured by Red Devil) , Ball mill, sand mill (such as “Dyno mill” manufactured by Shinmaru Enterprises), attritor, pearl mill (such as “DCP mill” manufactured by Eirich), coball mill, homomixer, homogenizer (such as “Clairemix” manufactured by M Technique) Dispersers such as a wet jet mill (“Genus PY” manufactured by Genus Co., Ltd., “Nanomizer” manufactured by Nanomizer Co., Ltd.), and a fine bead mill (“Super Apec Mill”, “Ultra Apec Mill” manufactured by Kotobuki Industries Co., Ltd.) can be used. When using media in the disperser, it is preferable to use glass beads, zirconia beads, alumina beads, magnetic beads, styrene beads, or the like. Regarding dispersion, two or more types of dispersers or two or more types of media having different sizes may be used and used in stages.

  The composition for forming an insulating film of the present invention can further contain various additives as long as the objects and effects of the present invention are not impaired. Specifically, photopolymerization initiator, photocurable compound, polymerization inhibitor, photosensitizer, leveling agent, surfactant, antibacterial agent, antiblocking agent, plasticizer, ultraviolet absorber, infrared absorber, oxidation Examples thereof include an inhibitor, a silane coupling agent, a conductive polymer, a conductive surfactant, an inorganic filler, a pigment, and a dye.

  The method for producing the composition for forming an insulating film containing components other than the compound (A), the metal oxide (B), and the solvent is not particularly limited, and several methods may be mentioned. Specifically, the compound (A) and the metal oxide (B) are first mixed and dispersed in an organic solvent to obtain a stable metal oxide dispersion, and then various other additives are added and adjusted. Examples of the production method include a method of dispersing and producing the compound (A), metal oxide (B), organic solvent and other additives from the beginning.

[Polymerization initiator]
The composition for forming an insulating film of the present invention can further contain a polymerization initiator, and at least one of the thermal polymerization initiator and the photopolymerization initiator can be used according to the curing conditions. Use of a thermal polymerization initiator and a photopolymerization initiator in combination is preferable because crosslinking of the acryloyl group can be efficiently advanced and solvent resistance is improved.

(Thermal polymerization initiator)
Examples of thermal polymerization initiators include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile) and dimethyl 2,2'-azobis (2-methylpropionate) ), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) ) Propane] and the like.

  Also, benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxy Organic such as 2-ethylhexanoate, tert-butylperoxyneodecanoate, tert-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide A peroxide is mentioned.

  Among these, from the viewpoint of storage stability and polymerizability, 2,2′-azobisisobutyronitrile and dibenzoyldioxydan, tert-butyl perbenzoate, tert-butyl peroxypivalate, tert-hexylperoxy Pivalate, octanoyl peroxide, lauroyl peroxide, and tert-butylperoxy-2-ethylhexanoate are preferred.

(Photopolymerization initiator)
The photopolymerization initiator is not particularly limited as long as it has a function capable of initiating vinyl polymerization of the acrylic group of the compound (A) by photoexcitation. For example, a monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, a benzoin ether compound, Acylphosphine oxide compounds, aminocarbonyl compounds, and the like can be used.

  Specifically, as the monocarbonyl compound, benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 4- (4-methylphenylthio) phenyl -Ethanone, 3,3'-dimethyl-4-methoxybenzophenone, 4- (1,3-acryloyl-1,3,3'-dimethyl-4-methoxybenzophenone, 4- (1,3-acryloyl-1,4) , 7,10,13-pentaoxotridecyl) benzophenone, 3,3 ′, ′, 4,4 ′ ″-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N, N-trimethyl-1 -Propanamine hydrochloride, 4-benzoyl-N, N-dimethyl-N-2- (1-oxo-2-propenyloxy) (Ciethyl) metaammonium oxalate, 2- / 4-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-hydroxy-3- (3 4-dimethyl-9-oxo-9H thioxanthone-2-yloxy-N, N, N-trimethyl-1-propanamine hydrochloride, benzoylmethylene-3-methylnaphtho (1,2-d) thiazoline, and the like.

Examples of dicarbonyl compounds include 1,2,2-trimethyl-bicyclo [2.1.1] heptane-2,3-dione, benzyl, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxobenzene. Examples include acetate and 4-phenylbenzyl.
Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-Isopropylphenyl) -2-hydroxy-di-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one Polymer, diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1-one, 2-methyl-1 -[4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethyla Mino-1- (4-morpholinophenyl) butan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2-morpholino -Propanonyl) -9-butylcarbazole and the like.

Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether.
Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-n-propylphenyl-di (2,6-dichlorobenzoyl) phosphine oxide, and the like.

Examples of aminocarbonyl compounds include methyl-4- (dimethoxyamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-n-butoxyethyl-4- (dimethylamino) benzoate, and isoamyl-4- (dimethylamino) benzoate. 2- (dimethylamino) ethyl benzoate, 4,4′-bis-4-dimethylaminobenzophenone, 4,4′-bis-4-diethylaminobenzophenone, 2,5′-bis (4-diethylaminobenzal) ) Cyclopentanone and the like.
Commercially available photopolymerization initiators include Irgacure 184, 651, 500, 907, 127, 369, 784, 2959, manufactured by Ciba Specialty Chemicals Co., Ltd., Lucilin TPO manufactured by BASF, Esacure One manufactured by Nippon Sibel Hegner, Inc. can give.

The polymerization initiator is not limited to the above compound, and any polymerization initiator may be used as long as it has the ability to initiate polymerization by heat or ultraviolet rays. These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator used is not particularly limited, but the total amount of the polymerizable compound including the compound (A) (in the case where a polymerizable compound other than the compound (A) is included, other than the compound (A) and the compound (A) The total amount of the polymerizable compounds) is preferably within the range of 0.5 to 20 parts by weight per 100 parts by weight.
Furthermore, the polymerization initiator can be used in combination with an initiator for cationic polymerization in addition to the initiator for radical polymerization. Moreover, a well-known organic amine etc. can also be added as a sensitizer.

