JP2010258378A - Insulating thin film, and thin-film transistor using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insulating film having a liquid form and capable of easily forming a thin film by handling and solution application, and usable for a passivation film, a gate insulating film or the like of an electronic component requiring a high insulation property in a low baking temperature condition, for instance, a thin-film transistor. <P>SOLUTION: In a thin film formable by applying a solution of a resin composition, and obtained by post bake below 170°C, the problem can be solved by this insulating thin film having a calorific value ≤5 J/g by DSC measurement. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  An object of the present invention is to provide a thin film excellent in electrical insulation under low temperature conditions and a thin film transistor using the thin film as a passivation film or a gate insulating film.

  In recent years, flexible displays such as OLED and electronic paper have been actively developed as next-generation displays, and a flexible resin film substrate is used as the substrate, which is transparent and has relatively high heat resistance PEN, Materials such as PES are being considered for application. However, because the resin film substrate has a large linear expansion and low heat resistance, conventional CVD transistor formation is not applicable, and it uses oxide semiconductors and organic semiconductor materials that can be formed at low temperatures and by simple methods such as printing. TFTs that have been attracting attention are being actively researched and developed.

  At this time, not only the formation of the semiconductor layer but also a low-temperature formation technique for the insulating film and the protective film is essential, and a low-temperature and simple process for forming an insulating film and materials are desired. For these reasons, attempts have been made to form organic materials such as polyvinyl alcohol, epoxy resins, and silicon-based polymers. However, gate insulating films using these organic materials are used as inorganic insulating films by CVD. Compared with reliability such as insulation, the insulating film material that can be effectively formed at a low temperature has not been obtained.

JP 2004-349319 A JP 2007-158147 A JP 2007-43055 A

  In view of the above circumstances, an object of the present invention is to provide an insulating thin film excellent in electrical insulation under low temperature conditions and a thin film transistor using the insulating thin film as a passivation film or 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). An insulating thin film which can be formed by applying a resin composition in a solution and which is obtained by post-baking at 170 ° C. or less and whose calorific value by DSC measurement is 5 J / g or less.

  2). The thin film according to 1), wherein the dielectric breakdown voltage is 4 MV / cm or more.

3). The thin film according to 1) or 2), wherein the leakage current when 30 V is applied has an insulating property of ²⁰ nA / cm ² or less.

  4). The resin composition according to any one of 1) to 3), wherein the resin composition contains a polysiloxane compound as a main component.

  5). The polysiloxane compound is a cyclic polysiloxane formed from 3 to 10 Si atoms in the molecule or a polysiloxane having a polyhedral skeleton formed from 6 to 24 Si atoms in the molecule. And the thin film according to 4).

  6). The thin film according to any one of 1) to 5), wherein the polysiloxane compound has a photopolymerizable functional group.

  7). The curable composition of Claim 6 whose photopolymerizable functional group is an alicyclic epoxy group or a glycidyl group.

  8). The resin composition has photolithography properties, and the thin film according to any one of 1) to 7).

  9). The resin composition has at least one photopolymerizable functional group and is selected from the group consisting of each structure represented by the following formulas (X1) to (X3), a phenolic hydroxyl group, and a carboxyl group. The thin film according to 8), which contains a compound having at least one kind in the molecule.

  10). The thin film according to any one of 5) to 9), wherein the polysiloxane compound is obtained by a hydrosilylation reaction between a cyclic siloxane compound having a SiH group and a compound having an alkenyl group.

  11). 10. The thin film according to 10), wherein the polysiloxane compound is a compound having a photopolymerizable functional group and a SiH group in one molecule.

  12). 11. The thin film according to 11), wherein the resin composition contains a compound having an alkenyl group.

  13). A thin film transistor according to any one of 1) to 12), wherein the thin film is a passivation film of a semiconductor layer or a gate insulating film.

  ADVANTAGE OF THE INVENTION According to this invention, the passivation film or gate insulating film excellent in electrical insulation on low-temperature baking temperature conditions, and a thin-film transistor using the same can be provided.

The details of the invention will be described.
Since the resin composition of the present invention is liquid and can be easily formed into a thin film by handling and solution coating, and the thin film has high insulation at a low temperature baking temperature, it can be used as an insulating film for electronic parts and semiconductors.

  The thin film obtained from the composition of the present invention can be applied to electronic parts that require high insulation properties, such as passivation films and gate insulating films of thin film transistors.

  In particular, organic semiconductors using compounds such as pentacene, oligothiophene, and phthalocyanine, and oxide-based semiconductors such as ZnO and InGaZnO, which are attracting attention as next-generation transistor materials in recent years, can be formed at low temperatures by printing or sputtering. Research and development has been actively conducted as a material suitable for driving a flexible display such as electronic paper using a film substrate.

