JP5589286B2 - THIN FILM TRANSISTOR MANUFACTURING METHOD, THIN FILM TRANSISTOR AND DISPLAY DEVICE - Google Patents

Description

  The present invention relates to a method for manufacturing a thin film transistor, a thin film transistor obtained by the manufacturing method, and a display device. More specifically, the present invention relates to a thin film transistor manufacturing method, a thin film transistor, and a display device that can be manufactured easily, efficiently, and at low cost, have high luminance, and are excellent in reliability.

  A thin film transistor is a switching element having terminals called a gate electrode, a source electrode, and a drain electrode, and is widely applied to an active element of an active matrix substrate of a display device such as an active matrix liquid crystal display or an organic EL.

  FIG. 1 is a diagram showing an outline of a conventional thin film transistor. In the thin film transistor shown in FIG. 1, the current flowing from the source electrode 12 to the drain electrode 14 through the semiconductor layer 13 changes according to the voltage applied to the gate electrode 11. Based on this principle, the luminance of each pixel of the display device is controlled.

  Many conventional thin film transistors have a structure in which a passivation film made of silicon nitride is formed on the surface of a semiconductor layer by sputtering, vapor deposition, or CVD. In the method of manufacturing a thin film transistor, the oxide film on the surface of the specific layer may be removed using hydrofluoric acid for the purpose of improving the adhesion between the specific layer other than the semiconductor layer and the passivation film.

  For example, Patent Document 1 discloses a process of removing an oxide film on an electrode surface made of a silicide layer. Also disclosed is a step of forming a passivation film comprising an oxide layer or a nitride layer and a mixed layer including the oxide layer or the nitride layer on the silicide layer from which the oxide film has been removed by a CVD method. Moreover, it is disclosed that the adhesiveness between the electrode and the passivation film is improved through the above-described steps.

  Patent Document 2 discloses a step of forming a gate electrode, a gate insulating film, a semiconductor layer, and source / drain electrodes on a substrate, a step of performing wet etching on the semiconductor layer itself using hydrofluoric acid, and a channel region formation. An etching process for is disclosed. In addition, a process of forming a passivation film made of a SiN film (silicon nitride film) after the above process is disclosed. In addition to the above steps, it is disclosed that a thin film transistor having high reliability is manufactured by forming a transparent conductive film between specific layers and controlling its shape.

  However, in both Patent Documents 1 and 2, the formation of a passivation film made of an inorganic material requires that the film be formed in a vacuum or ionized state in a vacuum, the equipment is large-scale, and the operation is There is a problem that it is complicated, and there is a problem that the transparency of the substrate to be manufactured is low. Also, if the passivation film made of an inorganic material is removed, or if the material or manufacturing method is changed to one that can be formed by a simpler film forming method or a method, the reliability deteriorates. There is.

JP-A-10-335258 JP 2007-329298 A

Therefore, an object of the present invention is to provide a thin film transistor that can be efficiently manufactured by a simple process in a short time, has high reliability, and has high transparency, and a manufacturing method thereof.
Still another object of the present invention is to provide a display device having the thin film transistor.

  As a result of intensive studies to achieve the above object, the present inventor used a passivation film containing an organic material in a method for manufacturing a thin film transistor, and a channel region of a semiconductor layer on which the passivation film is stacked. It has been found that by removing the oxide film on the surface of the semiconductor layer in a specific portion, a highly transparent thin film transistor can be efficiently produced with a simple process, and at the same time, the device reliability is excellent. Based on the above findings, the present invention has been completed.

Thus, according to the present invention, a step of forming a gate electrode, a gate insulating film, a semiconductor layer and source / drain electrodes on a substrate, a step of forming a channel region, and an oxide film on the surface of the semiconductor layer in the channel region are removed. There is provided a method of manufacturing a thin film transistor including a step, and a step of forming a passivation film containing an organic material following the step of removing the oxide film.
According to the invention, a step of forming a gate electrode on the substrate, a step of forming a gate insulating film covering the gate electrode, a step of forming a semiconductor layer on the gate insulating film, and the semiconductor layer Forming a source electrode and a drain electrode thereon; forming a channel region which is a region exposing the semiconductor layer between the source electrode and the drain electrode; and the semiconductor layer in the channel region Removing the oxide film formed on the surface; and forming an organic passivation film formed on the substrate so as to cover at least the source electrode, the drain electrode, and the channel region. method of manufacturing a thin film tiger Njisuta comprising the steps, a to is provided.