The composition for insulating film formation may contain other binder resin and polymerizable compounds other than the compound (A) in addition to the compound (A).
Examples of the binder resin include polyurethane resin, polyurea resin, polyurethane urea resin, polyester resin (excluding compound (A)), polyether resin, polycarbonate resin, epoxy resin, amino resin, styrene resin, acrylic resin, melamine resin, A polyamide resin, a phenol resin, a vinyl resin, etc. are mentioned. These resins may be used alone or in combination of two or more. The binder resin is preferably used within a range of 20 parts by weight or less based on the total amount of solids (components other than the solvent; hereinafter the same) of the composition for forming an insulating film as a reference (100 parts by weight).

  Examples of the polymerizable compound include compounds having a polymerizable unsaturated double bond group such as (meth) acrylic compounds, fatty acid vinyl compounds, alkyl vinyl ether compounds, α-olefin compounds, vinyl compounds, and ethynyl compounds. it can. These compounds having a polymerizable unsaturated double bond group may further have a functional group such as a hydroxyl group, an alkoxy group, a carboxyl group, an amide group, or a silanol group. This polymerizable compound is preferably used in a range of less than 50 parts by weight, particularly in a range of 5 to 40 parts by weight, based on the total solid content of the composition for forming an insulating film (100 parts by weight).

  Examples of the (meth) acrylic compound include benzyl (meth) acrylate, alkyl (meth) acrylate, alkylene glycol (meth) acrylate, a compound having a carboxyl group and a polymerizable unsaturated double bond, and a hydroxyl group (meta ) Acrylic compounds, nitrogen-containing (meth) acrylic compounds, and the like. Moreover, a monofunctional compound and a polyfunctional compound (except a compound (A)) can be used suitably. From the viewpoint of polymerizability and solvent resistance, polyfunctional ones are preferred.

  Specific examples of monofunctional (meth) acrylic compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl ( (Meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (medium) ) Acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, heneicosyl (meth) acrylate, alkylene (meth) acrylate having 1 to 22 carbon atoms such as docosyl (meth) acrylate. In the case of adjusting the polarity, it is preferable to use an alkyl group-containing (meth) acrylate having an alkyl group having 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms. For the purpose of adjusting the leveling property, it is preferable to use an alkyl (meth) acrylate having an alkyl group having 6 or more carbon atoms.

  Examples of alkylene glycol (meth) acrylates include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, and polyethylene glycol mono (meth). A polyoxyalkylene chain having a hydroxyl group at the terminal, such as acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol (meth) acrylate, etc. (Meth) acrylate having methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate , Methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate, n-butoxytetraethylene glycol (meth) acrylate, n- Pentaxytetraethylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxytetrapropylene glycol (meth) acrylate, ethoxytetrapropylene glycol (meth) ) Acrylate, propoxytetrapropylene glycol (meth) acrylate, n-butoxy Tetrapropylene glycol (meth) acrylate, n-pentoxytetrapropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol Mono (meth) acrylate having an alkoxy group at the terminal and having a polyoxyalkylene chain, such as (meth) acrylate; phenoxydiethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, Phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylic Examples thereof include polyoxyalkylene (meth) acrylates having a phenoxy or aryloxy group at the terminal, such as rate, phenoxypolyethylene glycol (meth) acrylate, and phenoxytetrapropylene ethylene glycol (meth) acrylate.

  Examples of the compound having a carboxyl group and a polymerizable unsaturated double bond include maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, phthalic acid β- (meth) acryloxyethyl monoester , Isophthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid and the like.

  Examples of hydroxyl group-containing (meth) acrylic compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and 4-hydroxyvinylbenzene. , 2-hydroxy-3-phenoxypropyl (meth) acrylate and the like.

  Nitrogen-containing (meth) acrylic compounds include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- ( Monoalkylol (meth) acrylamide such as (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, N, N-di (methylol) acrylamide, N-methylol-N- Methoxymethyl (meth) acrylamide, N, N-di (methylol) acrylamide, N-ethoxymethyl-N-methoxymethyl methacrylamide, N, N-di (ethoxymethyl) acrylaminide, N-ethoxymethyl-N-propoxy Methyl methacrylate N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) meta Acrylamide-type unsaturated compounds such as acrylamide, N, N-di (pentoxymethyl) acrylamide, dialalkylol (meth) acrylamide such as N-methoxymethyl-N- (pentoxymethyl) methacrylamide; dimethylaminoethyl (meth) acrylate , Unsaturated compounds having a dialkylamino group such as diethylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, diethylaminostyrene, and the like; and C-, Br-, I- Gen'ion or QSO3-: there are quaternary ammonium salts of dialkylamino group-containing unsaturated compound having a (Q alkyl group having 1 to 12 carbon atoms).

  Other unsaturated compounds include perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2- Perfluorooctylethyl (meth) acrylate, 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl (meth) Perfluoroalkanes having 1 to 20 carbon atoms such as acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctyl amyl (meth) acrylate, perfluorooctyl undecyl (meth) acrylate Can be mentioned perfluoroalkyl alkyl (meth) acrylates having an Le group.

  Furthermore, perfluoroalkyl group-containing vinyl monomers such as perfluoroalkyl, alkylene, etc. such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, and perfluorodecylethylene; vinyltrichlorosilane, vinyltris (β-methoxyethoxy) Examples include alkoxysilyl group-containing vinyl compounds such as silane, vinyltriethoxysilane, and γ- (meth) acryloxypropyltrimethoxysilane and derivatives thereof; glycidyl group-containing acrylates such as glycidyl acrylate and 3,4-epoxycyclohexyl acrylate.

  Examples of the fatty acid vinyl compound include vinyl acetate, vinyl butyrate, vinyl crotonic acid, vinyl caprylate, vinyl laurate, vinyl chloroacetate, vinyl oleate, and vinyl stearate. Examples of the alkyl vinyl ether compound include butyl vinyl ether and ethyl vinyl ether.

