JP2013199629A - Curable composition, thin film, and thin film transistor using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a gate insulating film for an organic TFT comprising a curable composition that gives a thin film excellent in insulation; and an organic thin film transistor using the same.SOLUTION: It has been found out that the problem can be solved by using a curable composition that has the following features. A curable composition comprises a curable resin that makes a polysiloxane that has a specified structure an essential component, is characterized in that a water contact angle on a thin film surface after curing is at least 95 degrees, excels in insulation and has high surface water repellency, thereby can be applied as an organic TFT insulating film, and gives an organic TFT element that expresses an excellent transistor characteristic.

Description

  The present invention relates to a thin film and a curable composition that have excellent insulating properties and give good characteristics when used as a gate insulating film for an organic TFT.

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 (for example, 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 (for example, Patent Document 1), polyimide-based polymers (for example, Patent Document 2), silicon, and the like. Although a transistor using an organic material such as a polymer based polymer (for example, Patent Document 3) as an insulating film has been proposed, it has been difficult to obtain good semiconductor characteristics only by using these materials as an insulating film. For this reason, a complicated process is required such that these films must be used after being surface-treated with a silane coupling agent or the like.

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 a curable composition that provides a thin film having excellent insulating properties and an organic thin film transistor using the same as a gate 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 resin composition having the following features, and the present invention has been completed. That is, the present invention has the following configuration.

  1). A curable composition containing a polysiloxane represented by the general formula (I) and having a water contact angle of 95 degrees or more on the cured product surface after curing.

(Wherein x is 1 to 150, y is an arbitrary integer of 1 to 150, and A represents an alkyl group having 1 to 30 carbon atoms, which may be different or the same).

  2). The curable composition according to 1), which contains any one of an epoxy group-containing compound, a (meth) acryloyl group-containing compound, a phenol group-containing compound, and a hydrosilylation reactive composition.

  3). 2. The curable resin composition according to 2), wherein the epoxy group-containing compound is an epoxy group-containing polysiloxane.

  4). The curable resin composition according to 2), wherein the (meth) acryloyl group-containing compound is a (meth) acryloyl group-containing polysiloxane.

  5). 2. The curable resin composition according to 2), wherein the phenol group-containing compound is a phenol group-containing polysiloxane.

  6). 2. The curable composition according to 2), wherein the hydrosilylation-reactive composition is an alkenyl group-containing compound, a compound having a SiH group-containing cyclic siloxane in the molecule, or a hydrosilylation reaction catalyst.

  7). Formula (II)

The curable composition as described in any one of 1) -6) characterized by including the compound which has a structure represented by these.

  8). A thin film obtained by curing the curable composition according to any one of 1) to 7).

  9). The organic thin-film transistor which uses the thin film as described in 8) as a gate insulating film.

  The thin film obtained from the curable composition of the present invention has excellent insulating properties, and when used as a gate insulating film for an organic thin film transistor, an organic thin film transistor having good transistor characteristics can be obtained without performing surface treatment of the insulating film.

Cross-sectional reference diagram of organic TFT 1 Cross-sectional reference diagram of organic TFT 2

The details of the invention will be described.
The curable composition of the present invention can provide a gate insulating film for organic TFTs having excellent insulating properties.
In general, epoxy resins composed of polyfunctional epoxy compounds, polyfunctional acrylate compounds, novolac resins, acrylic resins, phenol resins, etc. are applied as various typical curable resins for various purposes. After curing, insulation and chemical resistance Therefore, it is suitable for a member that requires strict insulation, for example, a member such as a gate insulating film for an organic TFT. However, when these resins are used for a gate insulating film of a TFT, the influence of semiconductor electron / carrier trapping is large, and it is the present situation that an element having good transistor characteristics cannot be obtained. The curable composition of the present invention 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. From the viewpoint that the surface is hardly oxidized and excellent in stability, Au and Pt are preferable, 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. Further, viscosity adjustment with a solvent may be appropriately performed in accordance with the state of the substrate to be formed and the method for forming the insulating film.

  In general, carrier mobility, threshold voltage, hysteresis, and ON / OFF current ratio are important characteristics for the stable driving of an active matrix flat panel display as a transistor to obtain a clear image. ing.