In the thin film transistor manufacturing method of the present invention, it is preferable that the step of forming the channel region is a step of forming the channel region by wet etching.
In the method for producing a thin film transistor of the present invention, it is preferable that the step of removing the oxide film uses a solution containing hydrofluoric acid.
In the thin film transistor manufacturing method of the present invention, it is preferable that the step of forming the channel region by wet etching uses a solution containing hydrofluoric acid.

  In the method for producing a thin film transistor of the present invention, it is preferable that the passivation film is a film formed of a resin composition containing a resin and an organic solvent.

  In the method for producing a thin film transistor of the present invention, it is preferable that the resin composition further contains a compound having an acidic group.

  In the method for producing a thin film transistor of the present invention, the resin composition further includes one atom selected from a silicon atom, a titanium atom, an aluminum atom, and a zirconium atom, and a hydrocarbyloxy group or a hydroxy group bonded to the atom. It is preferable to contain the compound which has this.

  In the method for producing a thin film transistor of the present invention, the resin composition further has a compound having an acidic group, and one atom selected from a silicon atom, a titanium atom, an aluminum atom, and a zirconium atom, and is bonded to the atom. It is preferable to contain a compound having a hydrocarbyloxy group or a hydroxy group.

  In the method for producing a thin film transistor of the present invention, the resin is preferably at least one selected from the group consisting of a cyclic olefin resin, an acrylic resin, a cardo resin, a polysiloxane resin, and a polyimide resin.

  Moreover, according to this invention, the thin-film transistor obtained by the said manufacturing method is provided.

  Moreover, according to this invention, the display apparatus which has a thin-film transistor obtained by the said manufacturing method is provided.

  According to the method for manufacturing a thin film transistor of the present invention, a thin film transistor having high transparency and high reliability even in a harsh atmosphere can be easily and inexpensively manufactured because a complicated operation is not required at the time of manufacturing.

It is a figure showing the specific aspect of the conventional thin-film transistor.

It is a figure showing an example of the specific aspect of the form which implements this invention.

DESCRIPTION OF SYMBOLS 11 ... Gate electrode 12 ... Source electrode 13 ... Semiconductor layer 14 ... Drain electrode 21 ... Substrate 22 ... Gate electrode 23 ... Gate insulating film 24 ... Semiconductor layer 25 ... Impurity addition semiconductor layer 26 ... Source / drain electrode 27 ... Source electrode 28 ... Drain electrode 29 ... Channel region 30 ... Impurity-added semiconductor layer in region where source electrode exists 31 ... Impurity-added semiconductor layer in region where drain electrode exists

The method of manufacturing a thin film transistor of the present invention includes a step of forming a gate electrode, a gate insulating film, a semiconductor layer, and a source / drain electrode on a substrate, a step of forming a channel region, and an oxide film on the surface of the semiconductor layer of the channel region. And a step of forming a passivation film containing an organic material following the step of removing and the step of removing the oxide film.
In the thin film transistor manufacturing method of the present invention, a gate electrode, a gate insulating film, a semiconductor layer, and a source / drain electrode are formed on a substrate, a channel region is formed by wet etching, and the channel region is formed. After the step, there is a step of forming a passivation film containing an organic material.

  In the present invention, the substrate to be used is not particularly limited, and for example, a glass substrate, a quartz substrate, a silicon substrate, a metal substrate, a stainless steel substrate, or a plastic substrate (including a film substrate) can be used. Note that the substrate may have a surface formed with an insulating film such as silicon nitride, silicon oxide, silicon nitride oxide, aluminum nitride, aluminum oxynitride, or aluminum oxide. The insulating film is not limited to the illustrated inorganic material, and may be a film made of an organic material.

  In the present invention, the material constituting the gate electrode, the gate insulating film, the source electrode and the drain electrode is not particularly limited. For example, Cr, Mo, Al, Cu, Ag, Au, Ti, Ta, Nb, W, Fe , Ni, Co, Rh, Nd, Pb, and the like, and alloys or silicides containing these metals can be used. In addition, a conductive material such as ITO or IZO can be used. The electrode may be formed of a single layer using the material alone, or may be formed of a plurality of layers (two or more layers) using a plurality of the materials.