Examples of the α-olefin compound include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and the like.
Examples of the vinyl compound include allyl compounds such as allyl acetic acid, allyl alcohol, allyl benzene, and allyl cyanide, vinyl cyanide, vinyl cyclohexane, vinyl methyl ketone, styrene, α-methyl styrene, 2-methyl styrene, chlorostyrene, and the like. It is done.
Examples of the ethynyl compound include acetylene, ethynylbenzene, ethynyltoluene, 1-ethynyl-1-cyclohexanol and the like.
These may be used alone or in combination of two or more.

Among these, as photocurable compounds other than the compound (A), polyurethane poly (meth) acrylate and polyepoxy poly (meth) acrylate having at least three functional groups from the viewpoints of coating film strength and scratch resistance. Poly (meth) acrylates such as polyfunctional acrylates having 3 or more acryloyl groups in the molecule can be suitably used.
Polyepoxy poly (meth) acrylate is obtained by esterifying an epoxy group of an epoxy resin with (meth) acrylic acid and converting the functional group to a (meth) acryloyl group, and (meth) acrylic to a bisphenol A type epoxy resin. There are acid addition products, (meth) acrylic acid addition products to novolac type epoxy resins, and the like.

  Polyurethane poly (meth) acrylate is, for example, one obtained by reacting diisocyanate with (meth) acrylate having a hydroxyl group, or isocyanate group-containing urethane obtained by reacting polyol and polyisocyanate under the condition of excess isocyanate group. Some are obtained by reacting a prepolymer with (meth) acrylates having a hydroxyl group. Alternatively, a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under hydroxyl-excess conditions can be obtained by reacting with a (meth) acrylate having an isocyanate group.

  Examples of polyols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentane glycol, neopentyl glycol, hexanetriol, trimellilol propane, polytetra Examples include methylene glycol and a condensation polymer of adipic acid and ethylene glycol.

Examples of the polyisocyanate include tolylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.
Examples of (meth) acrylates having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (Meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and the like.
Examples of the (meth) acrylates having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and (meth) acryloyl isocyanate.

The following can be illustrated as a commercial item of a polymeric compound.
Toa Gosei Co., Ltd .: Aronix M-400, Aronix M-402, Aronix M-408, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060,
Osaka Organic Chemical Industry Co., Ltd .: Biscote # 400
Kayaku Sartomer Co., Ltd .: SR-295,
Daicel UCB Co., Ltd .: DPHA, Ebecryl 220, Ebecryl 1290K, Ebecryl 5129, Ebecryl 2220, Ebecryl 6602,
Shin-Nakamura Chemical Co., Ltd .: NK Ester A-TMMT, NK Ester A-BPEF, NK Oligo EA-1020, NK Oligo EMA-1020, NK Oligo EA-6310, NK Oligo EA-6320, NK Oligo EA-6340 , NK oligo MA-6, NK oligo U-4HA, NK oligo U-6HA, NK oligo U-324A,
Manufactured by BASF: LaromerEA81,
Sannopco: Photomer 3016,
Arakawa Chemical Industries, Ltd .: beam set 371, beam set 575, beam set 577, beam set 700, beam set 710;
Manufactured by Negami Kogyo Co., Ltd .: Art Resin UN-3320HA, Art Resin UN-3320HB, Art Resin UN-3320HC, Art Resin UN-3320HS, Art Resin UN-9000H, Art Resin UN-901T, Art Resin HDP, Art Resin HDP -3, Art resin H61,
Nippon Synthetic Chemical Industry Co., Ltd .: Violet UV-7600B, Violet UV-7610B, Violet UV-7620EA, Violet UV-7630B, Violet UV-1400B, Violet UV-1700B, Violet UV-6300B,
Kyoeisha Chemical Co., Ltd .: Light acrylate PE-4A, Light acrylate DPE-6A, UA-306H, UA-306T, UA-306I,
Nippon Kayaku Co., Ltd .: KAYARAD DPHA, KAYARAD DPHA2C, KAYARAD DPHA-40H, KAYARAD D-310, KAYARAD D-330.
Osaka Gas Chemical Co., Ltd .: OGSOL EA-2000, OGSOL EA-3000, OGSOL GA-5000.

<Manufacture of insulating film forming composition and insulating film>
The composition for forming an insulating film of the present invention can be produced by dispersing the metal oxide (B) in the compound (A) and blending and mixing a polymerization initiator and other components as necessary. it can. When stirring and mixing, it may be prepared by stirring and mixing using a general-purpose device such as a uniaxial or multiaxial extruder, a kneader, or a dissolver equipped with a decompression device. Usually, the temperature at the time of stirring and mixing is preferably set to 10 to 60 ° C. By setting the temperature to 10 to 60 ° C., more uniform stirring and mixing are possible, and the curing reaction due to heat is suppressed, which is preferable.

  A known method may be used to apply the insulating film forming composition onto the substrate. Examples of the application method include an inkjet method, a spray method, a spin coating method, a dip method, a roll coating method, and a blade coating method. Method, doctor roll method, doctor blade method, curtain coating method, slit coating method, screen printing method, reverse printing method and the like.

The composition for forming an insulating film in the present invention is typically applied and used so that an insulating film having a thickness of 5000 nm or less is formed.
The thickness of the insulating film formed by coating is preferably 100 to 5000 nm, and more preferably 300 to 3000 nm. If the thickness of the insulating layer is 100 nm or less, the insulating property of the insulating film may be insufficient, and stable coating may be difficult. On the other hand, if the thickness of the resin layer exceeds 5000 nm, the function as a capacitor may be reduced and power consumption may be increased.

  There is no restriction | limiting in particular in a drying method, The thing using hot air drying, infrared rays, and the pressure reduction method is mentioned. As drying conditions, hot air heating of about 60 to 200 ° C. is usually used, although it depends on the crosslinked and cured form of the composition for forming an insulating film, the film thickness and the selected organic solvent. Moreover, when using plastic films, such as PET and PEN, as a base material, since a base material may deform | transform with heat, 60-150 degreeC is more preferable.

  The curing treatment can be performed by irradiating active energy rays such as ultraviolet rays, electron beams, visible rays having a wavelength of 400 to 500 nm, using a known technique. For example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used as a source (light source) of ultraviolet rays and visible light having a wavelength of 400 to 500 nm. As the electron beam source, a thermionic emission gun, an electrolytic emission gun, or the like can be used.