  Naturally, the formation temperature of a transistor using a plastic substrate must be lower than the deformation temperature and heat resistance temperature of the substrate material, and not only the semiconductor layer but also the passivation film and gate insulating film are formed under low temperature conditions by solution coating. In particular, it can be said that the thin film of the present invention is a suitable material for the insulating film. In order to form a transistor on a transparent resin substrate typified by PEN or PES as a substrate, it is preferably 170 ° C. or lower, and 155 ° C. or lower is preferable in consideration of dimensional stability, heat resistance, etc. of the resin substrate, Preferably it is 135 degrees C or less, More preferably, it is preferable to express insulation by heating under 100 degrees C.

  However, until now, various resin materials have been proposed as organic insulating films formed under low-temperature baking conditions (170 ° C. or lower). However, since the insulation reliability is low such as low dielectric breakdown voltage and large leakage current, FET At present, there is no effective material / means that can be applied to a gate insulating film or a passivation film.

  In general, when an insulating film is formed of a resin material, an annealing process is performed at a high temperature exceeding 200 ° C. to advance a crosslinking reaction, thereby eliminating an unreacted portion that can be a current leakage point and a dielectric breakdown point. Techniques to express sex are taken.

  The composition of the present invention is characterized in that it does not require annealing at a high temperature such as 200 ° C. or higher, but completes the crosslinking reaction under low-temperature baking conditions and exhibits high insulation properties. The progress of the reaction can be detected by DSC measurement. In this DSC measurement, when unreacted sites remain in the thin film, the amount of unreacted sites can be quantified by detecting the heat of reaction. Therefore, it can be seen as an index for functioning as a gate insulating film or a passivation film for an FET. From this viewpoint, the reaction heat in the DSC measurement in the organic insulating film is 5 J / g or less, more preferably 1 J / g or less.

  The calorific value here refers to the total calorific value generated when the temperature of the thin film of the present invention is raised from room temperature to 350 ° C. or higher by differential scanning calorimetry (DSC). The DSC measurement apparatus is not particularly limited, and a general-purpose DSC measurement apparatus can be used. About a measurement temperature range, since it needs to be a temperature range which all the crosslinking reaction heat in general curable resin detects, it is preferable to measure in the range of room temperature-400 degreeC. If the lower limit temperature is too high or the upper limit temperature is too low, the reaction heat may not be detected, which is not preferable. Further, when the temperature is 400 ° C. or higher, it is not preferable because heat generation / absorption other than the cross-linking reaction may be detected such as decomposition of the material.

  The heating rate is preferably 30 ° C./min or less. If it is faster than this, there is a possibility that the heat of reaction cannot be detected in detail, which is not preferable. The amount of the sample to be measured is preferably 0.1 mg or more and 100 mg or less. If the measurement is performed with the amount of the sample outside this range, the reaction heat may not be detected, which is not preferable.

  The dielectric breakdown voltage of the insulating film is often taken as an index of long-term reliability of semiconductor devices. Since dielectric breakdown of the insulating film occurs due to long-term voltage application or instantaneous overvoltage application, causing breakdown of the device, the dielectric breakdown voltage is preferably 4.0 MV / cm or more, more preferably 5. 0 MV / cm or more.

The amount of leakage current in the present invention is defined as the amount of leakage current per unit area between electrodes when a 30 V voltage is applied to a 0.5 μm ± 0.1 μm thin film formed between electrodes.
In the thin film of the present invention, the amount of leakage current is preferably smaller. Is preferably 20 nA / cm ² or less, it is preferably 15 nA / cm ² or less in consideration of the reliability of electronic components. When the amount of leakage current is large, for example, when the thin film according to the present invention is used as an insulating film of an electric device such as a TFT, there is a risk of signal response delay, malfunction, and device failure.

  The leak current measuring device is not particularly limited as long as it is a general-purpose semiconductor parameter analyzer capable of detecting a current of several pA level. The applied voltage is not a problem as long as the leakage current at a voltage applied as a normal TFT drive voltage is small, but it is preferably 0 in consideration of long-term reliability and instantaneous overvoltage immediately after application. It is preferably a low leakage current amount of the above level at any voltage value between -50V, more preferably 0-100V, and even more preferably between 0-200V regardless of AC voltage or DC voltage. It is preferable that the insulating property is maintained.

  Furthermore, it is desirable that this insulating film is also excellent in environmental resistance, and is 20% to 100% at a low temperature of -60 ° C to 0 ° C, a high temperature of 20 ° C to 100 ° C, and further 20 ° C to 90 ° C. Even when stored for a long time under the high temperature and high humidity condition of RH, it is desirable that the insulating property is maintained.

(Thin film formation method)
The method for forming a thin film using the composition of the present invention is not particularly limited, and the film can be formed by a method such as spin coating or slit coating. Further, viscosity adjustment with a solvent and surface tension adjustment with a surfactant may be appropriately performed in accordance with the state of the substrate on which the film is formed. In addition, the resin composition of the present invention can exhibit high insulation properties by allowing a crosslinking reaction to proceed with light or heat after film formation. The heating temperature after the film formation is not particularly limited, but is preferably 155 ° C. or less from the viewpoint of little influence on a member having low heat resistance around the transistor, for example, an organic semiconductor layer. In particular, the insulating property is exhibited even at a low temperature of 135 ° C. or lower, and an insulating film having a particularly good breakdown voltage can be formed.

