JP5890631B2 - Gate insulating film for organic TFT and organic TFT element having the insulating film - Google Patents

Description

  The present invention relates to a gate insulating film for an organic TFT comprising a curable composition that provides a thin film having excellent surface water repellency and insulating properties, and an organic TFT element having the insulating film.

  In order to develop flexible displays such as electronic paper, which has been attracting attention as the next generation display, organic thin-film transistors that can be easily formed by using a plastic film as a substrate at low temperatures and printing methods have been actively researched and developed. A TFT using a polythiophene compound (Patent Document 1) has been proposed, and a semiconductor material having characteristics similar to those of an aSi TFT used in a liquid crystal display has been found.

  On the other hand, various organic materials have been studied and developed not only for semiconductor materials but also for insulating films such as gate insulating films and passivation films, such as polyvinyl alcohol (Patent Document 1), polyimide-based polymer (Patent Document 2), and silicon-based polymer. A transistor using an organic material such as (Patent Document 3) as an insulating film has been proposed, but it does not show good semiconductor characteristics due to the presence of a polar group such as a hydroxyl group present on the surface of the insulating film. If it is not used after surface treatment, it does not function and requires a complicated process, and an organic insulating film material exhibiting satisfactory characteristics with a single layer without surface treatment has not been obtained.

JP 2007-027524 A JP 2004-349319 A JP 2007-43055 A

In view of the above circumstances, an object of the present invention is to provide an organic TFT gate insulating film made of a curable composition that gives a thin film excellent in surface water repellency and insulating properties, and an organic TFT element having the insulating film.

In view of the above circumstances, as a result of intensive studies by the present inventors, it has been found that the above problems can be solved by using a curable composition having the following features, and the present invention has been completed. That is, the present invention has the following configuration.

  1). For organic TFTs having a water contact angle of 95 degrees or more on the surface of a thin film after curing, which is a curable composition containing as a main component a compound selected from an epoxy group-containing compound, a (meth) acryloyl group-containing compound, and a phenol group-containing compound Gate insulation film.

  2). The gate insulating film for organic TFTs according to 1), wherein the curable composition contains a polysiloxane compound having an average weight molecular weight of 500 to 10,000.

  3). 2. The gate insulating film for an organic TFT according to 2), wherein the polysiloxane compound contains one kind of reactive functional group selected from vinyl group, SiH group, methacryl group, epoxy group, and amino group.

  4). The gate insulating film for an organic TFT according to any one of 1) to 3), wherein the epoxy group-containing compound, the (meth) acryloyl group-containing compound, and the phenol group-containing compound are polysiloxane compounds.

  5). The organic TFT according to any one of 1) to 4), wherein the epoxy group-containing compound, the (meth) acryloyl group-containing compound, and the phenol group-containing compound have an alkenyl group or SiH group in the same molecule. Gate insulation film.

  6). Epoxy group-containing compounds, (meth) acryloyl group-containing compounds, and phenol group-containing compounds are represented by the following general formula (I)

The gate insulating film for organic TFTs according to any one of 1) to 5), wherein the gate insulating film is a compound containing a structure represented by:

  7). It has alkali developability, The gate insulating film for organic TFTs as described in any one of 1) -6) characterized by the above-mentioned.

  8). The epoxy group-containing compound and the (meth) acryloyl group-containing compound contain at least one selected from the group consisting of each structure represented by the following formulas (X1) and (X2) and a carboxyl group. The gate insulating film for organic TFT as described in any one of 1) -7).

  9). The organic TFT element which has a gate insulating film as described in any one of 1) -8).

  The thin film obtained from the curable composition of the present invention is excellent in insulation and surface water repellency, functions as a gate insulating film for organic thin film transistors, and can provide an organic TFT element having good transistor characteristics.

Cross-sectional reference diagram of organic TFT

The details of the invention will be described.
The curable composition of the present invention can provide a gate insulating film for an organic TFT excellent in insulation and surface water repellency.
In general, a curable composition composed of a polyfunctional epoxy compound or a polyfunctional acrylate compound requires a stricter insulation after forming a thin film having excellent insulation and chemical resistance after curing, for example, a gate insulating film for an organic TFT, etc. It is suitable for these members. However, since the above resin contains a lot of hydrophilic functional groups and becomes hydrophilic on the surface of the thin film after curing, the influence of semiconductor electron / carrier trapping is great when TFTs are used, and there is a device with good transistor characteristics. I can't get it.
The curable composition of the present invention is excellent in insulation and surface water repellency and functions as a gate insulating film for an organic TFT having good transistor characteristics.

(About gate insulating film for organic TFT)
An organic thin film transistor (organic TFT) applied in the present invention refers to a field effect transistor (FET) in which a semiconductor layer is formed of an organic compound, and includes a three-terminal type formed from a source, a drain, and a gate electrode, and a back surface. A four-terminal transistor including a gate, which is a thin-film transistor that controls a current between a source and a drain by an electric field of a channel generated by applying a voltage to a gate electrode. As transistor structures, there are various combinations and arrangements depending on the display device structure to be applied, such as bottom-gate type, top-gate type, and source / drain electrode arrangements regarding the arrangement of gate electrodes, and bottom-contact type and top-contact type. Design is possible, and the structure is not particularly limited.

  Various organic semiconductor layers have been proposed as the organic semiconductor layer used, and examples thereof include pentacene-based, oligothiophene-based, and phthalocyanine-based compounds. Further, regarding the method for forming the semiconductor layer, various methods such as vapor deposition and coating have been proposed and are not particularly limited.

  The electrode material can also be used without particular limitation, but can be easily obtained, such as Au, Al, Pt, Mo, Ti, Cr, Ni, Cu, ITO, PEDOT / PSS, and other conductive polymers, conductive pastes, Metal ink or the like is preferably used. Al, Mo, Ti, Cr, Ni, Cu and the like are preferable because of low resistance and high conductivity, and ITO and PEDOT / PSS are preferable from the viewpoint of being applicable to places where transparency is required. Au and Pt are preferable from the viewpoint that the surface is hardly oxidized and excellent in stability, and conductive polymers such as PEDOT / PSS, conductive paste, and metal ink are preferably used because they can be formed by a printing process.

  The gate insulating film in the organic TFT referred to in the present invention is an insulating film formed between the gate electrode and the semiconductor layer, and even a minute current leak affects the operation failure, so that extremely high insulation reliability is required. It is a member.

  Regarding the formation method, various methods such as CVD, sputtering, vapor deposition, and coating have been proposed, but in the case of organic TFT, it can be formed by coating for low cost process by printing process and development for flexible display etc. Is preferred. Further, the coating method is not particularly limited, and the film can be formed by a method such as spin coating, dip coating, roll coating, screen coating, spray coating, spin casting, flow coating, screen printing, ink jet or drop casting. it can. Moreover, you may adjust the viscosity by a solvent suitably according to the state of the base material to form into a film.

  However, various resin compounds have been applied and studied as insulating film materials that can be formed by a coating process, but materials satisfying the following transistor characteristics and thin film transistors using the same have not been obtained. In general, carrier mobility, threshold voltage, hysteresis, and ON / OFF ratio are important characteristics for driving a stable active matrix flat panel display as a transistor and obtaining a clear image. Yes.