  Moreover, the process by thermosetting can also be used conveniently. Specifically, the same conditions as in the drying treatment can be used, and usually hot air heating at about 60 to 200 ° C. is used. It is also possible to form an insulating film only by curing with heat, or to form an insulating film by a combination of curing with active energy rays such as ultraviolet rays and thermal curing. Among these, a combination of curing with active energy rays and thermosetting is preferable.

<Gate insulation film>
The gate insulating film can be made into an insulating film by curing the composition for forming an insulating film of the present invention. For example, an insulating film can be obtained by applying and curing the insulating material of the present invention on a substrate. In order to form the insulating film, the insulating material of the present invention can be directly applied to the substrate to be formed by applying, coating, printing or the like and curing. Further, after being developed on another substrate or mold and cured, it may be used for various electronic members as an insulating film, and the insulating material is formed on a film by a known molding method such as extrusion molding. In addition, an insulating film obtained by curing may be used.

  As a base material used for the insulating film of the present invention, a plastic film, a metal plate, or a glass plate is used, and examples of the plastic film include transparency, coloring stability, mechanical strength, thermal stability, and moisture. Various films composed of a thermoplastic resin excellent in properties such as barrier properties, isotropic properties, and design properties are used, which are also referred to as various plastic sheets and are not particularly limited. Specific examples include, for example, polyvinyl alcohol films, polytriacetyl cellulose films, polyolefin films such as polypropylene, polyethylene, polycycloolefin, and ethylene-vinyl acetate copolymers, polyester films such as polyethylene terephthalate and polybutylene terephthalate, Polycarbonate film, polynorbornene film, polyarylate film, polyacrylic film, polyphenylene sulfide film, polystyrene film, polyvinyl chloride film, polyamide film, polyimide film, polyfluorine film and polyoxirane film A film etc. are mentioned. The thickness of the plastic film that can be laminated is not particularly limited. For example, a film having a thickness of 500 μm can be used.

  Among these, the composition for forming an insulating film of the present invention can cause a crosslinking reaction to proceed even under conditions of a low temperature of 150 ° C. or lower, even when using thermal polymerization, so a polyester film, a polycarbonate film, A plastic film such as a polyimide film is more preferable.

  In addition, plastic film has a surface with physical treatment such as corona discharge, plasma treatment, flame treatment, etc., chemical treatment that modifies the film surface with acid or alkali, etc. Film with increased surface area, or plastic film with deposited metal oxide such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, yttrium, or non-metallic inorganic oxide For the insulating film forming composition, those that have been subjected to an easy adhesion treatment and those that have been provided with functionality for each application can be suitably used.

<Thin film transistor>
Examples of electrode materials (gate electrode, source electrode, drain electrode) used in the thin film transistor of the present invention include metals such as gold, silver, copper, aluminum, and calcium, and inorganic materials such as carbon black, fullerenes, and carbon nanotubes. Furthermore, organic π conjugated polymers such as polythiophene, polyaniline, polypyrrole, polyfluorene, and derivatives thereof can be used.

  Generally, vacuum deposition, sputtering, etc. are used as the electrode formation method, but in order to simplify the manufacturing method, electrode formation methods by spray coating, printing, ink jet, etc. are proposed. Has been. In recent years, a coating method for forming a high-definition electrode pattern by partially changing the surface energy of the gate insulating film by ultraviolet irradiation has been proposed. Examples of electrode materials that can be applied include nano metal fine particles and organic π-conjugated polymers.

  When the electrode is formed by the coating method, the gate insulating film is required to have solvent resistance since it is applied onto the gate insulating film of the present invention. As the solvent used for the nano metal ink and the organic π-conjugated polymer, various alcohols are preferable. Also, N, N-dimethylformamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, n-ethyl-2-pyrrolidone, n-vinyl-2-pyrrolidone, N-methylcaprolactol Polar solvents such as dimethyl sulfoxide, tetramethylurea and the like are also preferable from the viewpoint of excellent solubility of the electrode material, but these are preferably used in a small amount within a range where damage to the gate insulating film of the present invention is small.

The material used for the semiconductor layer included in the thin film transistor of the present invention is not particularly limited as long as it can be formed on the gate insulating film of the present invention, on the above electrode, and on the above plastic substrate. Organic low molecular weight materials such as oligothiophene derivatives and phthalocyanine derivatives, π conjugated polymers such as polythiophene derivatives, polyphenylene vinylene derivatives and polyfluorene derivatives, oxides such as InGaZnO, InGaO, ZnGaO, InZnO, ZnO and SnO ₂ A semiconductor etc. are mentioned.

  As a method for forming these semiconductor materials, a sputtering method, a vacuum evaporation method, an inkjet method, a spray method, or the like can be used. In particular, coating methods such as an ink jet method and a spray method are preferable because they are simple and can reduce manufacturing costs.

Hereinafter, the present invention will be described in more detail based on production examples and examples. Unless otherwise specified, parts and% represent parts by mass and% by mass, respectively.
The raw materials used are as follows.

<Carboxylic anhydride>
BPDA: manufactured by Mitsubishi Chemical Corporation, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride BPAF: manufactured by JFE Chemical Corporation, 9,9-bis (3,4-dicarboxyphenyl) fluorene Diacid anhydride Ricacid BT-100: manufactured by Shin Nippon Rika Co., Ltd., 1,2,3,4-butanetetracarboxylic dianhydride PMDA: manufactured by Daicel Corporation pyromellitic dianhydride, 1,2, 4,5-benzenetetracarboxylic dianhydride phthalic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.)

<Compound (x2)>
KAYARAD PET-30: (Nippon Kayaku Co., Ltd., pentaerythritol triacrylate (1), including pentaerythritol tetraacrylate as a by-product)
A-TMM-3LM-N: (made by Shin-Nakamura Chemical Co., Ltd., pentaerythritol triacrylate (2), including pentaerythritol tetraacrylate as a by-product)
A-9570W: (Shin Nakamura Chemical Co., Ltd., dipentaerythritol pentaacrylate, including dipentaerythritol hexaacrylate as a by-product)
<Acrylate compound>
2HEA: Nippon Shokubai Co., Ltd., 2-hydroxyethyl acrylate

<Polymerization inhibitor>
Methylhydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.)