(Substrate and metal electrode)
The substrate on which a film is formed using the resin composition of the present invention can be used without any particular limitation. In order to form a transistor using the present composition on a substrate and adapt it to a display, those having high transparency are preferable, and glass or the like is preferably used. Further, in the case of creating a display having light weight and flexibility, a transparent resin substrate can be applied, and preferably, PMMA, PET, polycarbonate, PEN, PES and the like are mentioned. From the standpoint that the pixel size / position deviation is small with respect to the temperature at which the transistor is formed, it is preferably a highly heat-resistant material with low linear expansion at high temperatures, and PEN, PES, etc. are particularly preferably used. By using the composition, an insulating film can be formed without deformation of the substrate under low temperature conditions, and a transistor can be easily formed even on these substrates.

  Also, the metal electrode formed on the resin substrate is not particularly limited, but it may be AL, Mo, Ni, Ti, Au or the like used for pixel formation / wiring formation in a general display. It is not limited.

(Resin composition)
In addition, the resin composition of the present invention is particularly limited as long as it is a thin film that can be applied in a solution and exhibits high insulating properties by a cross-linking reaction that is given energy such as heat and light from the outside. It is not a thing.

  Examples of the cross-linking reaction include a condensation reaction between an amino group or a hydroxyl group and a carboxyl group, a condensation reaction between hydrolyzable silyl groups, a hydrosilylation reaction, a hydroxyl group, a phenol group, a carboxyl group, an amino group, etc. and an epoxy group or an isocyanate group. There are no particular limitations, such as addition reaction, epoxy group, oxetanyl group, cationic polymerization reaction of vinyl ether group, radical polymerization reaction of (meth) acryl group, vinyl group and the like. In particular, the hydrosilylation reaction is preferable from the viewpoint that the reaction easily proceeds at a low temperature and an electrically and thermally stable C—Si bond is formed after the reaction.

  Examples of the resin composition include epoxy compounds, acrylic compounds, phenolic compounds, benzoxazole compounds, imide compounds, cyanate compounds, fluorine compounds, polysiloxane compounds, and the like.

  In addition, the thin film to be formed is preferably a polysiloxane compound from the viewpoint of high transparency and excellent heat resistance.

  In addition, the polysiloxane compound contained in the resin composition is not particularly limited, but in particular, it preferably contains a cyclic polysiloxane formed of 3 to 10 Si atoms in the molecule, and is a liquid solution. The thin film can be applied and has a high cross-linking density after curing and a high insulating property. However, those having no cross-linking reaction point in the cyclic polysiloxane structure preferably have a cross-linkable reactive group because it causes deterioration of the reliability of the film, such as outgas and bleed.

Wherein R ¹ and R ² are non-crosslinkable organic groups having 1 to 6 carbon atoms, X is a hydrogen atom (SiH group), an epoxy group, a (meth) acryloyl group, an alkoxylyl group, or a vinyl group 1 represents an organic group having 0 to 10 carbon atoms having such a crosslinkable reactive group, and may be the same or different, and n represents 1 to 10 and m represents a number of 0 to 10). Examples thereof include cyclic organopolysiloxanes having at least one crosslinkable reactive group in the molecule. A compound having 3 to 12, more preferably 3 to 6 silicon atoms in the cyclic structure is preferred.

  Further, from the viewpoint of obtaining a tough thin film, an oligomer in which a cyclic siloxane having a crosslinkable functional group and another organic compound or polysiloxane compound are partially reacted in advance can also be used. 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 to be partially crosslinked is not particularly limited, and a cyclic siloxane having one or more SiH groups or alkenyl groups in one molecule and a siloxane compound having one or more alkenyl groups or SiH groups in one molecule or Organic compounds can be used in appropriate combination.

  Examples of the cyclic siloxane containing one or more SiH groups in one molecule 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-tetramethyl Cyclotetrasiloxane, 1,3,5-trihydrogen-7-hexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3 7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-trimethylcyclosiloxane, 1,3,5,7,9-pentahydrogen-1,3, Examples include 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.

  Other compounds having SiH groups include poly or oligosiloxanes whose ends are blocked with dimethylhydrosilyl groups, poly or oligosiloxanes having SiH groups in the side chains, tetramethyldisiloxane, dimethoxymethylsilane, methoxydimethylsilane, diethoxymethyl. Examples thereof include SiH compounds having an alkoxysilyl group such as silane, ethoxydimethylsilane, and triethoxysilane.

  A compound having one or more alkenyl groups in one molecule can be used without particular limitation regardless of a polysiloxane compound or an organic compound.

  Specific examples of linear polysiloxanes having alkenyl groups include poly or oligosiloxanes whose ends are blocked with dimethylvinylsilyl groups, poly or oligosiloxanes having vinyl groups in the side chains, tetramethyldivinyldisiloxane, hexa Examples of methyltrivinyltrisiloxane and the above cyclic siloxane containing SiH groups include those in which SiH groups are substituted with alkenyl groups such as vinyl groups and allyl groups.