The threshold voltage (V _th ) indicates the X intercept of the saturation linear region in the current transfer characteristic, and it can be said that the closer to 0 V, the better the transistor. Hysteresis indicates the reproducibility of current transfer characteristics with respect to transistor repetitive operation, and is represented by the difference in threshold voltage during repetitive operation. For stable driving when a display is used, the hysteresis is preferably 5 V or less, more preferably 3 V or less.

Also the ON / OFF current ratio, expressed as a ratio of the maximum current value and minimum current value of the current I _d flowing between the source / drain of the current transfer characteristics of the transistor (Ion / Ioff), as a switch larger It is preferably 10 ⁴ or more because it shows excellent function and enables driving of a system that requires a large current for driving.

The carrier mobility is also an important index indicating whether the TFT device is good or bad. A larger value indicates that the TFT device is more excellent, and is preferably 0.1 or more.
In particular, by using a thin film having high surface water repellency obtained by the present invention as a gate insulating film, an organic TFT having a small hysteresis and a large ON / OFF current ratio can be obtained.

(About surface water repellency)
In general, the surface state of the gate insulating film for organic TFT is important as a factor that affects transistor characteristics. Epoxy resins, acrylic resins, and phenol resins, which are commonly used as curable resins, are used as insulating films for various electronic components because thin films with excellent insulation and dielectric strength are obtained. However, since there are many polar groups on the surface of the cured product and thin film, there is a problem that good transistor characteristics are hardly exhibited when applied as a gate insulating film for organic TFTs.

  In order to solve this problem, the present inventor has found that good transistor characteristics can be exhibited by using a film having a high contact angle with water on the surface as the gate insulating film of the organic TFT. The contact angle is 95 ° or more, preferably 99 ° or more. In particular, 100 ° to 110 ° or 101 ° to 104 ° is preferable.

  In general, many resins that can provide a coating film with high surface water repellency are known. In particular, fluorine resins (for example, trade name: Cytop, manufactured by Asahi Glass) and cyclic olefin hydrocarbon resins (for example, trade names: ZEONEX, ZEONOR, manufactured by Zeon Corporation, trade name: Arton, manufactured by JSR), and polysiloxane resins that do not have an epoxy group or an acrylic group are included. Curable resin that is difficult to apply as an insulating film for TFT due to poor chemical resistance and substrate adhesion in TFT manufacturing processes such as etching liquids, and with a crosslinking reaction by heating. Is preferred.

  As the curable resin that can be used in the gate insulating film of the present invention, a curable composition containing as a main component a compound containing an epoxy group, an acryloyl group, or a phenol group can be used. These compositions are excellent in film formability, and the resulting film has excellent adhesion to the substrate and a high surface contact angle, and can be said to be suitable as an insulating film for organic TFTs.

(Epoxy group-containing compound)
The epoxy group of the epoxy group-containing compound referred to in the present invention can be selected from alicyclic epoxy groups and glycidyl groups. It functions as a film having excellent insulating properties by crosslinking by heating or light energy.

  Representative compounds include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, biphenol type epoxy resins, bixylenol type epoxy resins and the like, 1,2-dihydroxynaphthalene type Epoxy resin, 1,3-dihydroxynaphthalene type epoxy resin, 1,4-dihydroxynaphthalene type epoxy resin, 1,5-dihydroxynaphthalene type epoxy resin, 1,6-dihydroxynaphthalene type epoxy resin, 1,7-dihydroxynaphthalene type Epoxy resin, 1,8-dihydroxynaphthalene type epoxy resin, 2,3-dihydroxynaphthalene type epoxy resin, 2,6-dihydroxynaphthalene type epoxy resin, 2,7-dihydroxynaphthalene type epoxy resin Dihydroxynaphthalene type epoxy resins such as resin, triglycidyl isocyanurate, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl Ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neo Such as pentyl glycol diglycidyl ether Aliphatic epoxy compounds such as aliphatic epoxy compounds, hydrogenated bisphenol A type epoxy resins, hydrogenated biphenyl type epoxy resins, 1,4-cyclohexanediol type epoxy resins, 1,4-cyclohexanedimethanol type epoxy resins, etc. Is mentioned.

  Furthermore, in order to increase these insulating properties, an acid anhydride compound, an amine compound, a phosphorus compound, or the like may be added as a crosslinking agent.

  Moreover, it is preferable that it is a polysiloxane compound which has an epoxy group from a viewpoint from which the thin film which is excellent in chemical resistance is obtained. A method for obtaining a polysiloxane compound having an epoxy group is not particularly limited, but a method of condensing an alkoxysilane compound having an epoxy group, a compound having an epoxy group and an alkenyl group in the same molecule, and a poly having an SiH group. A method obtained by hydrosilylation reaction with a siloxane compound can be mentioned, but the latter method is preferable from the viewpoint that an unreacted site is hardly left and a thin film having excellent insulating properties is easily obtained.

  Examples of the epoxy compound used in this production method include vinylcyclohexene oxide, allyl glycidyl ether, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, and the like, from the viewpoint of excellent photopolymerization reactivity. Vinylcyclohexene oxide, which is a compound having an epoxy group, is particularly preferred. Examples of the compound having an oxetanyl group include allyl oxetanyl ether and vinyl oxetanyl ether. When using the compound which has oxetanyl group, it is preferable from a viewpoint that hardened | cured material intensity | strength improves.

  Examples of the polysiloxane compound having SiH groups include poly or oligosiloxanes whose ends are blocked with dimethylhydrosilyl groups, and cyclic or chain poly or oligosiloxanes having SiH groups in the side chains.

  Among them, it is preferable from the viewpoint that a film having excellent strength and solvent resistance can be easily obtained by applying cyclic siloxane. As a specific example, 1,3,5,7-tetrahydrogen-1,3,5,7- Tetramethylcyclotetrasiloxane, 1-methyl-3,5,7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-dimethyl-5,7-dihydrogen-1,3, 5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-dipropyl-5,7-dihydro Gen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-7-hexyl-1,3,5,7-tetramethylsilane Rotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-trimethylcyclosiloxane, 1,3, 5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexahydrogen-1,3,5,7,9 , 11-hexamethylcyclosiloxane and the like. In particular, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane is preferable from the viewpoint of availability.

  Further, when the polysiloxane compound having the photopolymerizable functional group is obtained by hydrosilylation reaction for the purpose of improving the strength and adhesion of the obtained film, the compound having the epoxy group and the alkenyl group in the same molecule is obtained. In addition, the following alkenyl compounds can be hydrosilylated at the same time. The alkenyl compound that can be used here is not particularly limited as long as it is a compound having a carbon-carbon double bond in one molecule, and can be used without any limitation regardless of a polysiloxane compound or an organic compound. it can. Moreover, about this alkenyl compound, the thing which does not have a photopolymerization functional group from a viewpoint from which the thin film which is more excellent in adhesiveness is obtained is preferable.

In particular, polysiloxane having an alkenyl group can be preferably applied from the viewpoint of transparency and curability of the cured product. Among these, from the viewpoint of compound availability, a polysiloxane compound having a vinyl group (Si—CH═CH ₂ group) bonded to a silicon group is preferable.

  Specific examples include poly or oligosiloxanes end-capped with dimethylvinylsilyl groups, poly or oligosiloxanes having vinyl groups in the side chains, tetramethyldivinyldisiloxane, hexamethyltrivinyltrisiloxane, SiH groups Examples of the cyclic siloxane include those in which the hydrogen atom of the SiH group is substituted with an alkenyl group such as a vinyl group or an allyl group.