<Catalyst>
1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.)
Dimethylbenzylamine (Wako Pure Chemical Industries, Ltd.)

<Epoxy group-containing compound>
Methacryl glycidyl ether (manufactured by Dow Chemical Japan Co., Ltd., GMA)
4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd., trade name: 4 hydroxybutyl acrylate glycidyl ether)
2-Phenylphenol glycidyl ether (manufactured by Sanko Co., Ltd., trade name: OPP-G)

<Synthesis of compound (A) having 6 or more acryloyl groups>
(Synthesis Example 1: Compound (A-1))
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 80.0 parts of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pentavalent hydroxyl group 122 mgKOH / g penta 250.0 parts of erythritol triacrylate (1), 0.24 parts of methylhydroquinone and 217.8 parts of cyclohexanone were charged, and the temperature was raised to 60 ° C. Next, 1.65 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780-cm and 1850 cm-1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this point, the acid value of the reaction product was measured by a conventional method and found to be 94 mgKOH / g.
Subsequently, 140.0 parts of 2-phenylphenol glycidyl ether and 91.0 parts of cyclohexanone were added to the solution, and then 2.65 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C. for 6 hours to be reacted. . Resin containing compound (A-1) by measuring the acid value of the reaction product periodically while continuing the reaction, when the acid value became 5.0 mgKOH / g or less, cooling to room temperature and stopping the reaction A varnish was obtained. The obtained resin varnish is light yellow and transparent, the solid content is 60%, and the final acid value is 3.0 mgKOH / g. Therefore, the compound (A) in the reaction product solid content of the obtained resin varnish The containing reactant is 79%.
The reactant containing the compound (A) represents a high molecular weight reactant derived from a byproduct containing a plurality of hydroxyl groups in the compound (x2) in addition to the compound (A). The ratio of the reaction product containing the compound (A) was calculated from the final acid value of the resin varnish. The rest represents a compound having no hydroxyl group or an unreacted raw material in the compound (x2) used in the reaction. In the table, the reactant containing the compound (A) is abbreviated as “reactant”. The same applies to the following synthesis 2 to 5.

(Synthesis Example 2 Compound (A-2))
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, pentaerythritol tris with 80.0 parts 1,2,3,4-butanetetracarboxylic dianhydride and hydroxyl value 113 mgKOH / g Acrylate (2) 402.0 parts, methylhydroquinone 0.33 part, cyclohexanone 318.0 parts were charged, and the temperature was raised to 60 ° C. Next, 2.41 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780-cm and 1850 cm-1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this point, the acid value of the reaction product was measured by a conventional method and found to be 95 mgKOH / g.
Subsequently, 182.9 parts of 2-phenylphenol glycidyl ether and 118.0 parts of cyclohexanone were added to this solution, and then 3.88 parts of dimethylbenzylamine was added as a catalyst, followed by stirring at 100 ° C. for 6 hours. A resin containing the compound (A-2) is measured by periodically measuring the acid value of the reactant while continuing the reaction, and when the acid value becomes 5.0 mgKOH / g or less, the reaction is stopped by cooling to room temperature. A varnish was obtained. The obtained resin varnish was light yellow and transparent, had a solid content of 60%, and the final acid value was 3.0 mgKOH / g. Therefore, the reaction product containing the compound (A) in the obtained reaction product solid content Is 73%.

(Synthesis Example 3 Compound (A-3))
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, 80.0 parts of 1,2,4,5-benzenetetracarboxylic dianhydride and pentaerythritol tris having a hydroxyl value of 113 mgKOH / g Acrylic (2) 364.9 parts, methylhydroquinone 0.31 part, cyclohexanone 294.1 parts were charged, and the temperature was raised to 60 ° C. Next, 2.22 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780-cm and 1850 cm-1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this point, the acid value of the reaction product was measured by a conventional method and found to be 93 mgKOH / g.
Subsequently, 166.0 parts of 2-phenylphenol glycidyl ether and 107.1 parts of cyclohexanone were added to this solution, and then 3.58 parts of dimethylbenzylamine was added as a catalyst, followed by stirring at 100 ° C. for 6 hours. The reaction was terminated by cooling to. A resin containing compound (A-3) is measured by periodically measuring the acid value of the reaction product while continuing the reaction, and when the acid value becomes 5.0 mgKOH / g or less, the reaction is stopped by cooling to room temperature. A varnish was obtained. The obtained resin varnish was light yellow and transparent, the solid content was 60%, and the final acid value was 3.2 mgKOH / g. Therefore, the reaction product containing the compound (A) in the obtained reaction product solid content Is 74%.

(Synthesis Example 4 Compound (A-4))
In a four-necked flask equipped with a stirrer, a reflux condenser, a dry air introduction tube, and a thermometer, 90.0 parts of 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, a hydroxyl value of 122 mgKOH / g 160.2 parts of pentaerythritol triacrylate (1), 0.16 parts of methylhydroquinone, and 158.8 parts of cyclohexanone were charged, and the temperature was raised to 60 ° C. Next, 1.20 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780-cm and 1850 cm-1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this point, the acid value of the reaction product was measured by a conventional method and found to be 82 mgKOH / g.
Thereafter, 79.0 parts of 2-phenylphenol glycidyl ether and 50.7 parts of cyclohexanone were added. Then, 1.93 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C. for 6 hours. The acid value of the reaction product was measured, and when the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature to obtain a resin varnish containing the compound (A-4). Since the obtained resin varnish was light yellow and transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH / g, the reaction containing the compound (A) in the solid content of the obtained resin varnish. The thing is 79%.

(Synthesis Example 5 Compound (A-5))
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 80.0 parts of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and a hydroxyl value of 85 mgKOH / g The mixture was charged with 359.0 parts of pentaerythritol pentaacrylate, 0.29 parts of methylhydroquinone and 290.1 parts of cyclohexanone and heated to 60 ° C. Next, 2.19 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780-cm and 1850 cm-1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this point, the acid value of the reaction product was measured by a conventional method and found to be 74 mgKOH / g.
Thereafter, 78.3 parts of methacryl glycidyl ether and 48.7 parts of cyclohexanone were added, and then 3.53 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C. for 6 hours. When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature to obtain a resin varnish containing the compound (A-5). The obtained resin varnish was light yellow and transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH / g. Therefore, the reaction product in the solid content of the obtained resin varnish is 69%. .