  Examples of the alkenyl group-containing organic compound do not include a siloxane unit (Si—O—Si) such as a polysiloxane-organic block copolymer or a polysiloxane-organic graft copolymer, and C, H, N, Particularly, if it is a compound composed of atoms selected from the group consisting of O, S and halogen, and is an organic compound having one or more carbon-carbon double bonds having reactivity with SiH group in one molecule It is not limited. 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 the compound 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, triallyl isocyanurate, diallyl monobenzyl isocyanurate, 1,2,4-trivinylcyclohexane, 1,4-butanediol Divinyl ether, nonanediol divinyl ether, 1,4-cyclohexane dimethanol divinyl ether, triethylene glycol divinyl ether, trimethylol propylene 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, vinylcyclohexene, 1,5-hexadiene, 1,9- Decadiene, diallyl ether, bisphenol A diallyl ether, 2,5-diallylphenol allyl ether, and oligomers thereof, 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1,2 ratio) 50-100% of those), allyl ether of novolak phenol, allylated polyphenylene oxide, and other ones such as replacing the allyl group all glycidyl groups of a conventionally known epoxy resins.

  Further, as the compound, a low molecular weight compound that is difficult to express by dividing into a skeleton portion and an alkenyl group (a carbon-carbon double bond having reactivity with the SiH group) can also be used. Specific examples of these low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene and decadiene, fats such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene. Examples thereof include aromatic cyclic polyene compound systems and substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene and vinylcyclohexene.

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

(Wherein R ³ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ³ may be different or the same, and at least one R ³ represents reactivity with a SiH group. The compound represented by the carbon-carbon double bond which has) is preferable.

R ^{3 in the} general formula (II) is preferably a monovalent organic group having 1 to 20 carbon atoms from the viewpoint that the heat resistance of the obtained cured product can be further increased. 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 ³ include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group and allyl group.

  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.

  In addition, it is also possible to introduce a functional group by reacting a compound containing a crosslinking reactive group and an alkenyl group in one molecule, epoxy compounds such as allyl glycidyl ether and vinyl cyclohexyl epoxide, allyl (meth) acrylate, An acryloyl compound such as vinyl (meth) acrylate, an alkoxysilyl compound such as trimethoxyvinylsilane, triethoxyvinylsilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, methoxydimethylvinylsilane, and ethoxydimethylvinylsilane can be used.

Further, in the resin composition of the present invention, a polysiloxane having a polyhedral skeleton formed from 6 to 24 Si atoms is included in the molecule, thereby forming a denser cross-linked structure in the thin film after the composition is cured. This is preferable because it is a thin film having higher insulation reliability.
As polysiloxane having a polyhedral structure, the number of Si atoms contained in the skeleton is preferably 6 to 24. Specifically, for example, silsesquioxane having a polyhedral structure represented by the following structure is exemplified. (Here, the number of Si atoms = 8 is exemplified as a representative example).

In the above formulas, R ^{4 to} R ¹¹ are alkenyl groups such as vinyl group, allyl group, butenyl group, hexenyl group, (meth) acryloyl group, epoxy group, mercapto group, amino group-containing organic group, hydrogen atom, methyl group , An alkyl group such as an ethyl group, a propyl group and a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group and a tolyl group, a methoxy group bonded via an oxygen atom, an ethoxy group, a propoxy group, It is selected from alkoxy groups such as butoxy groups, or chloromethyl groups, trifluoropropyl groups, cyanoethyl groups, etc. in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc. The same or different, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, unsubstituted or substituted monovalent hydrocarbon It is.

However, as with the cyclic polysiloxane, in order to form a crosslinked structure, at least one of R ^{4 to} R ¹¹ includes a hydrogen atom (SiH group), an epoxy group, a (meth) acryloyl group, an alkoxy group, It preferably has any crosslinkable reactive group selected from alkenyl groups.

  Further, as a polysiloxane having a polyhedral structure in the present invention, a more preferable example is a silylated silicic acid having a polyhedral structure represented by the following structure (here, the number of Si atoms = 8 is a representative example) As an example). In this compound, since the Si atom forming the polyhedral skeleton and the reactive group are bonded via a siloxane bond, the obtained cured product is not too rigid, and a good molded body can be obtained. it can.

In the above structure, R ^{12 to} R ³⁵ are alkenyl groups such as vinyl group, allyl group, butenyl group, hexenyl group, (meth) acryloyl group, epoxy group, mercapto group, amino group-containing organic group, hydrogen atom Alkyl groups such as methyl group, ethyl group, propyl group and butyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group and tolyl group, methoxy group bonded via oxygen atom, ethoxy group, From an alkoxy group such as a propoxy group or a butoxy group, or a chloromethyl group, a trifluoropropyl group, a cyanoethyl group, or the like in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom, a cyano group, or the like The same or different organic groups selected. However, at least one of these R ^{12 to} R ³⁵ is the same as the cyclic polysiloxane, but in order to form a crosslinked structure, at least one of R ^{4 to} R ¹¹ must be a hydrogen atom (SiH Group), an epoxy group, a (meth) acryloyl group, an alkoxy group, and an alkenyl group.