  In the present invention, the semiconductor layer material is not particularly limited, and organic semiconductor materials represented by pentacene, polythiophene derivatives, polyphenylene vinylene derivatives, polythienylene vinylene derivatives, polyallylamine derivatives, polyacetylene derivatives, acene derivatives, oligothiophenes, and the like. Oxide semiconductor materials composed of elements such as In, Ga, Zn, and O, represented by InGaZnO, ZnGaO, InZnO, InO, GaO, SnO, or a mixture thereof, amorphous silicon A silicon-based semiconductor material such as polysilicon can be used. Among these, a silicon-based material is preferable, and amorphous silicon is more preferable.

  In the present invention, the gate insulating film is not particularly limited, but an inorganic film such as SiNx or SiOx or an organic film such as an organic material thin film mainly containing pullulan can be used.

  Hereinafter, the best mode for carrying out the present invention will be described with reference to the accompanying drawings 2 (a) to 2 (g). Note that the attached drawings only schematically show the shape, size, and arrangement of the components to the extent that the invention can be understood, and the present invention is not particularly limited thereby. Therefore, elements unnecessary for the description of the present invention are omitted, and the shapes and dimensional ratios of the illustrated elements do not necessarily reflect actual ones. In addition, the present invention has ordinary knowledge in the art that various forms can be replaced, modified, and changed without departing from the technical idea of the present invention described in the claims. It is self-evident to those who are.

  First, as shown in FIG. 2A, a gate electrode 22 is formed on an insulating substrate 21 such as a glass substrate by a sputtering method.

  Next, using the photoresist as a mask, the gate electrode 22 is patterned by dry etching or wet etching as shown in FIG.

  Next, as shown in FIG. 2C, a gate insulating film 23, a semiconductor layer 24, and an impurity-added semiconductor layer 25 are sequentially deposited by a CVD method. The impurity-added semiconductor layer 25 is often formed when the semiconductor layer 24 is an amorphous silicon semiconductor layer, but may not be formed when another material is a semiconductor layer.

  Next, as shown in FIG. 2D, the semiconductor layer 24 and the doped semiconductor layer 25 are patterned by patterning the semiconductor layer 24 and the doped semiconductor layer 25 by dry etching or wet etching using a photoresist as a mask. An island-shaped semiconductor structure is formed.

  Next, as shown in FIG. 2E, source / drain electrodes 26 are formed by sputtering. As described above, the steps described in FIGS. 2A to 2E are described in the claims of the present invention as “a step of forming a gate electrode, a gate insulating film, a semiconductor layer, and a source / drain electrode on a substrate. ”.

  Next, using the photoresist as a mask, the source / drain electrode 26 is patterned by etching as shown in FIG. 2 (f) to form a source electrode 27 and a drain electrode 28. That is, the source electrode 27 and the drain electrode 28 are formed by separating the source / drain electrode 26 by patterning, and the source / drain electrode 26, the source electrode 27, and the drain electrode 28 are all made of the same material. The In general, the source / drain electrodes are etched by wet etching, but may be dry etching.

  Next, the impurity added semiconductor layer 25 is etched using the photoresist used for patterning the source / drain electrode 26 as it is, thereby forming a channel region as shown in FIG. In general, the impurity-doped semiconductor layer is etched by dry etching, but may be wet etching. Here, the channel region refers to the impurity-doped semiconductor layer in the gate electrode side end of the impurity-doped semiconductor layer 30 in the region where the source electrode 27 and the source electrode exist, and in the region where the drain electrode 28 and the drain electrode exist. 31 shows a portion of the semiconductor layer 29 sandwiched between the gate electrode side end portion 31. That is, the semiconductor layer in the portion indicated by the arrow between the dotted lines in FIG. 2G is the channel region. Therefore, the steps from FIG. 2F to FIG. 2G correspond to the “step of forming a channel region” described in the claims of the present invention. That is, the “step of forming a channel region” is a step of exposing a part of the surface of the semiconductor layer by removing the layer that is in contact with the semiconductor layer on the side opposite to the substrate. The surface of the semiconductor layer exposed in the process corresponds to the “semiconductor layer surface of the channel region” recited in the claims.