(Synthesis Example 6 Compound (A-6))
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 80.0 parts of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pentavalent hydroxyl group 122 mgKOH / g penta 250.0 parts of erythritol triacrylate (1), 0.24 parts of methylhydroquinone and 217.8 parts of cyclohexanone were charged, and the temperature was raised to 60 ° C. Next, 1.65 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780-cm and 1850 cm-1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this point, the acid value of the reaction product was measured by a conventional method and found to be 94 mgKOH / g.
Thereafter, 78.3 parts of methacryl glycidyl ether and 54.0 parts of cyclohexanone were added, and then 2.65 parts of dimethylbenzylamine was added as a catalyst, followed by stirring at 100 ° C. for 6 hours. When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature to obtain a resin varnish containing the compound (A-6). The obtained resin varnish was light yellow and transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH / g. Therefore, the reaction product in the solid content of the obtained resin varnish is 76%. .

(Synthesis Example 7 Compound (A-7))
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, pentaerythritol tris with 80.0 parts 1,2,3,4-butanetetracarboxylic dianhydride and hydroxyl value 113 mgKOH / g Acrylate (2) 402.0 parts, methylhydroquinone 0.34 parts, cyclohexanone 203.8 parts were charged, and the temperature was raised to 60 ° C. Next, 1.75 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780-cm and 1850 cm-1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this point, the acid value of the reaction product was measured by a conventional method and found to be 95 mgKOH / g.
Thereafter, 116.4 parts of methacryl glycidyl ether and 188.5 parts of cyclohexanone were added, and then 3.88 parts of dimethylbenzylamine was added as a catalyst and stirred at 100 ° C. for 6 hours. When the acid value was 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature to obtain a resin varnish containing the compound (A-7). The obtained resin varnish was light yellow and transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH / g. Therefore, the reaction product in the solid content of the obtained resin varnish is 71%. .

(Synthesis Example 8 Compound (A-8))
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 80.0 parts of 1,2,4,5-benzenetetracarboxylic dianhydride and pentaerythritol tris having a hydroxyl value of 122 mgKOH / g Acrylate (2) 268.7 parts, methylhydroquinone 0.25 parts, cyclohexanone 230.4 parts were charged, and the temperature was raised to 60 ° C. Next, 1.74 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780-cm and 1850 cm-1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this point, the acid value of the reaction product was measured by a conventional method and found to be 88 mgKOH / g.
Thereafter, 110 parts of 4-hydroxybutyl acrylate glycidyl ether and 69.1 parts of cyclohexanone were added, and then 2.80 parts of dimethylbenzylamine was added as a catalyst, stirred at 100 ° C. for 6 hours, and periodically while continuing the reaction. The acid value of the reaction product was measured, and when the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature to obtain a resin varnish containing the compound (A-8). Since the obtained resin varnish was light yellow and transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH / g, the reaction product in the solid content of the obtained resin varnish was 72%. .

(Comparative Synthesis Example 1: Comparative Compound (A-1))
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 80.0 parts of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2 of hydroxyl value 483 mgKOH / g -63.1 parts of hydroxyethyl acrylate, 0.11 part of methylhydroquinone and 94.6 parts of cyclohexanone were charged, and the temperature was raised to 60 ° C. Next, 0.72 part of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780-cm and 1850 cm-1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this point, the acid value of the reaction product was measured by a conventional method and found to be 215 mgKOH / g.
Thereafter, 78.3 parts of methacryl glycidyl ether and 51.1 parts of cyclohexanone were added, and then 1.15 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C. for 6 hours. When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature to obtain a resin varnish containing the comparative compound (A-1). Since the obtained resin varnish was light yellow and transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH / g, the reaction product in the solid content of the obtained resin varnish was 87%. .

(Comparative Synthesis Example 2: Comparative Compound (A-2))
In a 4-neck flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 80.0 parts 1,2,3,4-butanetetracarboxylic dianhydride, 2-hydroxy having a hydroxyl value of 483 mgKOH / g 93.7 parts of ethyl acrylate, 0.15 parts of methylhydroquinone and 114.8 parts of cyclohexanone were charged, and the temperature was raised to 60 ° C. Next, 0.87 part of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780-cm and 1850 cm-1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this point, the acid value of the reaction product was measured by a conventional method and found to be 264 mgKOH / g.
Thereafter, 116.4 parts of methacryl glycidyl ether and 76.2 parts of cyclohexanone were added, and then 1.4 parts of dimethylbenzylamine was added as a catalyst, followed by stirring at 100 ° C. for 6 hours. When the acid value was 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature to obtain a resin varnish containing the comparative compound (A-2). The obtained resin varnish was light yellow and transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH / g. Therefore, the reaction product in the solid content of the obtained resin varnish was 86%. .

(Comparative Synthesis Example 3: Comparative Compound (A-3))
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 80.0 parts of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2 of hydroxyl value 483 mgKOH / g -63.1 parts of hydroxyethyl acrylate, 0.11 part of methylhydroquinone and 94.6 parts of cyclohexanone were charged, and the temperature was raised to 60 ° C. Next, 0.72 part of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780-cm and 1850 cm-1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this point, the acid value of the reaction product was measured by a conventional method and found to be 215 mgKOH / g.
Thereafter, 123.1 parts of 2-phenylphenol glycidyl ether and 80.9 parts of cyclohexanone were added, and then 1.15 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C. for 6 hours. The acid value of the reaction product was measured, and when the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature to obtain a resin varnish containing the comparative compound (A-3). Since the obtained resin varnish was light yellow and transparent, the solid content was 60%, and the final acid value was 3.0 mgKOH / g, the reaction product in the solid content of the obtained resin varnish was 89%. .