  Further, similarly to the cyclic polysiloxane, an oligomer in which a polyhedral polysiloxane having a cross-linkable functional group and an organic compound or a siloxane compound are partially reacted in advance can also be used. By the above method using hydrosilylation, Higher insulation by using a polyhedral polysiloxane having one or more SiH groups or alkenyl groups in one molecule and a siloxane compound or organic compound having two or more alkenyl groups or SiH groups in one molecule A resin composition having properties can be obtained.

As the catalyst for the hydrosilylation reaction, for example, the following can be used. Platinum simple substance, alumina, silica, carbon black or the like supported on solid platinum, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone or the like, platinum-olefin complex (for example, Pt (CH _{2 = CH 2) 2 (PPh} 3) 2, Pt (CH 2 = CH 2) 2 Cl 2), platinum - vinylsiloxane complex _{(e.g., Pt (ViMe 2 SiOSiMe 2 Vi} ) n, Pt [(MeViSiO) 4] _m ), a platinum-phosphine complex (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), a platinum-phosphite complex (eg, Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄₎ (in the formula, Me represents a methyl group, Bu a butyl group, Vi is vinyl group, Ph represents a phenyl group, n, m is an integer.), Jikaruboni Dichloroplatinum, Karstedt catalyst, and the platinum-hydrocarbon complexes described in Ashby US Pat. Nos. 3,159,601 and 3,159,622, and Lamoreaux, US Pat. No. 3,220,972. Examples include platinum alcoholate catalysts described in the text. In addition, platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946 are also useful in the present invention.

Further, examples of catalysts other than platinum _{compounds, RhCl (PPh) 3, RhCl} 3, RhAl 2 O 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3, PdCl 2 · 2H 2 O, NiCl 2, TiCl 4 , Etc.

  Of these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity. Moreover, these catalysts may be used independently and may be used together 2 or more types.

Although the addition amount of the catalyst is not particularly limited, the lower limit of the preferable addition amount is sufficient for the SiH group of the compound (α1) and the compound (γ) to have sufficient curability and keep the cost of the resin composition relatively low. 1 mol of a carbon-carbon double bond having the reactivity of (hereinafter, simply referred to as “alkenyl group”) or 1 mol of an alkenyl group of the compound (α1), the compound (α2) and the compound (γ) is ^{10 -8} moles and more preferably ^{10 -6} moles relative to, the upper limit of the preferable amount is ^{10 -1} mol per alkenyl group 1 mole of the compound, more preferably ^{10 -2} moles.

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 co-catalyst is not particularly limited, the lower limit of the preferable amount of relative hydrosilylation catalyst 1 mole, 10 ^-2 mol, more preferably 10 ^-1 mol, the upper limit of the preferable amount is 10 ² Mol, more preferably 10 mol.

(Regarding photolithographic properties)
In addition, in order to partially provide contact holes in the insulating film to establish conduction between the upper and lower electrodes, it is preferable that the thin film can be partially removed by dry etching or lithography, and from the viewpoint of simplifying the process, photolithography The thing which has is preferable. The photolithographic property is not particularly limited and can be applied, and the exposure wavelength is not particularly limited.

  It is preferable to have at least one photopolymerizable functional group in one molecule for the expression of photolithography.

  The photopolymerizable functional group as used herein refers to a functional group that is polymerized and cross-linked by radicals or cationic species generated from a photopolymerization initiator when light energy is applied from the outside, and the reaction / crosslinking mode is particularly limited. It is not a thing.

  Among them, particularly from the viewpoint of reactivity and stability of the compound, at least one of the photopolymerizable functional groups is preferably an epoxy group, a crosslinkable silicon group, a (meth) acryloyl group, or a vinyloxy group. Among the epoxy groups, an alicyclic epoxy group and a glycidyl group are preferable from the viewpoint of stability, and an alicyclic epoxy group is particularly preferable from the viewpoint of excellent cationic polymerization by light and heat.

  Examples of the crosslinkable silicon group include hydrolyzable silicon groups such as an alkoxysilyl group, an acetoxysilyl group, a phenoxysilyl group, a silanol group, and a chlorosilyl group. From the viewpoint, an alkoxysilyl group is particularly preferable. Examples of the alkoxysilyl group include those in which the functional group bonded to silicon is a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a sec-butoxy group, or a tert-butoxy group, A methoxy group and an ethoxy group are particularly preferable from the viewpoint that residual components after curing hardly remain.

  The modified polyorganosiloxane compound only needs to have at least one photopolymerizable functional group, and each photopolymerizable functional group may be the same or may have two or more different functional groups. The modified polyorganosiloxane compound contained in the curable composition of the present invention may have at least one photopolymerizable functional group in one molecule, preferably two or more, more preferably three or more. It is. If it is three or more, there exists an advantage that the hardened | cured material with a high crosslinking density is obtained and it is excellent in heat resistance.