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), a function as a switch larger It is preferably 10 ⁴ or more, and more preferably 10 ⁵ or more, because it shows excellent performance 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. The larger the value, the better the TFT element. However, from the viewpoint of a good image display device, 0.1 or more, Is preferably 0.18 or more. Further, it is preferably 0.21 or more, particularly 0.45 or more. In particular, by using the thin film obtained in the present invention as a gate insulating film, an excellent organic TFT having a large ON / OFF current ratio and carrier mobility can be obtained.

(About TFT passivation film)
Moreover, the curable composition of this invention can be used suitably also as a passivation film for TFT. The TFT passivation film is an insulating film that serves to cover and protect the TFT element from above. Each can be used alone as a gate insulating film and a passivation film, but in particular, in a transistor in which both the gate insulating film and the passivation film are formed using the curable composition of the present invention, the adhesion between the layers is excellent. Therefore, even when the area is increased, it is preferable because there are few defects such as separation between the gate insulating film and the passivation film.

In particular, application to a TFT provided over a flexible substrate using a thin film substrate is preferable because defects such as peeling between films that are likely to occur during bending are reduced.
As the thin film substrate, metals and organic resins can be mentioned, but it is preferable to have transparency, and a substrate made of an organic resin is preferable because it also has insulating properties.

  The insulating support substrate made of organic resin is not particularly limited, but is represented by polyimide resin, polyester resin such as polyethylene terephthalate and polyethylene naphthalate, acrylic resin such as PMMA, ZEONEX, ARTON, etc. And cycloolefin resins, polyethersulfone resins, polycarbonate resins, polystyrene resins, and the like.

  Among these, polyethylene naphthalate and polyethylene terephthalate are preferable because of transparency, and polyethylene terephthalate is more preferable from the viewpoint of being inexpensive and easily available.

(About surface water repellency)
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, when applied as a gate insulating film for an organic TFT, there is a problem that good transistor characteristics are hardly exhibited.

  In order to solve this problem, the present inventor has found that good transistor characteristics can be exhibited by using a curable composition containing polysiloxane having a specific structure as an essential component. Furthermore, it has also been found that the contact angle with water on the film surface after curing must be greater than a certain value. The contact angle is 95 ° or more, preferably 99 ° or more. In particular, it is preferably 100 ° or more, more preferably 101 ° or more. The upper limit can be 110 °, and further 104 °.

  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 Nippon Zeon, trade name: Arton, manufactured by JSR), silicone resin having no epoxy group, acrylic group or hydrosilylation reactive group. However, with these materials, unevenness and repellency are likely to occur when forming a film on a substrate, and it is difficult to obtain a uniform film. Also, since these materials have poor chemical resistance and substrate adhesion to etching solutions used in TFT manufacturing processes. It was difficult to apply as an insulating film for TFT.

  The curable composition of the present invention is characterized by using a polysiloxane represented by the general formula (I). For example, an epoxy group, a (meth) acryloyl group, a phenol group, or a hydrosilyl group is used for the curable composition. A curable composition containing, as a main component, a compound having a curable group such as a fluorinated reactive group can be used.

  By using these compounds having a curable group and the polysiloxane represented by the general formula (I), an excellent insulating film can be obtained. The composition of the present invention is 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.

(About polysiloxane)
In the present invention, a thin film having a water contact angle of 95 degrees or more on the surface of a cured product after curing is obtained as an organic TFT, which contains a polysiloxane having a specific structure represented by the general formula (I). It has been found that an organic TFT having excellent transistor characteristics can be obtained when used as a gate insulating film.

(Wherein x is 1 to 150, y is an arbitrary integer of 1 to 150, and A represents an alkyl group having 1 to 30 carbon atoms, which may be different or the same) The number of x and y is preferably an arbitrary integer from 1 to 90, since water repellency on the surface of the cured film is less likely to be exhibited if the number of units is too small or too large. It is preferable that it is -50.
In addition, from the viewpoint of compatibility with the curable resin, the range is preferably 2 ≦ x + y ≦ 200, more preferably 2 ≦ x + y ≦ 150.