  Specifically, 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1,3,5,7-tetramethyl Cyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-trimethylcyclosiloxane, 1,3,5,7, 9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexavinyl-1,3,5,7,9,11-hexamethylcyclosiloxane, etc. The compound of this is mentioned.

  Examples of the alkenyl group-containing organic compound do not include a siloxane unit (Si—O—Si), but are composed of atoms selected from the group consisting of C, H, N, O, S and halogen as constituent elements. The compound is not particularly limited as long as it is an organic compound having a carbon-carbon double bond having reactivity with a SiH group in one molecule. Further, the bonding position of the carbon-carbon double bond having reactivity with the SiH group is not particularly limited, and may be present anywhere in the molecule.

  The organic compounds can be classified into organic polymer compounds and organic monomer compounds. Examples of the organic polymer compounds include polyether-based, polyester-based, polyarylate-based, polycarbonate-based, saturated hydrocarbon-based, unsaturated hydrocarbon-based compounds. Hydrogen-based, polyacrylic acid ester-based, polyamide-based, phenol-formaldehyde-based (phenolic resin-based), and polyimide-based compounds can be used.

  Examples of organic monomer compounds include aromatic hydrocarbons such as phenols, bisphenols, benzene and naphthalene: aliphatic hydrocarbons such as linear and alicyclic: heterocyclic compounds and their A mixture etc. are mentioned.

  Specific examples of monomeric compounds include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether 1,1,2,2-tetraallyloxyethane, diarylidenepentaerythritol, triallyl cyanurate, 1,2,4-trivinylcyclohexane, 1,4-butanediol diallyl ether, nonanediol diallyl ether, 1,4-cyclohexanedimethanol diallyl ether, triethylene glycol diallyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether , Diallyl ether of bisphenol S, divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-bis (allyloxy) adamantane, 1,3-bis (vinyloxy) Adamantane, 1,3,5-tris (allyloxy) adamantane, 1,3,5-tris (vinyloxy) adamantane, cyclopentadiene, cyclohexadiene, cyclooctadiene, tricyclopentadiene, norbornadiene, dicyclopentadiene, vinyl norbornene, vinylcyclo Hexene, vinylcyclopentene, butadiene, isoprene, octadiene, 1,5-hexadiene, 1,9-decadiene, diallyl ether, bisphenol A diallyl ether, 2,5-diallyl Nord allyl ether and the like.

  In particular, triallyl isocyanurate represented by the following general formula (II) and derivatives thereof are particularly preferable from the viewpoints of transparency, heat resistance, light resistance, and insulation properties.

(Wherein R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms, and each R ¹ may be different or the same).

As R < ¹ > of the said general formula (II), it is preferable that it is a C1-C20 monovalent organic group from a viewpoint that the heat resistance of the hardened | cured material obtained can become higher, and C1-C1 10 monovalent organic groups are more preferable, and monovalent organic groups having 1 to 4 carbon atoms are more preferable. Examples of these preferable R ¹ include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group and the like.

  Specific examples of these compounds include triallyl isocyanurate, diallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monobenzyl isocyanurate, diallyl monopropyl isocyanurate, and triallyl isocyanurate from the viewpoint of availability. It is done.

  Among these, from the viewpoint of good transistor characteristics, it is preferable to have an epoxy group, a SiH group, or a group represented by (X1) or (X2).

((Meth) acryloyl group-containing compound)
The (meth) acryloyl group-containing compound that can be used in the present invention is a compound that can be formed into a film by crosslinking by heating or light energy, like the epoxy group-containing compound. Specific examples of the (meth) acryloyl group-containing compound that can be used include allyl (meth) acrylate, vinyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (Meth) acrylic acid modified allyl glycidyl ether (manufactured by Nagase ChemteX, trade name: Denacol acrylate DA111), urethane (meth) acrylates, epoxy (meth) acrylates, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, ditrimethylolpropane (meth) tetraacrylate, dipentaerythritol hexa (meth) acrylate, butanediol di (meth) acrylate, nonanediol di (meth) acrylate, Polypropylene glycol (meth) acrylate, bisphenol A di (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, and (meth) acrylate group-containing polysiloxane.

  Moreover, it is preferable that it is a polysiloxane compound which has a (meth) acryloyl group from a viewpoint from which the thin film which is excellent in chemical resistance is obtained. A method for obtaining a polysiloxane compound having a (meth) acryloyl group is not particularly limited, but a method of condensing an alkoxysilane compound having a (meth) acryloyl group, a compound having a (meth) acryloyl group, and a poly having an SiH group A method obtained by hydrosilylation reaction with a siloxane compound can be mentioned, but the latter method is preferable from the viewpoint that an unreacted site is hardly left and a thin film having excellent insulating properties is easily obtained.

  As the (meth) acryloyl group-containing compound that can be used in this production method, the above-mentioned (meth) acryloyl group-containing compound can be used.

  As the polysiloxane compound having a SiH group, a compound that can be used as the epoxy group-containing compound can be used.

  Further, when the polysiloxane compound having the photopolymerizable functional group is obtained by hydrosilylation reaction for the purpose of improving the strength and adhesion of the obtained film, the alkenyl compound having no photopolymerizable functional group is simultaneously hydrosilylated. It can also be made to be the same as in the case of the epoxy group-containing compound.

(Phenol group-containing compound)
Examples of the phenol group-containing compound in the present invention include polyvinylphenol resins and polysiloxane resins having a phenol group. In order to further increase the insulating properties, a melamine compound may be added as a crosslinking agent.

  Moreover, it is preferable that it is a polysiloxane compound which has a phenol group from a viewpoint from which the thin film excellent in chemical resistance is obtained. A method for obtaining a polysiloxane compound having a phenol group is not particularly limited, but a method in which an alkoxysilane compound having a phenol group is condensed, an allyl group-containing compound having a phenol group, and a polysiloxane compound having a SiH group are hydrosilylated. Although the method obtained by making it react is mentioned, the latter method is suitable from a viewpoint that it is easy to become a thin film which is hard to leave an unreacted part and is excellent in insulation.

  As the phenol group-containing compound that can be used in this production method, a phenol group-containing compound such as allylphenol can be used.

  As the polysiloxane compound having a SiH group, a compound that can be used as the epoxy group-containing compound can be used.

  Furthermore, for the purpose of improving the strength and adhesion of the resulting film, it is also possible to add crosslinkable compounds such as (meth) acrylic compounds and epoxy compounds, and hydrosilylation reactive compounds (SiH group-containing compounds and alkenyl compounds). it can.

(About polysiloxane compounds)
In the present invention, the effect of surface water repellency can be obtained by adding a polysiloxane compound. The polysiloxane compound used preferably has an average weight molecular weight of 10,000 or less from the viewpoint of compatibility with a compound selected from an epoxy group-containing compound, an acryloyl group-containing compound, and a phenol group-containing compound. Since it is hard to isolate | separate from an acrylate group containing compound and a phenol group containing compound, and hardened | cured material does not produce unevenness, it is more preferable that it is 8000 or less. The average molecular weight is preferably 500 or more from the viewpoint of being less volatile at the time of forming a thin film, and more preferably 1000 or more from the viewpoint that a water repellency effect is more easily exhibited. The molecular weight at this time is a numerical value in terms of polystyrene.