  Further, in development at the time of lithography, those that can be developed with an alkaline developer mainly used as a general resist developer are more preferable than a special developer or an organic solvent developer from the viewpoint of recyclability and cost.

  In the resin composition of the present invention, each structure having at least one photopolymerizable functional group in one molecule and further represented by the following formula:

Having at least one selected from the group consisting of a phenolic hydroxyl group and a carboxyl group in the same molecule facilitates dissolution in an alkaline aqueous solution, and is preferable in terms of expressing lithography properties that allow alkali development.

  When the resin composition has lithographic properties, it is preferable from the viewpoint that a multi-step process such as dry etching or patterning with a resist can be largely omitted when forming a thin film transistor. Further, in development, it is preferable from the viewpoint of cost saving and recycling that development can be performed with an alkaline developer generally used as a resist developer in an LCD manufacturing process or the like.

  Further, examples of the compound that can obtain a thin film having alkali developability, high transparency, and excellent heat resistance include polysiloxane compounds having the specific structure shown above. The method for obtaining the polysiloxane compound having the specific structure shown above is not particularly limited, but from the viewpoint of reaction selectivity and the like, an alkenyl group-containing compound having a specific structure and a silicon compound having a SiH group are used. It is preferable to use a hydrosilylation reaction.

  Examples of the alkenyl group-containing compound having a specific structure include vinylphenol, allylphenol, butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid, undecylenic acid, diallyl isocyanuric acid, monoallyl isocyanuric acid, diallyl bisphenol A, diallyl bisphenol S, Vinylphenol and allylphenol can be mentioned, and diallyl isocyanuric acid and monoallyl isocyanuric acid are particularly preferable from the viewpoint of transparency of the cured product.

(Cationic polymerization initiator)
In the resin composition of the present invention, it is necessary to appropriately select a photopolymerization initiator depending on the functional group type. In the case of having a cationic polymerizable functional group such as an epoxy group or an alkoxysilyl group, it is necessary to add a cationic polymerization initiator. As the cationic polymerization initiator, a cationic species or a Lewis acid is generated by active energy rays. Any active energy ray cationic polymerization initiator or thermal cationic polymerization initiator that generates a cationic species or a Lewis acid by heat can be used without particular limitation.

Examples of active energy ray cationic polymerization initiators include metal fluoroboron complex salts and boron trifluoride complex compounds as described in US Pat. No. 3,379,653; bis (perfluoroalkyls) as described in US Pat. No. 3,586,616. Sulfonyl) methane metal salts; aryldiazonium compounds as described in US Pat. No. 3,708,296; aromatic onium salts of group VIa elements as described in US Pat. No. 4,058,400; described in US Pat. Aromatic onium salts of Group Va elements such as: dicarbonyl chelates of Group IIIa to Va elements as described in US Pat. No. 4068091; thiopyrylium salts as described in US Pat. No. 4,139,655; US Pat. No. 4,161,478 MF6 ^- anions as described in the issue (here And M is selected from phosphorus, antimony and arsenic); arylsulfonium complex salts as described in US Pat. No. 4,231,951; aromatic iodonium complex salts as described in US Pat. No. 4,256,828 and Aromatic sulfonium complex salts; R. Bis [4- (diphenylsulfonio) phenyl] sulfide-bishexafluoro as described by Watt et al. In “Journal of Polymer Science, Polymer Chemistry Edition”, Vol. 22, page 1789 (1984). Metal salts (for example, phosphates, arsenates, antimonates, etc.); one or more of aromatic iodonium complex salts and aromatic sulfonium complex salts whose anions are B (C ₆ F ₅ ) ₄ ^— are included.

  Preferred cationic 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) As a product.

  The amount of the cationic polymerization initiator used is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the modified polyorganosiloxane compound. When the amount of the cationic polymerization initiator is small, it takes a long time for curing or a cured product that is sufficiently cured cannot be obtained. When the amount of the initiator is large, the color of the initiator remains in the cured product, coloring or bulging due to rapid curing, or the heat and light resistance of the cured product is impaired.

(Radical polymerization initiator)
In addition, when the resin composition of the present invention has a radical polymerization functional group such as an acryloyl group, it is necessary to use a radical polymerization initiator, but active energy ray radical polymerization is initiated, which generates radical species by active energy rays. Any agent 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.

  The amount of radical polymerization initiator used is preferably 0.1 to 15 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the modified polyorganosiloxane compound. When the amount of the cationic polymerization 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.

(Sensitizer)
When the resin composition of the present invention is cured with light energy, the light sensitivity is improved and light having a high wavelength such as g-line (436 nm), h-line (405 nm), or i-line (365 nm) is used. In order to provide sensitivity, 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-diethoxyanthracene from the viewpoint of excellent compatibility with the resin composition. Etc. are preferred.

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.