  The ratio of x and y is preferably set in the range of 0.01 ≦ x / y ≦ 100. If the alkyl group A is too small in the molecule, the water repellent effect on the insulating film surface is reduced. In addition, if there are too few SiH groups, they are not incorporated into the bridge and adversely affect the TFT characteristics as impurities. Therefore, it is more preferable that 0.1 ≦ x / y ≦ 10, particularly preferably 0.2 ≦ x / y ≦. 5.

  In addition, the structure of the alkyl group A in the polysiloxane is preferably composed only of carbon atoms and hydrogen atoms from the viewpoint of easy development of water repellency to the cured film surface. From the viewpoint of good compatibility, the carbon number is preferably 1 to 25, more preferably 3 to 20, and more preferably 5 to 15 from the viewpoint of more excellent TFT characteristics.

  The structure of the alkyl group A is not particularly limited as long as it is a chain structure, a branched structure, or a ring structure. In particular, the viewpoint that the crystalline state of the semiconductor laminated on the film is likely to be improved and the TFT characteristics are easily improved. Therefore, it is preferably a chain, and is preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, or an n-nonyl group. , N-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group and the like.

  Further, from the viewpoint of good compatibility with the compound having a curable group, it is preferably branched or cyclic, and is isopropyl group, isobutyl group, isopentyl group, isohexyl group, isoheptyl group, isooctyl group, isononyl group, Isodecyl group, isododecyl group, isotetradecyl group, isohexadecyl group, isooctadecyl group, tert-butyl group, tert-pentyl group, tert-hexyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, Examples include a norbornyl group, a dicyclopentyl group, and an isobornyl group.

  When there are a plurality of A, they may be different or the same. One or more alkyl groups having a chain, branched or cyclic structure can be selected and used according to the required characteristics of the insulating film.

  The method for obtaining the polysiloxane of the present invention is not particularly limited, but the simplest method includes, for example, a SiH group-containing polysiloxane represented by the following general formula (III) and an olefin compound having a carbon number to be introduced. It can be obtained by hydrosilylation.

(In the formula, m is 1 to 300, and n is an arbitrary integer of 0 to 150)
From the viewpoint of availability, those having only a SiH group as the functional group are preferable. Specific examples include TSF484 (made by Momentive), KF-99 (made by Shin-Etsu Chemical), SH1107 (made by Toray Dow Corning), and the like. It is done.
Further, from the viewpoint of adjusting the compatibility, a copolymer with dimethylsiloxane may be used. Specific examples of the compound include HMS-301 and HMS-501 (manufactured by Gelest).

  The olefin compound used for hydrosilylation can be used without particular limitation as long as it is an olefin compound having a carbon number to be introduced. Specifically, 1-pentene, 4-methyl 1- Pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, other linearene 124, linearlen 148, linearlen 168, linearlen Dimer A-20, linearlen 2024 (manufactured by Idemitsu Kosan) and the like are suitable. Further, from the viewpoint of compatibility, 4-methyl 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-dodecene are preferable.

  The content of the polysiloxane having the specific structure represented by the general formula (I) in the curable composition is preferably used in a range (weight) not exceeding the weight of the compound having a curable group. 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 the compound having a curable group, which will be described later, which is the main component.

  If the addition amount is small, the water repellency on the surface of the thin film obtained by curing is difficult to stabilize, and if the addition amount is large, there is a problem in that it is not compatible and separated, and film formation failure occurs due to repellency during coating.

  Examples of the curable group that can be used in the present invention include an epoxy group, a (meth) acryloyl group, a phenoz group, and a combination of an alkenyl group and a SiH group. The compound having a curable group is a composition of an epoxy group-containing compound, a (meth) acryloyl group-containing compound, a phenol group-containing compound, an alkenyl group-containing compound and a SiH group-containing compound each having a curable group. Can be mentioned.