Next, the photoresist used at the time of patterning is removed using a stripping solution. Since organic residue may remain on the substrate or contamination may occur during the removal, the photoresist is stripped using a stripping solution, and then a cleaning process using UV irradiation, oxygen as a main component, CF ₄ or Plasma can be generated using a gas mixed with N ₂ or the like, and an ashing process using generated oxygen radicals, a combination process thereof, or the like can be appropriately incorporated.

Next, the oxide film on the surface of the semiconductor layer 29 in the channel region is removed. As a method for removing the oxide film, sputter etching using argon ions, CF ₄ gas, etc .; physical treatment such as annealing; and nitric acid, hydrofluoric acid, buffered hydrofluoric acid, hydrochloric acid, sulfuric acid, acetic acid, oxalic acid, etc. And chemical treatment such as chemical etching using an acidic solution, an aqueous solution thereof, a mixture thereof, or the like. Here, the oxide film on the surface of the semiconductor layer refers to a film in which the semiconductor material is oxidized and exists on the surface of the semiconductor layer exposed by the step of forming the channel region. When the material of the semiconductor layer is an organic semiconductor material, the oxide layer of the organic substance existing on the surface or the oxide layer on the surface having a higher oxygen ratio than the inside of the semiconductor layer, the inside of the semiconductor layer when the material is an oxide semiconductor material When the surface oxide layer having a higher oxygen ratio is a silicon-based semiconductor material, the silicon oxide layer or the silicon oxide layer having a higher oxygen ratio than the inside of the semiconductor layer corresponds to the oxide film.

  Among the oxide film removing steps, the high oxide film removing ability can reduce the manufacturing lead time, reduce the manufacturing cost of the thin film transistor, improve the manufacturing yield, and manufacture a plurality of thin film transistors on a large substrate. Even in this case, since the stability of the thin film transistor characteristics can be improved uniformly, oxide film removal using a solution containing hydrofluoric acid is preferable, and oxide film removal using hydrofluoric acid is more preferable. Further, since the stability of thin film transistor characteristics can be improved even when a plurality of thin film transistors are manufactured on a large substrate, the concentration of hydrofluoric acid is preferably 0.01% to 10%, preferably 0.1% to It is more preferably 5%, and further preferably 0.1% to 1%. Here, the solution containing hydrofluoric acid refers to a solution to which an acid other than hydrogen fluoride is added, a solution to which ammonium fluoride is added, a solution to which an additive such as a surfactant is added, and the like. Here, hydrofluoric acid refers to an aqueous hydrogen fluoride solution.

Note that the step of forming the channel region is performed by wet etching, so that both the step of forming the channel region and the step of removing the oxide film on the surface of the semiconductor layer in the channel region can be performed. As a method in which both the step of forming the channel region and the step of removing the oxide film on the surface of the semiconductor layer of the channel region are performed, the step of etching the source / drain electrode 26 and then the etching of the source / drain electrode 26 are performed. A method of performing a step of wet etching the impurity-added semiconductor layer 25 as a step of removing the used photoresist using a stripping solution and a step of forming a channel region can be given. In addition, as another method in which the step of forming the channel region and the step of removing the oxide film on the surface of the semiconductor layer of the channel region are combined, a step of etching the source / drain electrode 26, and then forming the channel region As the step of performing, there is a method of performing a step of etching the doped semiconductor layer 25 using the photoresist used in the patterning of the source / drain electrode 26 as it is. In this case, the step of peeling the photoresist is performed after the step of forming the channel region and the step of removing the oxide film on the surface of the semiconductor layer of the channel region. In both methods, if necessary, a cleaning process using UV irradiation or a gas mainly composed of oxygen and mixed with CF ₄ , N ₂ or the like is used to generate a plasma to a degree that does not cause inconvenience. It is possible to appropriately incorporate an ashing process using oxygen radicals.