(Lithography method)
When forming a pattern with a thin film using the composition of the present invention for the purpose of forming a contact hole or the like, it can be carried out by a method similar to a developing method of a normal resist material, and is not particularly limited. As a light source for sensitization, 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 usually containing a wavelength in the range of 200 to 450 nm, for example, a high-pressure mercury lamp, an ultra-high pressure Mercury lamps, metal halide lamps, high power metal halide lamps, xenon lamps, carbon arc lamps, light emitting diodes, and 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, a pattern may not be formed due to overexposure.

  Further, for the purpose of removing the solvent and improving the physical properties of the cured product, pre-baking and after-baking may be performed by applying heat before and after photocuring. The curing temperature can be variously set, but a preferable temperature range is 60 to 300 ° C, more preferably 80 to 200 ° C, and particularly preferably 80 to 155 ° C. Further, it can be formed into a film having good insulating characteristics even at a low temperature of 80 to 135 ° C.

  The developer can be used without particular limitation as long as it is a commonly used alkaline developer, but specific examples include organic alkaline aqueous solutions such as tetramethylammonium hydroxide aqueous solution and choline aqueous solution, and potassium hydroxide. Examples thereof include an aqueous solution, an aqueous solution of sodium hydroxide, an aqueous solution of potassium carbonate, an aqueous solution of sodium carbonate, an aqueous solution of lithium carbonate and the like, and an aqueous solution containing alcohol or a surfactant added to adjust the dissolution rate.

  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.

(solvent)
In the resin composition of the present invention, it is also possible to adjust the viscosity using a solvent for film forming property adjustment. 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 resin 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 resin composition of the present invention includes ion traps such as colorants, mold release agents, flame retardants, flame retardant aids, surfactants, antifoaming agents, emulsifiers, leveling agents, anti-fogging agents, and antimony-bismuth. Agent, thixotropic agent, tackifier, storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, reactive diluent, antioxidant, thermal stabilizer, conductivity imparting Agents, antistatic agents, radiation blocking agents, nucleating agents, phosphorus peroxide decomposing agents, lubricants, pigments, metal deactivators, thermal conductivity imparting agents, physical property modifiers, etc. It can be added in a range not present.

Using the composition, characteristics evaluation was performed at a baking temperature condition of 150 ° C. by the following electrical characteristics evaluation procedure. Table 1 shows the results of the evaluation of the characteristics of the curable compositions obtained in Examples and Comparative Examples.

As can be seen from the results, it can be seen that a thin film having high electrical characteristics is obtained under the baking conditions of 150 ° C. or less according to the present invention.

(Film thickness measurement)
The thin film formed on the glass / AL substrate was calculated by measuring the UV-vis spectrum. A thin film prepared using the resin composition of the present invention has excellent insulating properties and can be applied as a thin film insulating material that can be formed by solution coating.

(Total calorific value)
10 mg of the obtained curable composition was put in an aluminum pan (6 mmΦ), and baked on a hot plate at a predetermined temperature for 30 minutes to form a thin film. The sample was heated from room temperature to 400 ° C. at 10 ° C./min using DSC (manufactured by Shimadzu Corporation), and the total heat generation amount was measured.

(Electrical characteristics evaluation)
The following electrical property evaluation samples were prepared for dielectric breakdown voltage evaluation and leakage current measurement evaluation. A glass substrate on which a 2000-nm-thick Mo film was sputtered as a lower electrode was spin-coated (rotation speed: 2000 rpm, 30 seconds) with the resin compositions obtained in the examples and comparative examples, and predetermined for 30 min on a hot plate. A thin film was formed by baking at temperature. Further, an AL electrode (3 mmΦ) was formed as an upper electrode on the thin film to prepare a sample.

(Dielectric breakdown voltage measurement)
The dielectric breakdown voltage was evaluated by applying a voltage between the electrodes (AL-Mo) of the above-mentioned electrical property evaluation sample, and using the voltage when the leakage current amount exceeded 10 mA as the breakdown voltage value. A curve tracer (manufactured by Sony) was used for the measurement.

(Leakage current measurement)
The amount of leakage current was evaluated by measuring the amount of leakage current per electrode unit area when applying 30V between the electrodes (AL-Mo) of the above electrical property evaluation sample in steps of 0.5V from 0 to 50V. It was. For the measurement, a semiconductor parameter measurement device (Agilent 4156C) was used.

(Alkali developability)
The composition obtained from the curable compositions obtained in Examples and Comparative Examples was applied to a glass plate (50 × 100 × 0.7 mm) by spin coating to prepare a sample with a simple mask as shown in FIG. Then, the integrated light amount was exposed to 200 mJ / cm ² with a conveyor type exposure apparatus (high pressure mercury lamp, LH6 manufactured by Fusion).

  The exposed sample is immersed in an alkaline developer (TMAH 2.38% aqueous solution) for 60 seconds and then washed with water, and a development contrast is obtained (the exposed portion resin remains and the unexposed portion is removed). Those not attached were evaluated as alkali developability with x.