(Epoxy group-containing compound)
The epoxy group of the epoxy group-containing compound that can be used in the present invention can be selected from alicyclic epoxy groups and glycidyl groups. It functions as a film with excellent insulation properties by crosslinking by heating or light energy. Typical examples are bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenol type epoxy resin, and bixylenol. Type epoxy resins, bisphenol type epoxy resins, 1,2-dihydroxynaphthalene type epoxy resins, 1,3-dihydroxynaphthalene type epoxy resins, 1,4-dihydroxynaphthalene type epoxy resins, 1,5-dihydroxynaphthalene type epoxy resins 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-dihi Roxynaphthalene type epoxy resin, dihydroxynaphthalene type epoxy resins such as 2,7-dihydroxynaphthalene type epoxy 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 di Glycidyl ether, 1,6-hexanediol Linear aliphatic epoxy compounds such as glycidyl ether and neopentyl glycol diglycidyl ether, hydrogenated bisphenol A type epoxy resin, hydrogenated biphenyl type epoxy resin, 1,4-cyclohexanediol type epoxy resin, 1,4-cyclohexane Examples include alicyclic epoxy compounds such as dimethanol type epoxy resin.

  Furthermore, in order to improve these curability, chemical resistance, and insulation, a cationic polymerization initiator, an acid anhydride compound, an amine compound, a phosphorus compound, and the like described later may be added as a crosslinking agent.

  Among these, an epoxy resin containing an epoxy group-containing polysiloxane is preferable from the viewpoint that a thin film having excellent chemical resistance can be easily obtained. The method for obtaining the epoxy group-containing polysiloxane is not particularly limited, but includes a method of condensing an alkoxysilane having an epoxy group, a compound having an epoxy group and an alkenyl group in the same molecule, and a polysiloxane having an SiH group. A method obtained by hydrosilylation reaction and the like can be mentioned, but the latter method is preferable from the viewpoint that an unreacted site hardly remains and a thin film having excellent insulating properties is easily obtained.

  Compounds having an epoxy group and an alkenyl group in the same molecule that can be used in this production method include vinylcyclohexene oxide, allyl glycidyl ether, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, glycidyl methacrylate, Examples thereof include hydroxybutyl acrylate glycidyl ether, allyl oxetanyl ether, and vinyl oxetanyl ether. From the viewpoint of excellent photopolymerization reactivity, vinyl cyclohexene oxide which is a compound having an alicyclic epoxy group is particularly preferable. When using the compound which has oxetanyl group, it is preferable from a viewpoint that hardened | cured material intensity | strength improves.

  Examples of polysiloxanes having SiH groups include polysiloxanes whose ends are blocked with dimethylhydrosilyl groups, cyclic siloxanes containing SiH groups, and linear polysiloxanes containing SiH groups in the main chain (eg, TSF484, manufactured by Momentive). It is done.

  Among them, it is preferable from the viewpoint that a film excellent in strength and solvent resistance can be easily obtained by applying a SiH group-containing cyclic siloxane. Specific examples include 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 Dihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-7-hexyl-1,3,5,7-te Lamethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-1,3,5- 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.

  In order to improve the strength of the film, a partial reaction product obtained by hydrosilylating a compound having two or more alkenyl groups in one molecule and SiH group-containing polysiloxane in advance as a polysiloxane having SiH groups should also be used. You can also.

  The compound having two or more alkenyl groups referred to here can be used without particular limitation. Specific examples 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, diarylidene pentaerythritol, triallyl cyanurate, 1,2,4- Trivinylcyclohexane, 1,4-butanediol diallyl ether, nonanediol diallyl ether, 1,4-cyclohexane dimethanol diallyl ether, triethylene glycol diallyl ether, trimethylo Rupropane 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, dicyclopentadiene, cyclopentadiene, cyclohexadiene, cyclooctadiene, tricyclo Pentadiene, norbornadiene, vinylnorbornene, vinylcyclohexene, vinylcyclopentene, butadiene, isoprene, octadiene, 1,5-hexadiene, 1,5-hexadiene, , 9-decadiene, diallyl ether, bisphenol A diallyl ether, bisphenol S diallyl ether, 2,5-allylphenol allyl ether.

  In particular, it is particularly preferable to use an alkenyl compound having a structure represented by the following general formula (II) from the viewpoint of easily forming a cured product / thin film having high transparency, heat resistance, light resistance, and insulation.