(Comparative Synthesis Example 4: Comparative compound (A-4))
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 80.0 parts of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and a hydroxyl value of 85 mgKOH / g The mixture was charged with 359.0 parts of pentaerythritol pentaacrylate, 0.29 parts of methylhydroquinone and 290.1 parts of cyclohexanone and heated to 60 ° C. Next, 2.19 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. After confirming that the peaks of acid anhydride groups, that is, peaks near 1780-cm and 1850 cm-1, disappeared by IR measurement of the reaction product, the reaction product was cooled to stop the reaction. At this point, the acid value of the reaction product was measured by a conventional method and found to be 74 mgKOH / g.
The resin varnish containing the comparative compound (A-4) was obtained without carrying out the subsequent reaction with the epoxy group-containing compound. The obtained resin varnish was light yellow transparent and had a solid content of 60%.

  Table 1 shows an outline of the compounds obtained in Synthesis Examples 1 to 8 and Comparative Synthesis Examples 1 to 4.

BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride PMDA: 1,2,4,5-benzenetetracarboxylic dianhydride BPAF: 9,9-bis (3,4-dicarboxy) Phenyl) fluorene dianhydride BT-100: 1,2,3,4-butanetetracarboxylic dianhydride PET30: mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate A-TMM-3LM-N: pentaerythritol tri Mixture of acrylate and pentaerythritol tetraacrylate DPPA: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate 2HEA: 2-hydroxyethyl acrylate OPP-G: 2-phenylphenol glycidyl ether GMA: Glycidi Methacrylate 4HBAGE: 4- hydroxybutyl acrylate glycidyl ether DBU: 1,8-diazabicyclo [5.4.0] DMBA: dimethylbenzylamine

<Preparation of metal oxide dispersion paste>
(Adjustment of metal oxide dispersion pastes (P-1) to (P-28))
Using the resin varnish containing each of the synthesized compounds, the metal oxide (B) was dispersed according to the formulation shown in Tables 2 and 3 to prepare a metal oxide dispersion paste. A compounding quantity shows solid content. Dispersion method uses zirconia beads (0.5 mm) as a medium, disperses for 1 hour with a paint shaker (pre-dispersion), and then uses zirconia beads (0.1 mm) as a medium. It was carried out in two stages of this dispersion at −015.

In Tables 2 and 3,
TiO ₂ : “MT-05” (average primary particle size: 10 nm) manufactured by Teika Co., Ltd.
ZrO ₂ : “PCS-60” manufactured by Nippon Electric Works Co., Ltd. (average primary particle size: 20 nm)
BaTiO ₃ -1: “KZM-50” manufactured by Sakai Chemical Industry Co., Ltd. (average primary particle size: 20 nm)
BaTiO ₃ -2: “Barium titanate” manufactured by Kanto Denka Kogyo Co., Ltd. (average primary particle size: 25 nm)
ZnO: “FINEX-50” manufactured by Sakai Chemical Industry Co., Ltd. (average primary particle size: 20 nm)
SiO ₂ : “AEROSIL50” manufactured by Nippon Aerosil Co., Ltd. (average primary particle size: 50 nm)
MEK: methyl ethyl ketone IPA: isopropyl alcohol

<Dispersibility evaluation of metal oxide dispersion paste>
[State immediately after distribution]
The state of the obtained metal oxide dispersion paste was visually observed and evaluated according to the following criteria.
A: There is fluidity.
B: Solidified, but fluidity can be confirmed if shaken vigorously.
C: Solidified.

[D50 particle size]
The D50 particle size of the obtained metal oxide paste was measured using “Nanotrack UPA” manufactured by Nikkiso Co., Ltd. Practically, it must be 200 nm or less.

<Manufacture of composition for insulating film formation>
[Examples 1 to 16, Comparative Examples 1 to 9]
(Production of insulating film forming compositions (S-1) to (S-33))
As shown in Tables 4 and 5, with respect to 100 parts of each metal oxide paste obtained above, 1.0 part of photopolymerization initiator (“Irgacure 184” manufactured by BASF) and thermal polymerization initiator (day “Perbutyl O” manufactured by Oil Co., Ltd.) and 27 parts of solvent cyclohexanone were mixed, stirred and dissolved to obtain insulating film forming compositions (S-1) to (S-33).

<Evaluation of composition for insulating film formation>
[Creation of insulating film]
The obtained composition for forming an insulating film was dropped onto a 200 μm aluminum plate and a 120 μm PEN film with a syringe with a 1 μm pore filter, and each was applied by spin coating. Then, after irradiating ultraviolet rays of 400 mJ / cm ² with a high-pressure mercury lamp, heat treatment was performed at 130 ° C. for 30 minutes to obtain an aluminum plate and a PEN film coated with an insulating film having a thickness of 1000 nm. The following evaluation was performed about the obtained insulating film. The results are shown in Tables 4 and 5.

[Solvent resistance test]
Using a PEN film with an insulating film, several drops of o-dichlorobenzene and butyl carbitol acetate were dropped with a dropper, exposed to each solvent for 5 minutes and 60 minutes, wiped off, and the appearance was evaluated in three stages. In the case of “△” evaluation or higher, there is no problem in actual use.
○: No change in appearance after 60-minute immersion.
Δ: No change in appearance after immersion for 5 minutes, but some peeling and swelling of the insulating film are observed after immersion for 60 minutes.
X: Peeling and swelling of the insulating film are observed in part after immersion for 5 minutes.

[Adhesion (cross cut tape test)]
Using a cutter knife, 11 cuts were made on the PEN film with an insulating film at intervals of 1 mm reaching the PEN film, and 100 grids were created. A cellophane tape was strongly pressure-bonded to the cross-cut portion, the end of the tape was peeled off at a 45 ° angle, and the cross-cut state was visually observed and evaluated in three stages. In the case of “△” evaluation or higher, there is no problem in actual use.
○: There is no peeling of the eyes of any lattice.
(Triangle | delta): Peeling has arisen in the range of the area of less than 35% of the coating film partially and entirely along the cut line.
X: The coating film peeled off partially or entirely along the cut line in an area of 35% or more.