Example 1
A 500 mL four-necked flask was charged with 100 g of toluene and 75 g of 1,3,5,7,9-pentahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane. The mixture was heated and stirred at a temperature of 105 ° C. A mixed liquid of 10.0 g of triallyl isocyanurate, 10.0 g of toluene, and 8 mg of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was dropped. Six hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more, and the reaction was terminated by cooling. Unreacted 1,3,5,7,9-pentahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a polysiloxane compound.

  To 1.5 g of the obtained polysiloxane compound, add 1 g of triallyl isocyanurate, 2.5 mg of a platinum vinylsiloxane complex xylene solution (containing 3 wt% as platinum), and 7.5 g of 2-acetoxy-1-methoxypropane. A composition was obtained.

  Using the composition, characteristics evaluation was performed at a baking temperature condition of 150 ° C. according to the procedure of electrical characteristics evaluation.

(Example 2)
A 500 mL four-necked flask was charged with 100 g of toluene and 57 g of 1,3,5,7,9-pentahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane. The mixture was heated and stirred at a temperature of 105 ° C. A mixed solution of 10.0 g of diallyl isocyanuric acid, 70.0 g of 1,4-dioxane and 18.5 mg of a platinum vinylsiloxane complex in xylene (containing 3 wt% as platinum) was added dropwise. Six hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more, and the reaction was terminated by cooling.

Unreacted 1,3,5,7,9-pentahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a colorless and transparent liquid “Reactant A”. . A 100 mL four-necked flask was charged with 20 g of toluene and 10 g of “Reactant A”, the gas phase was replaced with nitrogen, and then heated at an internal temperature of 105 ° C. A mixed liquid of 3.0 g of vinylcyclohexene oxide and 3.0 g of toluene. 3 hours after the addition, it was confirmed by ¹ H-NMR that the reaction rate of the vinyl group was 95% or more. The reaction solution was cooled to obtain a polysiloxane compound.

To 1 g of the above polysiloxane compound, 5.88 g of 2-acetoxy-1-methoxypropane, 0.005 g of anthracene, 0.01 g of RHODORSIL-PI2074 (cationic polymerization initiator, Rhodia), 0.5 g of triallyl isocyanurate, platinum 1.47 mg of a xylene solution of vinylsiloxane complex (containing 3 wt% as platinum) was added to obtain a resin composition.
Using the composition, characteristics evaluation was performed at a baking temperature condition of 150 ° C. according to the procedure of electrical characteristics evaluation.

(Example 3)
Using the same curable composition obtained in Example 2, the characteristics were evaluated at a baking temperature condition of 130 ° C. according to the procedure for evaluating the electrical characteristics.

(Comparative Example 1)
To 1 g of ethyl silicate 40 (manufactured by Colcoat Co., Ltd.) is added a resin composition by adding 8 g of methyl isobutyl ketone and 0.05 g of a 2-acetoxy-1-methoxypropane 25 wt% solution of RHODORSIL-PI2074 (cationic polymerization initiator, manufactured by Rhodia) did.
Using the composition, characteristics evaluation was performed at a baking temperature condition of 150 ° C. according to the procedure of electrical characteristics evaluation.

(Comparative Example 2)
Poly (melamine-co-formaldehyde) methacrylate (manufactured by Aldrich) 0.1 g and PGMEA 2 g were added to 0.4 g of polyvinylphenol (manufactured by Aldrich) to obtain a resin composition.

Claims (13)

An insulating thin film which can be formed by applying a resin composition in a solution and which is obtained by post-baking at 170 ° C. or less and whose calorific value by DSC measurement is 5 J / g or less. The thin film according to claim 1, which has a dielectric breakdown voltage of 4 MV / cm or more. The thin film according to claim 1 or 2, wherein the thin film has an insulating property with a leakage current of 20 nA / cm ² or less when 30 V is applied. 4. The thin film according to claim 1, wherein the resin composition contains a polysiloxane compound as a main component. The polysiloxane compound is a cyclic polysiloxane formed from 3 to 10 Si atoms in the molecule or a polysiloxane having a polyhedral skeleton formed from 6 to 24 Si atoms in the molecule. The thin film according to claim 4. The thin film according to any one of claims 1 to 5, wherein the polysiloxane compound has a photopolymerizable functional group. The curable composition of Claim 6 whose photopolymerizable functional group is an alicyclic epoxy group or a glycidyl group. The thin film according to claim 1, wherein the resin composition has photolithography properties. The resin composition has at least one photopolymerizable functional group and is selected from the group consisting of each structure represented by the following formulas (X1) to (X3), a phenolic hydroxyl group, and a carboxyl group. The thin film of Claim 8 containing the compound which has at least 1 type in a molecule | numerator.

The thin film according to any one of claims 5 to 9, wherein the polysiloxane compound is obtained by subjecting a cyclic siloxane compound having a SiH group and a compound having an alkenyl group to a hydrosilylation reaction. The thin film according to claim 10, wherein the polysiloxane compound is a compound having a photopolymerizable functional group and a SiH group in one molecule. The thin film according to claim 11, wherein the resin composition contains a compound having an alkenyl group. A thin film transistor, wherein the thin film according to claim 1 is a passivation film of a semiconductor layer or a gate insulating film.