  Note that there is no particular limitation on the etchant used when the step of forming the channel region is performed by wet etching, as long as the channel region can be formed and the oxide film can be removed. Acids, buffered hydrofluoric acid, hydrochloric acid, sulfuric acid, acetic acid, oxalic acid and other acidic liquids, aqueous solutions thereof, mixtures thereof and the like can be mentioned. Among these, the ease of wet etching and the high ability to remove oxide films can reduce the manufacturing lead time, reduce the manufacturing cost of thin film transistors, improve the manufacturing yield, and more than one on a large substrate. Also when manufacturing a thin film transistor, the oxide film removal using a solution containing hydrofluoric acid is preferable because the stability of thin film transistor characteristics can be improved uniformly.

  Next, a passivation film made of an organic material is formed. In addition, between the series of steps from FIGS. 2A to 2G and the step of forming a passivation film made of an organic material, the steps in FIGS. 2A to 2G have been described. To the extent that the effect of removing the oxide film on the surface of the semiconductor layer in the channel region is not lost, the substrate on which the thin film transistor is formed may be left or other steps may be performed. However, since the surface of the semiconductor layer in the channel region is exposed through the processes of FIGS. 2A to 2G, the channel region is again formed by leaving it in the atmosphere for a long time or inserting a harsh process. There is a possibility that an oxide film is formed on the surface of the semiconductor layer. Therefore, it is necessary to avoid leaving the process for a long time so that the effect of removing the oxide film is lost, and putting many processes or severe processes in the middle. As described above, the passivation film made of the organic material is formed from the step after the “step of forming the channel region” described in the claims of the present invention in FIGS. 2 (f) to 2 (g). The steps up to the step correspond to the “step of forming a passivation film containing an organic material following the step of removing the oxide film” described in the claims of the present invention.

  In the present invention, the passivation film made of an organic material is not particularly limited, but can be formed by a plasma CVD method, a vapor deposition method, a film lamination method, a coating method, or the like. Among these, a film lamination method or a coating method is preferable because a film can be easily and efficiently formed, and a coating method is more preferable.

In film formation by a coating method, a passivation film made of an organic material can be formed from a resin composition containing a resin and an organic solvent because a highly reliable thin film transistor can be formed in a simple and short process. Is preferred.
The coating method is a method of removing the solvent after coating the resin composition on the substrate over which the thin film transistor that has gone through the process of removing the oxide film on the surface of the semiconductor layer in the channel region is applied. Examples of the method of applying the resin composition on the substrate include a spray method, a spin coating method, a roll coating method, a die coating method, a doctor blade method, a spin coating method, a bar coating method, and a screen printing method. it can. Solvent removal is performed by drying, preferably heat drying, the coating film. In that case, although drying temperature can be suitably selected according to the kind and compounding agent of each component, it is 30-250 degreeC normally. Although drying time can be suitably selected according to the kind and compounding ratio of each component, it is 0.5 to 150 minutes normally.
In the film lamination method, the resin composition is applied onto a B-stage film forming substrate such as a resin film or a metal film, the solvent is removed to obtain a B-stage film, and then this B-stage film is placed on the substrate. It is a method of laminating. Solvent removal is performed by drying, preferably heat drying, the B-stage film-forming substrate after coating. In that case, although drying conditions can be suitably selected according to the kind and mixture ratio of each component, drying temperature is 30-150 degreeC normally, and drying time is 0.5-90 minutes normally. It is. Film lamination can be performed using a pressure bonding machine such as a pressure laminator, a press, a vacuum laminator, a vacuum press, or a roll laminator.

  Thus, a passivation film made of an organic material is formed on the substrate on which the thin film transistor is formed. The thickness of the passivation film is usually 0.1 to 100 μm, preferably 0.5 to 50 μm, more preferably 0.5 to 30 μm, and most preferably 0.5 to 10 μm. When the thickness of the passivation film is in the above range, a thin film transistor having high reliability can be easily manufactured even in a harsh atmosphere. If the thickness of the passivation film is too thin, the protection performance is deteriorated and the reliability is deteriorated, or the yield is deteriorated due to particles at the time of manufacture and the defective product rate is increased. If the thickness is too large, the stress of the passivation film increases, so that the protection performance is lowered and the reliability is deteriorated.