  Moreover, as a polysiloxane compound, what has a reactive functional group in a molecule | numerator from a viewpoint that it is excellent in the solvent resistance in the thin film after hardening is preferable. As a reactive functional group, a vinyl group, SiH group, a hydroxyl group, an epoxy A group, a methacryl group, an amino group and the like can be mentioned and are not particularly limited. Of these, compounds having a hydrosilylation reactivity vinyl group and SiH group that are less likely to generate polar groups after the reaction can be suitably used.

  Examples thereof include poly or oligosiloxanes whose ends are blocked with dimethylhydrosilyl groups, and cyclic or chain poly or oligosiloxanes having SiH groups in the side chains. Specific examples thereof include SiH group-containing dimethylpolysiloxanes (manufactured by gelst, trade names DMS-H03, DMS-H11, DMS-H21, and DMS-H11).

  As the polysiloxane compound having a vinyl group, a compound having a preferable molecular weight described above is preferable. For example, a poly or oligosiloxane whose end is blocked with a dimethylvinylsilyl group, a poly or oligosiloxane having a vinyl group in a side chain, or tetramethyldivinyl. Illustrative examples of disiloxane, hexamethyltrivinyltrisiloxane, and cyclic siloxane containing SiH groups include those in which the hydrogen atoms of SiH groups are substituted with alkenyl groups such as vinyl groups and allyl groups.

Among these, from the viewpoint of availability, linear polysiloxanes whose ends are blocked with dimethylvinylsilyl groups are preferred, and specifically, those having (Me ₂ SiO—) units of 5 or more and 20 or less are preferred. From the viewpoint that the effect of improving the contact angle is easily manifested in a small amount, those having 7 or more and 15 or less are more preferable. Specific examples thereof include vinyl group-containing dimethylpolysiloxanes (manufactured by gelst, trade names DMS-V03, DMS-V05, DMS-V21, DMS-V22).

  Other cyclic siloxane compounds include 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1,3,5, 7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-trimethylcyclosiloxane, 1,3 5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexavinyl-1,3,5,7,9,11-hexa Examples thereof include compounds such as methylcyclosiloxane and vinyl group-containing siloxane oligomer (manufactured by Clariant, trade names MQV5 and MQV7).

  In addition, a polysiloxane compound having a SiH group and a polysiloxane compound having a vinyl group can be suitably used by hydrosilylation reaction and molecular weight adjustment, and the compounds exemplified above are not particularly limited in any combination. be able to.

  The polysiloxane compound is preferably used in an amount (weight) that does not exceed the weight of the compound selected from an epoxy group-containing compound, an acryloyl group-containing compound, and a phenol group-containing compound. Specifically, it is preferably used in an amount of 0.05 to 50 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of a compound selected from an epoxy group-containing compound, an acryloyl group-containing compound, and a phenol group-containing compound.

  When the amount used is small, it is difficult to stably increase the contact angle with water. When the amount used is large, when an insulating film is formed and further laminated on the film, there is a tendency that a part where the laminate is repelled appears.

(Hydrosilylation catalyst)
A known hydrosilylation catalyst may be used as a catalyst for the hydrosilylation reaction suitably used as a method for obtaining the polysiloxane compound.
From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable. Moreover, these catalysts may be used independently and may be used together 2 or more types.

The addition amount of the catalyst is not particularly limited, but the lower limit of the preferred addition amount is a carbon-carbon double bond having reactivity with the SiH group charged at the time of the reaction (hereinafter simply referred to as “additional amount”). It may be referred to as an “alkenyl group.”) 10 ⁻⁸ mol, more preferably 10 ⁻⁶ mol per 1 mol, and the upper limit of the preferable addition amount is 10 ⁻¹ per mol of the alkenyl group of the above compound. Mol, more preferably ^10-2 mol.

In addition, a cocatalyst can be used in combination with the above catalyst. Examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, 2-hydroxy-2-methyl-1 Examples include acetylene alcohol compounds such as butyne and 1-ethynyl-1-cyclohexanol, and sulfur compounds such as simple sulfur. The addition amount of the cocatalyst is not particularly limited, but the lower limit of the preferable addition amount relative to 1 mol of the hydrosilylation catalyst is 10 ⁻² mol, more preferably 10 ⁻¹ mol, and the upper limit of the preferable addition amount is 10 ^2. Mol, more preferably 10 mol.

(About alkali developability)
In the epoxy group-containing compound and the (meth) acryloyl group-containing compound of the present invention, each of the structures represented by the following formulas (X1) to (X2) and a structure of any of the groups consisting of carboxyl groups are included in the molecule. It is preferable to use a curable composition because the curable composition can be dissolved in an alkaline aqueous solution and a photoresist function capable of alkali development can be provided.

  In particular, as a method for easily obtaining a compound having the following specific structure, each structure having an alkenyl group and represented by the following formulas (X1) to (X2):

It can be obtained by partially hydrosilylating a compound having at least one selected from the group consisting of carboxyl groups in the same molecule and a polysiloxane compound having an epoxy group or a (meth) acryloyl group and a SiH group.

  Among these organic structures, a structure selected from the above formulas (X1) to (X2) and a phenolic hydroxyl group is preferable from the viewpoint that the obtained cured product is excellent in heat resistance. Specifically, diallyl isocyanuric acid, mono Allyl isocyanuric acid, vinyl phenol, allyl phenol, diallyl bisphenol A, diallyl bisphenol S,

Is preferred.

Among these, diallyl isocyanuric acid and monoallyl isocyanuric acid are particularly preferable from the viewpoint of transparency of the cured product.
In the case of a compound having alkali developability, it is necessary to contain a photopolymerization initiator. It is necessary to select and add appropriately depending on the type of photopolymerizable functional group. In the case of epoxy groups, alkoxysilyl groups, etc., a cationic polymerization initiator is used, and in the case of radical polymerizable groups such as allyloxy, methacryloxy groups, etc. A radical initiator is used.

(Cationic polymerization initiator)
The cationic polymerization initiator is particularly limited as long as it is an active energy ray cationic polymerization initiator that generates a cationic species or Lewis acid by active energy rays, or a thermal cationic polymerization initiator that generates a cationic species or Lewis acid by heat. It can be used without being.

Active energy ray cationic polymerization initiators include metal fluoroboron complex salts and boron trifluoride complex compounds, bis (perfluoroalkylsulfonyl) methane metal salts, aryldiazonium compounds, aromatic onium salts of group VIa elements, group Va elements aromatic onium salts of, dicarbonyl chelate thio pyrylium compounds IIIa~Va group element, MF6 ^- form of VIa elements anion (wherein M is selected from phosphorus, antimony and arsenic), arylsulfonium complex salts, aromatic Group iodonium complex salt and aromatic sulfonium complex salt, bis [4- (diphenylsulfonio) phenyl] sulfide-bishexafluorometal salt (for example, phosphate, arsenate, antimonate, etc.); anion is B (C ₆ F ₅ ) ₄ ^- is an aromatic iodonium complex salts and one or more aromatic sulfonium complex salt Is included.

  Preferred active energy ray cationic polymerization initiators include arylsulfonium complex salts, aromatic sulfonium or iodonium salts of halogen-containing complex ions, and aromatic onium salts of Group II, Group V and Group VI elements. Some of these salts are FX-512 (3M), UVR-6990 and UVR-6974 (Union Carbide), UVE-1014 and UVE-1016 (General Electric), KI-85 (Degussa) ), SP-152 and SP-172 (Asahi Denka Co., Ltd.), Sun-Aid SI-60L, SI-80L and SI-100L (Sanshin Chemical Industry Co., Ltd.), WPI113 and WPI116 (Wako Pure Chemical Industries, Ltd.), RHODORSIL PI2074 (Rhodia) ), BBI-102, BBI-103, and BBI-105 (Midori Chemical).