  Specific examples of these compounds include triallyl isocyanurate, diallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monobenzyl isocyanurate, diallyl monopropyl isocyanurate, monoallyl dibenzyl isocyanurate, diallyl monomethyl isocyanurate, monoallyl dimethyl. An isocyanurate is mentioned, and a triallyl isocyanurate is mentioned especially from a viewpoint of availability.

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.

  Specifically, 1,3,5,7-tetravinyl-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-hexamethylcyclo Examples thereof include compounds such as siloxane.

((Meth) acryloyl group-containing compound)
As the (meth) acryloyl group-containing compound that can be used in the present invention, a compound that can be formed into a film by crosslinking by heating or light energy can be used as in the case of 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 polysiloxane 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 having a (meth) acryloyl group is not particularly limited, but a method of condensing an alkoxysilane having a (meth) acryloyl group, a compound having a (meth) acryloyl group, and a polysiloxane having a SiH group A method obtained by hydrosilylation reaction of the compound, and the like can be mentioned, but the latter method is preferred from the viewpoint of easily forming a thin film having unreacted sites and less insulating properties.

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

  Moreover, as polysiloxane which has SiH group, the compound which can be used with the said epoxy group containing compound can be used.

(Phenol group-containing compound)
Examples of the phenol group-containing compound that can be used in the present invention include polyvinyl phenol resins, novolac resins, resole resins, and polysiloxane resins having a phenol group. In order to further increase the insulation and chemical resistance, a melamine compound may be added as a crosslinking agent.

  Moreover, it is preferable that it is a polysiloxane which has a phenol group from a viewpoint from which the thin film which is excellent in chemical resistance is obtained. A method for obtaining a polysiloxane having a phenol group is not particularly limited, but a method of condensing an alkoxysilane having a phenol group, a hydrosilylation reaction of an allyl group-containing compound having a phenol group and a polysiloxane having a SiH group. However, the latter method is preferable from the viewpoint that an unreacted site does not easily remain and the thin film is excellent in insulation.

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

  Moreover, as polysiloxane which has SiH group, the compound which can be used with the said 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.

(Hydrosilylation reactive composition)
As the curable composition of the present invention, a hydrosilylation reactive composition having an alkenyl group-containing compound, a SiH group-containing compound, and a hydrosilylation catalyst as essential components can also be applied. This composition is excellent in reactivity and easily obtains a thin film having excellent insulating properties even under low temperature conditions, and is also suitable as an insulating film for thin film transistors.

  As a compound which has an alkenyl group here, and a SiH group containing compound, if it is a compound which can be used when obtaining the above-mentioned epoxy group containing polysiloxane, it can use without limitation. As the compound having an alkenyl group, in particular, from the viewpoint that a film obtained by curing has a high cross-linking density and is easy to obtain an excellent insulating property, one or more and 20 or less, and further 3 or more per molecule. Those having 15 or less alkenyl groups are preferred. Practically, it is preferable to use a compound having two or more alkenyl groups.

  Specifically, triallyl isocyanurate, triallyl cyanurate, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclosiloxane, 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 and the like. . As the SiH group-containing compound, a compound having a SiH group-containing cyclic siloxane in the molecule is preferable from the viewpoint of being easily a cured product / thin film having excellent insulating properties.

  A well-known hydrosilylation catalyst may be a known hydrosilylation catalyst. 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.

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-methyl-1-butyne-2- Examples thereof include acetylene alcohol compounds such as all 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 with respect 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.

(Cationic polymerization initiator)
In the curable composition of the present invention, a cationic polymerization initiator can be appropriately used hereinafter.
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 salts and aromatic sulfonium complex salts, bis [4- (diphenylsulfonio) phenyl] sulfide-bishexafluorometal salts (for example, phosphates, arsenates, antimonates, etc.); anions of B (C ₆ F ₅ ) ₄ ^- one or more kinds of aromatic iodonium complex salts and aromatic sulfonium complex salts include an It is.

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

  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. As a curing method, curing by heat, curing by light, or a combination of a curing method of heat and light can be used.

  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.