In the present invention, the resin (A) is not particularly limited, and examples thereof include cyclic olefin resin, acrylic resin, acrylamide resin, polysiloxane, epoxy resin, phenol resin, cardo resin, polyimide, polyamideimide, polycarbonate, polyethylene terephthalate, and the like. It is done. Among these, it is preferable to include at least one selected from the group consisting of a cyclic olefin resin, an acrylic resin, a cardo resin, a polysiloxane, and a polyimide resin, and among these, from the viewpoint of the reliability of the thin film transistor, the cyclic olefin resin is More preferred is a cyclic olefin resin having a protic polar group.
These resins may be used alone or in combination of two or more.

  The proton polar group refers to a group containing an atom in which a hydrogen atom is directly bonded to an atom belonging to Group 15 or Group 16 of the Periodic Table. The atom belonging to group 15 or 16 of the periodic table is preferably an atom belonging to the first or second period of group 15 or 16 of the periodic table, more preferably an oxygen atom, nitrogen atom or sulfur An atom, particularly preferably an oxygen atom.

Specific examples of the protic polar group include polar groups having an oxygen atom such as a hydroxyl group, a carboxy group (hydroxycarbonyl group), a sulfonic acid group, and a phosphoric acid group; a primary amino group, a secondary amino group, and a primary group. A polar group having a nitrogen atom such as a secondary amide group or a secondary amide group (imide group); a polar group having a sulfur atom such as a thiol group; Among these, those having an oxygen atom are preferable, and a carboxy group is more preferable.
In the present invention, the number of protic polar groups bonded to the cyclic olefin resin having a protic polar group is not particularly limited, and different types of protic polar groups may be included.

In the present invention, the cyclic olefin resin is a homopolymer or copolymer of a cyclic olefin monomer having a cyclic structure (alicyclic ring or aromatic ring) and a carbon-carbon double bond. The cyclic olefin resin may have a unit derived from a monomer other than the cyclic olefin monomer.
The ratio of the cyclic olefin monomer unit in the total structural units of the cyclic olefin resin is usually 30 to 100% by weight, preferably 50 to 100% by weight, and more preferably 70 to 100% by weight.

  In the cyclic olefin resin having a protic polar group, the protic polar group may be bonded to the cyclic olefin monomer unit or may be bonded to a monomer unit other than the cyclic olefin monomer, It is desirable that it is bonded to a cyclic olefin monomer unit.

As a monomer for constituting a cyclic olefin resin having a protic polar group, a cyclic olefin monomer having a protic polar group (a), a cyclic olefin monomer having a polar group other than a protic polar group (B), a cyclic olefin monomer having no polar group (c), and a monomer other than the cyclic olefin (d) (these monomers are hereinafter simply referred to as monomers (a) to (d)). .). Here, the monomer (d) may have a protic polar group or other polar group, or may not have a polar group at all.
In the present invention, the cyclic olefin resin having a protic polar group is preferably composed of the monomer (a), the monomer (b) and / or the monomer (c). More preferably, it is composed of (a) and the monomer (b).

Specific examples of the monomer (a) include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene and 5-methyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene. Ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-dihydroxycarbonylbicyclo [2.2.1] hept-2-ene, 9-hydroxycarbonyltetra Cyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9,10-dihydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . Carboxy group-containing cyclic olefin such as 0 ^2,7 ] dodec-4-ene; 5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5- (4-hydroxy Phenyl) bicyclo [2.2.1] hept-2-ene, 9- (4-hydroxyphenyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9- (4-hydroxyphenyl) tetracyclo [6.2.1.1 ^3,6 . Hydroxyl group-containing cyclic olefins such as 0 ^2,7 ] dodec-4-ene and the like are mentioned, among which carboxy group-containing cyclic olefins are preferable. These cyclic olefin monomers (a) having a protic polar group may be used alone or in combination of two or more.

  Specific examples of polar groups other than protic polar groups possessed by the cyclic olefin monomer (b) having polar groups other than protic polar groups are generically referred to as ester groups (alkoxycarbonyl groups and aryloxycarbonyl groups). .), N-substituted imide group, epoxy group, halogen atom, cyano group, carbonyloxycarbonyl group (acid anhydride residue of dicarboxylic acid), alkoxy group, carbonyl group, tertiary amino group, sulfone group, acryloyl group Etc. Among these, an ester group, an N-substituted imide group, and a cyano group are preferable, an ester group and an N-substituted imide group are more preferable, and an N-substituted imide group is particularly preferable.