(Radical polymerization initiator)
Any active energy ray radical initiator that generates radical species by active energy rays can be used without any particular limitation.

  Active energy ray radical polymerization initiators include acetophenone compounds, benzophenone compounds, acylphosphine oxide compounds, oxime ester compounds, benzoin compounds, biimidazole compounds, α-diketone compounds, titanocene compounds, polynuclear compounds Quinone compounds, xanthone compounds, thioxanthone compounds, triazine compounds, ketal compounds, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, thiuram compounds, fluoroamine compounds, etc. Can be used.

  Specific examples of acetophenone compounds include 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, 1- (4′-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2′-hydroxyethoxy) phenyl (2-hydroxy-2) -Propyl) ketone, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- (4'-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4′-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2 -Dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one Etc.

  Specific examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.

  Specific examples of oxime ester compounds include 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone 1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like.

  Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, methyl 2-benzoylbenzoate and the like.

  Specific examples of the benzophenone compounds include benzyl dimethyl ketone, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like.

  Specific examples of the α-diketone compound include diacetyl, dibenzoyl, methylbenzoylformate, and the like.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2 , 2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4 , 6-trichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1, 2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4, 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1 , 2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2, 4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bi (2,4,6-bromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole.

  Specific examples of the polynuclear quinone compound include anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1,4-naphthoquinone, and specific examples of the xanthone compound include xanthone, thioxanthone, and 2-chloro. Examples include thioxanthone and 2,5-diethyldioxanthone.

  Specific examples of the triazine compound include 1,3,5-tris (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1, 3-bis (trichloromethyl) -5- (4′-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-methoxyphenyl) -s-triazine, 1,3-bis (Trichloromethyl) -5- (4′-methoxyphenyl) -s-triazine, 2- (2′-furylethylidene) -4,6-bis (trichloromethyl) -s-triazine, 2- (4′-methoxy) Styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( '-Methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2'-bromo-4'-methylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(2'-thiophenylethylidene) -4,6-bis (trichloromethyl) -s-triazine and the like.

  In particular, from the viewpoint of excellent thin film curability, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-hydroxy-1- [4- [ 4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one, 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime) )], Ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred.

  In particular, from the viewpoint that the cured product is excellent in transparency, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- ( 4′-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2′-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, 2,2-dimethoxyacetophenone preferable.

  Moreover, these photoinitiators may be used independently and may be used together 2 or more types. The amount used is preferably 0.1 to 15 parts by weight, more preferably 0 to 100 parts by weight of the total weight of the compound selected from an epoxy group-containing compound, a (meth) acryloyl group-containing compound and a phenol group-containing compound. .1 to 10 parts by weight. When the amount of the photopolymerization initiator is small, there is a tendency that the curing is insufficient and a contrast cannot be obtained during alkali development. A large amount of initiator is not preferable because the cured film itself is colored.

(Method for adjusting curable composition and curing method)
The preparation method of a curable composition is not specifically limited, It can prepare with various methods. Various components may be mixed and prepared immediately before curing, or may be stored at a low temperature in a one-component state in which all components are mixed and prepared in advance.

  The method of using the curable composition of the present invention is not particularly limited, and can be used by spin coating, slit coating, dispensing potting, or the like. Further, viscosity adjustment with a solvent and surface tension adjustment with a surfactant may be appropriately performed according to the state of the substrate.

  Moreover, the resin composition of this invention can be made into hardened | cured material by making a crosslinking reaction advance by light irradiation. As a light source that can be used at that time, a light source that emits light having an absorption wavelength of a polymerization initiator or a sensitizer to be used may be used, and a light source having a wavelength in the range of 200 to 450 nm is preferable. Specifically, for example, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a high power metal halide lamp, a xenon lamp, a carbon arc lamp, a light emitting diode, or the like can be used.

The exposure amount is not particularly limited, but a preferable exposure amount range is 1 to 5000 mJ / cm ² , more preferably 1 to 1000 mJ / cm ² . If the exposure is small, it will not cure. If the exposure amount is large, the color may change due to rapid curing. A preferred curing time range is 1 to 120 seconds, more preferably 1 to 60 seconds. When the curing time is long, the characteristics of rapid curing of photocuring are not utilized.

  The heating temperature after the film formation is not particularly limited, but is preferably 250 ° C. or less, and preferably 200 ° C. or less from the viewpoint that the influence on the peripheral low heat-resistant member is small. When using a resin substrate or the like, the temperature is preferably 160 ° C. or lower in consideration of dimensional stability and the like.

(About photolithography)
In the case where the curable composition of the present invention has alkali developability, it can be finely patterned by development. The patterning formation is not particularly limited, and a desired pattern can be formed by dissolving / removing the unexposed portion by a commonly used developing method such as an immersion method or a spray method.

  Alkaline development enables the formation of large areas using photolithographic equipment used in general semiconductor manufacturing and display manufacturing, and the improvement of pattern accuracy uniformity. This is preferable because it is advantageous in terms of cost.

  The developer used for development can be used without particular limitation as long as it is generally used. Specific examples include organic solvents that are available at low cost, for example, ketone solvents such as acetone, MEK, and MIBK. And alcohol solvents such as methanol and ethanol, and ester solvents such as ethyl acetate and butyl acetate. In the case of alkaline development, an organic alkaline aqueous solution such as tetramethylammonium hydroxide aqueous solution or choline aqueous solution, or an inorganic alkaline aqueous solution such as potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium carbonate aqueous solution, sodium carbonate aqueous solution or lithium carbonate aqueous solution. And those obtained by adding an alcohol or a surfactant to these aqueous solutions in order to adjust the dissolution rate and the like.

  The aqueous solution concentration is preferably 25% by weight or less, more preferably 10% by weight or less, still more preferably 5% by weight or less from the viewpoint that the contrast between the exposed part and the unexposed part is easily obtained. preferable.

(Sensitizer)
In the curable composition of the present invention, when cured with light energy, the sensitivity of light is improved, and high wavelengths such as g-line (436 nm), h-line (405 nm), and i-line (365 nm) are called. In order to give sensitivity to light, a sensitizer can be appropriately added. These sensitizers can be used in combination with the above cationic polymerization initiator and / or radical polymerization initiator to adjust the curability.

  Examples of the compound to be added include anthracene compounds and thioxanthone compounds.

  Specific examples of the anthracene compound include anthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-di. Ethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 2-tert-butylanthracene, 2,6-di-tert-butylanthracene, 9,10-diphenyl-2,6-di- tert-butylanthracene and the like can be mentioned, and from the viewpoint of easy availability, anthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene and the like preferable.

  Anthracene is preferable from the viewpoint of excellent transparency of the cured product, and 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-diethoxy from the viewpoint of excellent compatibility with the curable composition. Anthracene and the like are preferable.

  Specific examples of the thioxanthone series include thioxanthone, 2-chlorothioxanthone, 2,5-diethyldioxanthone and the like.