  The curable composition of the present invention can be cured by proceeding with a crosslinking reaction by light irradiation. However, by adopting a curing method by light irradiation, the curing time can be shortened or the present invention can be applied to a desired location. It is preferable because a film made of the composition can be formed (patterning). As a light source that can be used for curing by light irradiation, a light source that emits 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, it becomes difficult to take advantage of the rapid curing characteristics of photocuring.

  For the purpose of removing the solvent contained in the curable composition and improving the physical properties of the cured product, it is preferable to perform heat curing (post-baking) by applying heat after photocuring to sufficiently advance the curing. In addition, a thermosetting operation can be performed before the photocuring operation to partially cure the curable composition.

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 that can 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- Examples include tert-butylanthracene.

  Anthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene and the like are particularly preferable from the viewpoint of easy availability.

  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.

(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 adhesiveness 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 curable composition. 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 can be added to the curable composition of the present invention for the purpose of modifying the properties. Various types of thermoplastic resins can be used.

  Specifically, for example, a methyl methacrylate homopolymer 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.), butyl acrylate, etc. Acrylic resins represented by homopolymers or polybutyl acrylate resins such as random, block or graft polymers of butyl acrylate and other monomers, bisphenol A, 3,3,5-trimethylcyclohexylidene bisphenol, etc. A polycarbonate resin such as a polycarbonate resin (for example, APEC manufactured by Teijin Ltd.), a norbornene derivative, a resin obtained by homopolymerizing or copolymerizing a vinyl monomer, a norbornene derivative with a ring-opening metathesis weight Cycloolefin-based resins such as hydrogenated products thereof (for example, APEL manufactured by Mitsui Chemicals, ZEONOR, ZEONEX manufactured by Nippon Zeon, ARTON manufactured by JSR, etc.), and olefins such as 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, Po Amide resin, a silicone resin, other like fluorine resin, natural rubber, but the rubber-like resin is exemplified such EPDM, but 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 compatibility with polysiloxane is likely to be good. . 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 5 to 20 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.

(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 phenols. Various types of hindered phenol-based anti-aging agents 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 polysiloxane 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, ester solvents such as butyl acetate, isobutyl acetate, butyl butyrate and isobutyl isobutyrate, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, propylene glycol-1-monomethyl ether-2-acetate ( PGMEA), glycol solvents such as ethylene glycol diethyl ether, and halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used.

  In particular, from the viewpoint of being less likely to be uneven during film formation and easily forming a uniform film, ethylene glycol diethyl ether, 1,4-dioxane, propylene glycol-1-monomethyl ether-2-acetate, isobutyl butyrate, isobutyl isobutyrate, butyl acetate Is preferred.

  The amount of the solvent to be used can be appropriately set, but the lower limit of the preferred amount of use with respect to 1 g of the curable composition 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 1-9, Comparative Examples 1-3)
The curable compositions obtained in Examples and Comparative Examples 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 and Comparative Examples were formed on a glass substrate 30 × 30 mm to a thickness of 1.5 μm by spin coating, dried at 100 ° C. for 2 minutes on a hot plate, and 100 mJ / cm on an exposure machine. ^{2 A} thin film sample was obtained by heating at 150 ° C. for 30 minutes after 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 curable compositions obtained in Examples and Comparative Examples are applied thereon by spin coating under conditions of 1000 rpm and 30 sec. After drying at 100 ° C. for 2 minutes using a hot plate and 100 mJ / cm ² UV irradiation using an exposure machine, post-baking was performed at 150 ° C. for 30 minutes to form a gate insulating film 3. Further, a pentacene organic semiconductor layer 4 having a thickness of 500 nm is formed by vapor deposition to a thickness of 500 nm, and source / drain Au electrodes 5 and 6 having a thickness of 300 mm are formed by vapor deposition using a mask having a channel length of 100 μm and a channel width of 5 mm. A thin film transistor was formed.

(Transistor characteristic evaluation)
For organic thin film transistors created by using the gate insulating films of Examples and Comparative Examples using the method of the present invention, the ON / OFF from the curve of current transfer characteristics under the following driving conditions using the semiconductor characteristic evaluation system 4200 (manufactured by Keithley) The OFF ratio was evaluated.

Driving conditions In a state where a voltage of −40 V is applied between the source and the drain in the fabricated transistor, the current amount (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.