[Dielectric breakdown voltage]
Using an aluminum plate with an insulating film, the insulation withstand voltage was evaluated using a TM650 withstand voltage tester (manufactured by Tsuruga Electric Co., Ltd.) and evaluated in three stages. In the case of “△” evaluation or higher, there is no problem in actual use.
○: Dielectric breakdown voltage is 2.0 MV / cm or more.
Δ: Dielectric breakdown voltage is 1.0 MV / cm or more and less than 2.0 MV / cm.
X: Dielectric breakdown voltage is less than 1.0 MV / cm.

[Specific permittivity measurement]
Using an aluminum plate with an insulating film, an aluminum electrode having a thickness of 500 mm and a thickness of 14 mmφ was formed on the insulating film using a vacuum deposition apparatus, and a capacitor was formed. About the created capacitor | condenser, the electrostatic capacitance C (F) of the thin film at the time of 1 kHz and 10V application was measured using the impedance analyzer. The film thickness of the insulating film was measured using a step gauge (manufactured by ULVAC, Dektak). The relative dielectric constant ε of the insulating film was calculated by the following formula and evaluated in three stages. A higher dielectric constant is more preferable because it can increase the capacitance of the capacitor.
ε = C × t / ε ₀ × A
C: capacitance (F), ε ₀ : vacuum dielectric constant (8.85 × 10 ⁻¹² ), t: film thickness (m), A: area (m ² )

○: The relative dielectric constant is 10.0 or more.
Δ: The relative dielectric constant is 5.0 or more and less than 10.0.
X: The relative dielectric constant is less than 5.0.

[Transistor characteristics evaluation]
(Making transistors)
A gate electrode 2 having a thickness of 500 mm is formed on the PEN film (base material) using aluminum (Al), and the insulating film forming composition obtained thereon is applied by spin coating under the conditions of 2000 rpm and 30 sec. The gate insulating film 3 was formed by heat treatment at 130 ° C. for 30 minutes. Further, pentacene is vapor-deposited at a substrate temperature of room temperature and a rate of 0.1 nm / sec to form an organic semiconductor layer 4 having a thickness of 1000 mm, and a mask having a channel length (L) of 80 μm and a channel width (W) of 2 mm. A thin film transistor was manufactured by forming source / drain Au electrodes 5 and 6 having a thickness of 300 mm by vapor deposition. About the created organic thin-film transistor, ON / OFF ratio was evaluated from the curve of the current transfer characteristic on the following drive conditions using the semiconductor characteristic evaluation system 4200 (made by Keithley).

<Drive conditions>
In the manufactured transistor, a source / drain current amount (Id) when a voltage of 20 to −40 V was applied to the gate electrode in a state where a voltage of −40 V was applied between the source and drain was plotted to obtain transfer characteristics.

(ON / OFF current ratio)
The on-state current Ion is the maximum current value in the saturation region in the current transfer characteristic curve, and the off-state current Ioff is obtained from the off-state minimum current. The ON / OFF current ratio Ion / Ioff was calculated from the ratio between the maximum current value in the on state and the minimum current value in the off state. In the case of “△” evaluation or higher, there is no problem in actual use.
A: ON / OFF current ratio is 1.0 × 10 ⁴ or more.
Δ: The ON / OFF current ratio is 1.0 × 10 ³ or more and less than 1.0 × 10 ⁴ .
×: ON / OFF current ratio is less than 1.0 × 10 ³ .

Abbreviations in Tables 4 and 5 are as follows.
Photopolymerization initiator: “Irgacure 184” manufactured by BASF
Thermal polymerization initiator: NOF Corporation "Perbutyl O" (tert-butylperoxy-2-ethylhexanoate)
* 1: Cannot be created because the metal oxide paste was poorly dispersed

As shown in Table 4, the composition for forming an insulating film shown in Examples 1 to 24 is excellent in solvent resistance, and can form an insulating film characterized by having excellent insulating properties and a high dielectric constant. You can see that Among them, the composition for forming an insulating film in which TiO ₂ or BaTiO ₃ is dispersed has high dispersibility stability, and it is easy to achieve both high relative permittivity, solvent resistance, and insulating properties. Furthermore, the composition for forming an insulating film using the compound (A-1) in which R ₁ is (x1-2) having a biphenyl skeleton and R ₃ is a structure represented by the formula (3) is particularly excellent. It was a result. Moreover, the improvement of solvent resistance has been confirmed by using a photoinitiator and a thermal polymerization initiator together. Furthermore, in Comparative Example 1 having only two acryloyl groups, the crosslink density was low, resulting in poor solvent resistance and insulation.

  The composition for forming an insulating film according to the present invention can be suitably used particularly for a plastic film that needs to be crosslinked at a low temperature of 200 ° C. or lower, and is used by applying it to a flexible film by printing, or the gate thereof The present invention can be preferably applied to an organic transistor using an insulating film.

Claims (8)

The composition for insulating film formation containing the compound (A) which has six or more acryloyl groups represented by following General formula (1), a metal oxide (B), and a solvent.
General formula (1)

[In General Formula (1), R ₁ represents any one of the following tetravalent organic residues.

In general formula (1), R ₂ represents any of the following monovalent organic residues.

In general formula (1), R ₃ represents a monovalent organic residue. ]   Furthermore, the composition for insulating film formation of Claim 1 containing a polymerization initiator.   The composition for forming an insulating film according to claim 2, wherein the polymerization initiator includes a thermal polymerization initiator and a photopolymerization initiator.   The insulation according to any one of claims 1 to 3, wherein the metal oxide (B) contains at least one element selected from the group consisting of titanium, zinc, zirconium, indium, tin, aluminum, silicon and phosphorus. Film forming composition.   The composition for forming an insulating film according to any one of claims 1 to 4, wherein the metal oxide (B) is titanium oxide or barium titanate.   The composition for forming an insulating film according to any one of claims 1 to 5, wherein the metal oxide (B) has a D50 particle size of 0.005 to 0.200 µm.   The insulating film which is a hardened | cured material of the composition for insulating film formation as described in any one of Claims 1-6.   A thin film transistor provided with the hardened | cured material of the composition for insulating film formation as described in any one of Claims 1-6 as a gate insulating film.

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