  These sensitizers may be used alone or in combination of two or more. Furthermore, in order to function more satisfactorily as a gate insulating film, it is important to develop a high insulating property, and by applying a crosslinking reaction and a hydrosilylation reaction of an epoxy group or (meth) acryloyl group in the above composition. Further, it is more preferable because it becomes a denser cross-linked body and an insulating film having excellent insulation reliability can be formed.

  The hydrosilylation reactive composition refers to a resin composition containing an alkenyl group, a SiH group, and a hydrosilylation catalyst. The epoxy group or (meth) acryloyl group-containing compound and the hydrosilylation reactive compound may be mixed and used, or the epoxy group or (meth) acryloyl group and the hydrosilylation reactive group may be combined in the same molecule. You may use the compound which has. When a compound having an epoxy group or a (meth) acryloyl group has an alkenyl group or SiH group in the same molecule, hydrosilylation catalyst can be added by adding the compound having one of the functional groups not present and a hydrosilylation catalyst. The chemical reactivity can be imparted.

  Moreover, about the compound which has an alkenyl group, if it is an alkenyl compound of the said illustration, it can be used without limitation. Among these, the following general formula (II)

(In the formula, R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms, and each R ¹ may be different or the same). It is preferable from the viewpoint that it becomes an upper dense film and can be an insulating film excellent in insulation and pressure resistance.

  A technique for introducing the structure into the curable composition is not particularly limited, and a technique for adding a general-purpose isocyanuric ring-containing compound may be mentioned. Examples of isocyanuric ring-containing compounds include triallyl isocyanurate, diallyl isocyanurate, monoallyl isocyanurate, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monopropyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monobenzyl isocyanurate And the like can be appropriately selected according to the crosslinking reaction of the curable composition.

  About the compound which has SiH group, the compound in the said illustration can be used without limitation. From the viewpoint of obtaining a tough thin film, it is also preferable to use an oligomer in which polysiloxane compounds or organic compounds and polysiloxane compounds are partially reacted in advance. The partial cross-linking reaction is not particularly limited, but forms an electrically and thermally stable C—Si bond after the reaction as compared with hydrolysis condensation, and the reaction control is easy. It is preferable to apply a hydrosilylation reaction from the viewpoint that a crosslinking group hardly remains.

  The monomer for partial crosslinking is not particularly limited, and the siloxane compound having an SiH group and the siloxane compound or organic compound having an alkenyl group can be used in appropriate combination. As the catalyst for the hydrosilylation reaction, a known hydrosilylation catalyst may be used. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable. Moreover, these catalysts may be used independently and may be used together 2 or more types.

(Adhesion improver)
An adhesion improver can also be added to the curable composition of the present invention. In addition to commonly used adhesives as adhesion improvers, for example, various coupling agents, epoxy compounds, oxetane compounds, phenol resins, coumarone-indene resins, rosin ester resins, terpene-phenol resins, α-methylstyrene -Vinyl toluene copolymer, polyethyl methyl styrene, aromatic polyisocyanate, etc. can be mentioned.

  An example of the coupling agent is a silane coupling agent. The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handling. From the viewpoints of adhesion and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

  Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Methacrylic or acrylic groups such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Alkoxysilanes which can be exemplified.

  The addition amount of the silane coupling agent can be variously set, but is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 10 parts by weight, and still more preferably 0 to 100 parts by weight of the modified polysiloxane compound. 0.5 to 5 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the curability and the physical properties of the cured product may be adversely affected. These coupling agents, silane coupling agents, epoxy compounds, etc. may be used alone or in combination of two or more.

(Thermoplastic resin)
Various thermoplastic resins may be added to the curable composition for the purpose of modifying the properties. Specifically, for example, a homopolymer of methyl methacrylate or a random, block or graft polymer of methyl methacrylate and other monomers, a polymethyl methacrylate resin (for example, Optretz manufactured by Hitachi Chemical Co., Ltd.), a butyl acrylate alone Polymers or acrylic resins represented by polybutyl acrylate resins such as random, block or graft polymers of butyl acrylate and other monomers, bisphenol A, 3,3,5-trimethylcyclohexylidene bisphenol, etc. Polycarbonate resins such as polycarbonate resins contained as monomer structures (for example, APEC manufactured by Teijin Limited), norbornene derivatives, resins obtained by homopolymerizing or copolymerizing vinyl monomers, and ring opening metathesis polymerization of norbornene derivatives Or olefins such as hydrogenated products thereof (for example, APEL manufactured by Mitsui Chemicals, ZEONOR, ZEONEX manufactured by Nippon Zeon, ARTON manufactured by JSR, etc.), and copolymers of ethylene and maleimide Maleimide resins (eg, TI-PAS manufactured by Tosoh Corporation), bisphenols such as bisphenol A and bis (4- (2-hydroxyethoxy) phenyl) fluorene, diols such as diethylene glycol, and phthalates such as terephthalic acid and isophthalic acid Polyester resins such as polyester obtained by polycondensation of acids and aliphatic dicarboxylic acids (for example, O-PET manufactured by Kanebo Co., Ltd.), polyethersulfone resins, polyarylate resins, polyvinyl acetal resins, polyethylene resins, polypropylene resins, polystyrene resins, Poly Bromide resins, silicone resins, other like fluorine resin, not natural rubber, but the rubber-like resin is exemplified such EPDM is not limited thereto.

  The thermoplastic resin may have a crosslinkable group. Examples of the crosslinkable group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. From the viewpoint that the heat resistance of the obtained cured product tends to be high, it is preferable to have one or more crosslinkable groups in one molecule on average.

  The molecular weight of the thermoplastic resin is not particularly limited, but the number average molecular weight is preferably 10,000 or less and more preferably 5000 or less in that the compatibility with the modified siloxane compound tends to be good. preferable. On the contrary, the number average molecular weight is preferably 10,000 or more, and more preferably 100,000 or more in that the obtained cured product tends to be tough. The molecular weight distribution is not particularly limited, but the molecular weight distribution is preferably 3 or less, more preferably 2 or less, in that the viscosity of the mixture tends to be low and the moldability tends to be good. More preferably, it is as follows.

  Although there is no limitation in particular as a compounding quantity of a thermoplastic resin, the range of the preferable usage-amount is 5 to 50 weight% of the whole curable composition, More preferably, it is 10 to 30 weight%. If the amount added is small, the resulting cured product tends to be brittle. If the amount added is large, the heat resistance (elastic modulus at high temperature) tends to be low. A single thermoplastic resin may be used, or a plurality of thermoplastic resins may be used in combination.

  The thermoplastic resin may be dissolved in the modified polysiloxane compound and mixed in a uniform state, may be pulverized and mixed in a particle state, or may be in a dispersed state by dissolving in a solvent and mixing. . In the point that the obtained hardened | cured material tends to become more transparent, it is preferable to melt | dissolve in a modified polysiloxane compound and to mix as a uniform state. Also in this case, the thermoplastic resin may be directly dissolved in the modified polysiloxane compound, or may be uniformly mixed using a solvent, etc., and then the solvent is removed to obtain a uniform dispersed state and / or mixed state. It is good.

  When the thermoplastic resin is dispersed and used, the average particle diameter can be variously set, but the lower limit of the preferable average particle diameter is 10 nm, and the upper limit of the preferable average particle diameter is 10 μm. There may be a distribution of the particle system, which may be monodispersed or have a plurality of peak particle sizes, but from the viewpoint that the viscosity of the curable composition is low and the moldability tends to be good, The diameter variation coefficient is preferably 10% or less.