-Carrier mobility The carrier mobility μ was calculated from the following formula.
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 : Maximum value between saturation regions (gate voltage V _g = 30 to 40 V) in the source-drain current-current transfer characteristic was adopted.

(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”. It was confirmed by ¹ H-NMR measurement that it was an epoxy group-containing polysiloxane having 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, the disappearance of vinyl group and allyl group-derived peaks 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 B”. ¹ H-NMR measurement confirmed that the epoxy group-containing polysiloxane 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, the disappearance of vinyl group and allyl group-derived peaks 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 C”. ^{By 1} H-NMR measurement, it was confirmed that it was an epoxy group-containing polysiloxane 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 methacryloyl 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”. It was confirmed by ¹ H-NMR measurement that it was a methacryloyl group-containing polysiloxane having a methacryloyl group of 7.0 mmol / g 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”. Phenol group-containing polysiloxane having a phenol group of 2.0 mmol / g, an epoxy group of 1.8 mmol / g, and an SiH group of 6.0 mmol / g in terms of equivalent when the standard substance is dibromoethane by ¹ H-NMR measurement. It was confirmed that.

(Synthesis Example 6: Synthesis of SiH 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 105 ° C. A mixed liquid of 2.76 g of triallyl isocyanurate, 0.0019 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) and 2.76 g of toluene was added dropwise. After dropping, the disappearance of the peak derived from the allyl group 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 F”. It was confirmed by ¹ H-NMR measurement that the polysiloxane compound had 9.2 mmol / g SiH group in terms of equivalent when the standard substance was dibromoethane.

(Synthesis Example 7: Synthesis of polysiloxane)
Into a 200 mL four-necked flask, put 30 g of toluene and 5 g of SiH group-containing polysiloxane (TSF484, manufactured by Momentive, molecular weight 6600, ratio of m and n represented by the general formula (III): m = 110, n = 0). After replacing the phase part with nitrogen, the internal temperature was set to 105 ° C., and a mixed solution of 4.4 g of 1-hexene, 4.4 g of toluene and 0.0019 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise. It was confirmed by ¹ H-NMR that the alkenyl group had disappeared, and the reaction was terminated by cooling. The solvent toluene was distilled off under reduced pressure to obtain polysiloxane 1 (a ratio of xy represented by the general formula (I): x = 17, y = 33, a compound in which A is an n-hexyl group).

(Synthesis Example 8: Synthesis of polysiloxane)
Into a 200 mL four-necked flask is placed 30 g of toluene and 5 g of SiH group-containing polysiloxane (HMS-501, manufactured by Gelest, molecular weight 1000, m / n ratio represented by formula (III): m = 8, n = 8). After replacing the gas phase with nitrogen, the internal temperature was set to 105 ° C., and a mixed solution of 3.1 g of 1-dodecene, 6.1 g of toluene, and 0.0019 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was dropped. did. It was confirmed by ¹ H-NMR that the alkenyl group had disappeared, and the reaction was terminated by cooling. The solvent toluene was distilled off under reduced pressure to obtain polysiloxane 2 (the ratio of xy represented by the general formula (I): x = 3, y = 5, and A is an n-dodecyl group).

(Adjustment of the curable composition used in Examples 1-9 and Comparative Examples 1-3)
Reactants A to F obtained in Synthesis Examples 1 to 8, polysiloxanes 1 and 2, and photopolymerization initiator 1 (photoacid generator, manufactured by Midori Chemical Co., Ltd., trade name: BBI-103), photopolymerization initiator 2 (photo radical generator, manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184), hydrosilylation catalyst (NE Chemcat, trade name: PT-VTS3.0X), D4V (1,3,5,7-tetramethyl-1 , 3,5,7-tetravinylcyclosiloxane), TSF484 (SiH group-containing polysiloxane, manufactured by Momentive) and solvent (isobutyl isobutyrate) in the proportions (parts by weight) shown in Table 1 to prepare a curable composition. It was adjusted.