Specific examples of the monomer (b) include the following cyclic olefins. Examples of the cyclic olefin having an ester group include 5-acetoxybicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl- 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 9-acetoxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-n-propoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-isopropoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-n-butoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-ethoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-n-propoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-isopropoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-n-butoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene and the like.

Examples of the cyclic olefin having an N-substituted imide group include N-phenylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -1-isopropyl. -4-methylbicyclo [2.2.2] oct-5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2, Examples include 3-dicarboximide, N-[(2-ethylbutoxy) ethoxypropyl] -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide.
Examples of the cyclic olefin having a cyano group include 9-cyanotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-cyanotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 5-cyanobicyclo [2.2.1] hept-2-ene and the like.
Examples of the cyclic olefin having a halogen atom include 9-chlorotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-chlorotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene and the like.
These cyclic olefin monomers (b) having a polar group other than the protic polar group may be used alone or in combination of two or more.

Specific examples of the cyclic olefin monomer (c) having no polar group include bicyclo [2.2.1] hept-2-ene (also referred to as “norbornene”), 5-ethyl-bicyclo [2. 2.1] Hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene- Bicyclo [2.2.1] hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [5.2.1.0 ^2,6 ] deca-3,8 - diene (common name: dicyclopentadiene), tetracyclo [10.2.1.0 ^2,11. 0 ^4,9 ] pentadeca-4,6,8,13-tetraene, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene (also referred to as “tetracyclododecene”), 9-methyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylidene-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidene-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-vinyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-propenyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, pentacyclo [9.2.1.1 ^3,9 . 0 ^2,10] pentadeca-5,12-diene, cyclopentene, cyclopentadiene, 9-phenyl - tetracyclo [6.2.1.1 ^{3, 6.} 0 ^2,7] dodeca-4-ene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene, pentacyclo [9.2.1.1 ^3,9 . 0 ^2,10] pentadeca-12-ene, and the like.
These cyclic olefin monomers (c) having no polar group may be used alone or in combination of two or more.

A specific example of the monomer (d) other than the cyclic olefin includes a chain olefin. Examples of the chain olefin include ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, C2-C20 α-olefins such as 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; 1,4-hexadiene, 4-methyl-1 , 4-hexadiene, 5-methyl-1,4-hexadiene, non-conjugated dienes such as 1,7-octadiene, and the like.
Monomers (d) other than these cyclic olefins can be used alone or in combination of two or more.

  The cyclic olefin resin having a protic polar group used in the present invention is obtained by polymerizing the monomer (a) together with a monomer selected from the monomers (b) to (d) as desired. . The polymer obtained by polymerization may be further hydrogenated. A hydrogenated polymer is also included in the cyclic olefin resin having a protic polar group used in the present invention.

In addition, the cyclic olefin resin having a protic polar group used in the present invention introduces a protic polar group into a cyclic olefin resin having no protic polar group using a known modifier, and optionally hydrogenated. It can be obtained also by the method of performing. Hydrogenation may be performed on the polymer before introduction of the protic polar group. Further, the cyclic olefin resin having a protic polar group may be further modified to introduce a protic polar group.
A polymer having no protic polar group can be obtained by polymerizing the monomers (b) to (d) in any combination.

As the modifier for introducing a protic polar group, a compound having a protic polar group and a reactive carbon-carbon unsaturated bond in one molecule is usually used.
Specific examples of such compounds include acrylic acid, methacrylic acid, angelic acid, tiglic acid, oleic acid, elaidic acid, erucic acid, brassic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, atropaic acid. Unsaturated carboxylic acids such as acids and cinnamic acids; allyl alcohol, methyl vinyl methanol, crotyl alcohol, methallyl alcohol, 1-phenylethen-1-ol, 2-propen-1-ol, 3-butene-1- All, 3-buten-2-ol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl- Saturation of 3-buten-1-ol, 4-penten-1-ol, 4-methyl-4-penten-1-ol, 2-hexen-1-ol, etc. Alcohol; and the like.
The modification reaction of the cyclic olefin resin using this modifier may be performed in accordance with a conventional method, and is usually performed in the presence of a radical generator.