(Anti-aging agent)
An aging inhibitor may be added to the curable composition of the present invention. Examples of the anti-aging agent include citric acid, phosphoric acid, sulfur-based anti-aging agent and the like in addition to the anti-aging agents generally used such as hindered phenol type. As the hindered phenol-based anti-aging agent, various types such as Irganox 1010 available from Ciba Specialty Chemicals are used.

  Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylic acid esters, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides. Moreover, these anti-aging agents may be used independently and may be used together 2 or more types.

(UV absorber)
An ultraviolet absorber may be added to the curable composition of the present invention. Examples of the ultraviolet absorber include 2 (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate and the like. Can be mentioned. Moreover, these ultraviolet absorbers may be used independently and may be used together 2 or more types.

(solvent)
When the modified polysiloxane compound used in the curable composition of the present invention has a high viscosity, it can be used by dissolving in a solvent. Solvents that can be used are not particularly limited. Specific examples include hydrocarbon solvents such as benzene, toluene, hexane, and heptane, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether, and the like. Ether solvents, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, glycol solvents such as propylene glycol-1-monomethyl ether-2-acetate (PGMEA), ethylene glycol diethyl ether, chloroform, methylene chloride, A halogen-based solvent such as 1,2-dichloroethane can be preferably used.

  As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane, propylene glycol-1-monomethyl ether-2-acetate, and chloroform are preferable.

  Although the amount of solvent to be used can be set as appropriate, the lower limit of the preferred amount of use with respect to 1 g of the curable composition to be used is 0.1 mL, and the upper limit of the preferred amount of use is 10 mL. If the amount used is small, it is difficult to obtain the effect of using a solvent such as a low viscosity, and if the amount used is large, the solvent tends to remain in the material, causing problems such as thermal cracks, and also from a cost standpoint. It is disadvantageous and the industrial utility value decreases. These solvents may be used alone or as a mixed solvent of two or more.

(Other additives)
The curable composition of the present invention includes other ions such as a colorant, a release agent, a flame retardant, a flame retardant aid, a surfactant, an antifoaming agent, an emulsifier, a leveling agent, an anti-fogging agent, and antimony-bismuth. Trapping agent, thixotropic agent, tackifier, storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, reactive diluent, antioxidant, heat stabilizer, conductivity The purpose and effect of the present invention include an imparting agent, an antistatic agent, a radiation shielding agent, a nucleating agent, a phosphorus peroxide decomposing agent, a lubricant, a pigment, a metal deactivator, a thermal conductivity imparting agent, and a physical property modifier. It can be added as long as it is not impaired.

Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to the following.

(Examples 1-8, Comparative Examples 1-4)
The curable compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 4 were evaluated using the following methods. The results are shown in Table 1.

The thin film formed from the curable composition of the present invention exhibits higher surface water repellency than the composition of the comparative example, and the organic TFT element using this thin film as a gate insulating film functions as a transistor element exhibiting excellent characteristics. To do.

(Contact angle evaluation method)
The curable compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 4 were formed on a glass substrate 30 × 30 mm to a thickness of 1.5 μm by spin coating, dried on a hot plate at 100 ° C. for 2 minutes, and exposed. A thin film sample was obtained by heating at 180 ° C. for 60 minutes (120 ° C., 10 minutes for Examples 7 and 8 and Comparative Examples 2 and 3 in Examples 7 and 8) after 100 mJ / cm ² UV irradiation. The contact angle meter (manufactured by Kyowa Interface Chemical Co., Ltd., DM-301) was used to measure the water contact angle on the membrane surface.

(Transistor creation method)
A gate electrode 2 having a thickness of 500 mm is formed on a glass substrate 1 using aluminum (Al), and the resin compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 4 are formed on the glass substrate 1 under conditions of 2000 rpm and 30 sec. The gate insulating film 3 was formed by spin-coating and post-baking at 180 ° C. for 60 min (Examples 7 and 8 and Comparative Examples 2 and 3 under heating conditions of 120 ° C. and 10 min). 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.

(Dielectric constant measurement method)
The resin compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 4 were coated on a glass substrate with a Mo film (2000 mm) by spin coating under the conditions of 2000 rpm and 30 seconds, and 180 ° C., 60 min (Example 7, 8 and Comparative Examples 2 and 3 were post-baked at 120 ° C. for 10 min to form thin films. Furthermore, the aluminum electrode 3 having a thickness of 500 mm and 3 mmφ was formed by a vacuum deposition apparatus, and a capacitor was manufactured.

About the produced capacitor | condenser, the electrostatic capacitance C (F) of the thin film created in the Example and comparative example at the time of 1kHz and 10V application was measured using the semiconductor parameter analyzer (Keithley 4200). The film thickness of the insulating film is measured using a step meter (manufactured by ULVAC, Dektak), and ε = C × t / ε ₀ × A
C: Capacitance (F)
ε ₀ : dielectric constant of vacuum (8.85 × 10 ⁻¹² )
t: Film thickness (m)
A: Area (m ² )
The dielectric constant ε of the insulating film was calculated by the above formula.

(Transistor characteristic evaluation)
For organic thin film transistors prepared using the gate insulating films of the following examples and comparative examples using the method of the present invention, the semiconductor characteristic evaluation system 4200 (manufactured by Keithley) is used to turn on the current transfer characteristic curve under the following driving conditions. / OFF ratio and carrier mobility were evaluated.

Driving conditions In a state where a voltage of −40 V is applied between the source and the drain in the manufactured transistor, the amount of current (I _d ) between the source and the drain when applied to the gate electrode at 20 to −40 V is plotted to determine the transfer characteristics. did.

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.

・ Threshold voltage (V _th )
As the threshold voltage, the X-intercept voltage value of the tangent line between the current saturation regions in the current transfer characteristics (gate voltage V _g = 30 to 40 V) was used as the threshold voltage.

Carrier mobility μ = 2 (L × I _d ) / (W × (ε / d) × (V _g −V _th ) ² )
L: Channel length (80 μm) W: Channel width (2 mm)
ε: dielectric constant (2.57E-11) d: film thickness V _g : gate voltage V _th : threshold voltage
I _d : Source-drain current Carrier mobility μ was calculated by substituting the I _d value at the gate voltage V _g = 40 V in the current transfer characteristic using the above calculation formula.

(Synthesis Example 1: Synthesis of epoxy group-containing compound)
A 500 mL four-necked flask was charged with 100 g of toluene and 20 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase portion was purged with nitrogen, and then heated and stirred at an internal temperature of 90 ° C. A liquid mixture of 20.67 g of vinylcyclohexene oxide, 0.0017 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) and 20.67 g of toluene was added dropwise. After dropping, the disappearance of the vinyl group-derived peak was confirmed by ¹ H-NMR, and the reaction was completed.

Toluene was distilled off under reduced pressure to obtain a colorless and transparent liquid “Reactant A”. ¹ H-NMR measurement confirmed that the polysiloxane compound had an epoxy group of 5.0 mmol / g and an SiH group of 4.0 mmol / g in terms of equivalent when the standard substance was dibromoethane.

(Synthesis Example 2: Synthesis of epoxy group-containing compound)
A 500 mL four-necked flask was charged with 100 g of toluene and 20 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase portion was purged with nitrogen, and then heated and stirred at an internal temperature of 90 ° C. A mixed liquid of 7.90 g of triallyl isocyanurate, 10.33 g of vinylcyclohexene oxide, 0.0017 g of xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) and 10.33 g of toluene was added dropwise. After dropping, ¹ H-NMR confirmed the disappearance of vinyl group and allyl group-derived peaks, and the reaction was completed.