(Examples 10-15, 16-20)
On the thin film transistors obtained in Examples 1 to 6, the curable compositions obtained in Examples 1 to 6 were applied by spin coating under the conditions of 2000 rpm and 20 sec, respectively, and heated on a hot plate heated to 65 ° C. Heat for 2 minutes using an exposure apparatus through a 50 μm square pattern mask on a hot plate heated to 65 ° C. after irradiation with 100 mJ / cm ² UV, and further post-baked at 150 ° C. for 30 min to obtain a thickness of 2. A 0 μm passivation film 7 was formed, and a thin film transistor was manufactured (Examples 10 to 15).

  Further, on the thin film transistor obtained in Example 1, a passivation film 7 was formed in the same manner as in Examples 10 to 15 using the curable compositions obtained in Examples 2 to 6, respectively, thereby producing a thin film transistor ( Examples 16-20).

  Similar to the transistors obtained in Examples 1 to 6, these thin film transistors showed good carrier mobility and ON / OFF ratio.

(Example 21)
(Synthesis Example 9: Synthesis of polysiloxane)
A 300 mL four-necked flask was charged with 72.4 g of toluene and 72.4 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase was purged with nitrogen. Then, a mixed solution of 10 g of toluene and 0.0063 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise. It was confirmed by ¹ H-NMR that the allyl group had disappeared, and the reaction was terminated by cooling.

Toluene was distilled off under reduced pressure to obtain “Reactant G”. It was confirmed by ¹ H-NMR measurement that it was a polysiloxane compound having a SiH group of 9.2 mmol / g in terms of equivalent when the standard substance was dibromoethane.

  1.5 g of the reaction product G thus obtained, 1 g of triallyl isocyanurate, 0.0025 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum), 0.25 g of 2-methyl-3-butyn-2-ol, 0050 g and propylene glycol monomethyl ether acetate (solvent, PGMEA) 7.5 g were mixed to prepare a curable composition.

  A gate electrode 2 having a thickness of 500 mm is formed on a flexible polyethylene terephthalate substrate 1 using aluminum (Al), and the curable composition obtained thereon is applied by spin coating under conditions of 1000 rpm and 30 sec. The gate insulating film 3 was formed by post-baking for 1 h. Further, pentacene organic semiconductor layer 4 is formed to a thickness of 500 mm by vapor deposition, and source / drain Au electrodes 5 and 6 having a thickness of 300 mm are formed by vapor deposition using a mask having a channel length of 100 μm and a channel width of 5 mm. A thin film transistor was manufactured. Furthermore, the passivation film 7 was formed using the curable composition, and the flexible thin-film transistor was manufactured.

This thin film transistor was flexible and exhibited good carrier mobility and ON / OFF ratio.
In addition, the water contact angle of the film | membrane surface which consists of this curable composition showed 100 degree | times or more.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Gate electrode 3 Gate insulating film 4 Organic semiconductor layer 5 Source electrode 6 Drain electrode 7 Passivation film

Claims (9)

A curable composition containing a polysiloxane represented by the general formula (I) and having a water contact angle of 95 degrees or more on the cured product surface after curing.
(Wherein x is 1 to 150, y is an arbitrary integer of 1 to 150, and A represents an alkyl group having 1 to 30 carbon atoms, which may be different or the same). The curable composition according to claim 1, comprising any one of an epoxy group-containing compound, a (meth) acryloyl group-containing compound, a phenol group-containing compound, and a hydrosilylation reactive composition. The curable resin composition according to claim 2, wherein the epoxy group-containing compound is an epoxy group-containing polysiloxane. The curable resin composition according to claim 2, wherein the (meth) acryloyl group-containing compound is a (meth) acryloyl group-containing polysiloxane. The curable resin composition according to claim 2, wherein the phenol group-containing compound is a phenol group-containing polysiloxane. The curable composition according to claim 2, wherein the hydrosilylation-reactive composition is an alkenyl group-containing compound, a compound having a SiH group-containing cyclic siloxane in the molecule, or a hydrosilylation reaction catalyst. Formula (II)
The curable composition as described in any one of Claims 1-6 containing the compound which has a structure represented by these. The thin film obtained by hardening | curing the curable composition as described in any one of Claims 1-7. The organic thin-film transistor which uses the thin film of Claim 8 as a gate insulating film.