Toluene was distilled off under reduced pressure to obtain a colorless and transparent liquid “Reaction product B”. ¹ H-NMR measurement confirmed that the polysiloxane compound had an epoxy group of 4.3 mmol / g and a SiH group of 4.0 mmol / g in terms of equivalent when the standard substance was dibromoethane.

(Synthesis Example 3: Synthesis of epoxy group-containing compound)
A 500 mL four-necked flask was charged with 100 g of toluene and 20 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase portion was purged with nitrogen, and then heated and stirred at an internal temperature of 90 ° C. A mixed solution of 7.90 g of diallyl isocyanurate, 10.33 g of vinylcyclohexene oxide, 0.0017 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) and 10.33 g of toluene was added dropwise. After dropping, ¹ H-NMR confirmed the disappearance of vinyl group and allyl group-derived peaks, and the reaction was completed.

Toluene was distilled off under reduced pressure to obtain a colorless and transparent liquid “Reaction product C”. It was confirmed by ¹ H-NMR measurement that it was a polysiloxane compound having an epoxy group of 3.5 mmol / g and an SiH group of 4.5 mmol / g in terms of equivalent when the standard substance was dibromoethane.

(Synthesis Example 4: Synthesis of acryloyl group-containing compound)
A 500 mL four-necked flask was charged with 100 g of toluene and 20 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase was purged with nitrogen, and then heated and stirred at an internal temperature of 80 ° C. A mixed solution of 50 g of allyl methacrylate, xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) (0.00078 g) and 20.67 g of toluene was added dropwise. After dropping, the disappearance of the SiH group-derived peak was confirmed by ¹ H-NMR, and the reaction was completed.

Toluene was distilled off under reduced pressure to obtain a colorless and transparent liquid “Reaction product D”. ¹ H-NMR measurement confirmed that the polysiloxane compound had 7.0 mmol / g of methacryloyl group in terms of equivalent when the standard substance was dibromoethane.

(Synthesis Example 5: Synthesis of a phenol group-containing compound)
A 500 mL four-necked flask was charged with 100 g of toluene and 20 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase was purged with nitrogen, and then heated and stirred at an internal temperature of 80 ° C. A mixed liquid of 20 g of o-allylphenol, 10 g of vinylcyclohexene oxide and 0.0017 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) and 20.67 g of toluene was dropped. After dropping, the disappearance of the SiH group-derived peak was confirmed by ¹ H-NMR, and the reaction was completed.

Toluene was distilled off under reduced pressure to obtain a colorless and transparent liquid “Reaction product E”. ^{According to 1} H-NMR measurement, a polysiloxane compound having a phenol group of 2.0 mmol / g, an epoxy group of 1.8 mmol / g, and a SiH group of 6.0 mmol / g in terms of equivalent when the standard substance is dibromoethane. I confirmed that there was.

(Synthesis Example 6: Synthesis of epoxy group-containing compound)
A 500 mL four-necked flask was charged with 80 g of toluene and 20 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase portion was purged with nitrogen, and then heated and stirred at an internal temperature of 105 ° C. A mixed liquid of 6.29 g of diallyl isocyanurate, 3.16 g of triallyl isocyanurate, 0.0186 g of platinum vinylsiloxane complex in xylene (containing 3 wt% as platinum) and 41.83 g of dioxane was added dropwise. After the dropwise addition, the disappearance of the peak derived from the allyl group was confirmed by ¹ H-NMR. After the reaction was completed, toluene and unreacted cyclosiloxane were distilled off under reduced pressure to obtain a colorless transparent liquid reaction product.

Furthermore, what added 40g of toluene again to 10g of this obtained reaction material was heated and mixed at 105 degreeC. A mixed liquid of 2.53 g of vinylcyclohexene oxide and 2.53 g of toluene was added dropwise. After dropping, the disappearance of the vinyl group-derived peak was confirmed by ¹ H-NMR to complete the reaction.
Toluene was distilled off under reduced pressure to obtain a colorless and transparent liquid “Reaction product F”. ¹ H-NMR measurement confirmed that the polysiloxane compound had an epoxy group of 2.5 mmol / g and an SiH group of 3.5 mmol / g in terms of equivalent when the standard substance was dibromoethane.

(Examples 1-8, Comparative Examples 1-4)
Reactants A to F obtained in Synthesis Examples 1 to 6, photopolymerization initiator (1) (photoacid generator, manufactured by Rhodia, trade name: PI2074), photopolymerization initiator (2) (photoradical generator) , Manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184), photopolymerization initiator (3) (photo acid generator, product of Midori Chemical, trade name: BBI-103), dimethylpolysiloxane containing vinyl groups at both ends as a polysiloxane compound (Manufactured by gelest, trade name DMS-V05, average weight molecular weight: 800), SiH group-containing dimethylpolysiloxane (manufactured by gelst, trade name DMS-H11, average weight molecular weight: 1100), vinyl group-containing siloxane oligomer (manufactured by Clariant) , Trade name MQV7, average weight molecular weight: 1000), triallyl isocyanurate, PTVTSC3.0X A platinum vinyl siloxane complex (manufactured by NE Chemcat), 2-methyl-3-butyn-2-ol, and a solvent (PGMEA: propylene glycol-1-monomethyl ether-2-acetate) were prepared in the proportions shown in Table 1 and photocurable composition. I adjusted things.

1 Substrate 2 Gate electrode 3 Organic insulating film 4 Organic semiconductor layer 5 Source electrode 6 Drain electrode

Claims (7)

A compound selected from an epoxy group-containing polysiloxane compound, a (meth) acryloyl group-containing polysiloxane compound, and a phenol group-containing polysiloxane compound , and
A gate insulating film for an organic TFT comprising a cured product of a curable composition containing a polysiloxane compound having an average weight molecular weight of 500 to 10,000 and having a water contact angle of 95 degrees or more on the surface of the thin film. Polysiloxane compound having an average weight molecular weight 500 to 10,000 is a vinyl group, SiH group, methacryl group, an epoxy group, and, according to claim 1, characterized in that it contains one reactive functional group selected from amino group Gate insulating film for organic TFT. Epoxy group-containing polysiloxane compound, (meth) acryloyl group-containing polysiloxane compound, and, according to claim 1 or 2, characterized in that a phenol group-containing polysiloxane compound having an alkenyl group or SiH group in the same molecule The gate insulating film for organic TFTs described in 1. An epoxy group-containing polysiloxane compound, a (meth) acryloyl group-containing polysiloxane compound, and a phenol group-containing polysiloxane compound are represented by the following general formula (I):
The organic TFT gate insulating film according to any one of claims 1 to 3, characterized in that a compound containing a structure represented by the. It has alkali developability, The gate insulating film for organic TFTs as described in any one of Claims 1-4 characterized by the above-mentioned. The epoxy group-containing polysiloxane compound and the (meth) acryloyl group-containing polysiloxane compound are at least one selected from the group consisting of each structure represented by the following formulas (X1) and (X2) and a carboxyl group The gate insulating film for organic TFTs according to any one of claims 1 to 5 , comprising:
The organic TFT element which has a gate insulating film as described in any one of Claims 1-6 .