The polymerization method for polymerizing the monomer (a) together with a monomer selected from the monomers (b) to (d) as desired may be in accordance with a conventional method, for example, ring-opening polymerization method or An addition polymerization method is employed.
As the polymerization catalyst, for example, metal complexes such as molybdenum, ruthenium and osmium are preferably used. These polymerization catalysts can be used alone or in combination of two or more. The amount of the polymerization catalyst is usually from 1: 100 to 1: 2,000,000, preferably from 1: 500 to 1: 1,000,000, more preferably in the molar ratio of metal compound to cyclic olefin in the polymerization catalyst. Is in the range of 1: 1,000 to 1: 500,000.

Hydrogenation of the polymer obtained by polymerizing each monomer is usually performed using a hydrogenation catalyst.
As the hydrogenation catalyst, for example, those generally used for hydrogenation of olefin compounds can be used. Specifically, a Ziegler type homogeneous catalyst, a noble metal complex catalyst, a supported noble metal catalyst, and the like can be used.
Among these hydrogenation catalysts, no side reactions such as functional group modification occur, and noble metals such as rhodium and ruthenium can be selectively hydrogenated from the main chain carbon-carbon unsaturated bonds in the polymer. A complex catalyst is preferable, and a nitrogen-containing heterocyclic carbene compound having a high electron donating property or a ruthenium catalyst coordinated with a phosphine is particularly preferable.

The hydrogenation rate of the main chain of the hydrogenated polymer is usually 90% or more, preferably 95% or more, more preferably 98% or more. When the hydrogenation rate is within this range, the resin (A) is particularly excellent in heat resistance and suitable.
The hydrogenation rate of the resin (A) can be measured by ¹ H-NMR spectrum. For example, it can obtain | require as a ratio with respect to the carbon-carbon double bond mole number before hydrogenation of hydrogenated carbon-carbon double bond mole number.

  In the present invention, as the cyclic olefin resin having a protic polar group, those having a structural unit represented by the formula (I) as shown below are particularly suitable, and a structure represented by the formula (I) What has a unit and the structural unit represented by Formula (II) is more suitable.

Wherein ^(I), R 1 ~R ⁴ are each independently a hydrogen atom or _-X n -R 'group (X is a divalent organic group; n is 0 or 1; R' Is an alkyl group which may have a substituent, an aromatic group which may have a substituent, or a protic polar group. At least one of R ^{1 to} R ⁴ is a —X _n —R ′ group in which R ′ is a protic polar group. m is an integer of 0-2. ]

[In formula (II), R < ⁵ > -R < ⁸ > is 3-5 membered heterocyclic ring which contains an oxygen atom or a nitrogen atom as a ring-constituting atom with two carbon atoms to which they are couple | bonded. A structure is formed, and this heterocyclic ring may have a substituent on the heterocyclic ring. k is an integer of 0-2. ]

In the general formula (I), examples of the divalent organic group represented by X include a methylene group, an ethylene group, and a carbonyl group.
The alkyl group which may have a substituent represented by R ′ is usually a linear or branched alkyl group having 1 to 7 carbon atoms, and examples thereof include a methyl group, an ethyl group, n -A propyl group, an isopropyl group, etc. are mentioned. The aromatic group which may have a substituent is usually an aromatic group having 6 to 10 carbon atoms, and examples thereof include a phenyl group and a benzyl group. Examples of substituents for these alkyl groups and aromatic groups include alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl groups; phenyl groups And aryl groups having 6 to 12 carbon atoms such as xylyl group, tolyl group and naphthyl group.
Examples of the protic polar group represented by R ′ include the groups described above.

In the general formula (II), examples of the 3-membered heterocyclic structure formed by R ^{5 to} R ⁸ together with two carbon atoms to which R ^{5 to} R ⁸ are bonded include an epoxy structure. Similarly, examples of the 5-membered heterocyclic structure include dicarboxylic anhydride structure [—C (═O) —O—C (═O) —], dicarboximide structure [—C (═O) —N— C (= O)-] and the like. Examples of the substituent bonded to the heterocyclic ring include a phenyl group, a naphthyl group, and an anthracenyl group.

  The acrylic resin used in the present invention is not particularly limited, but a homopolymer having at least one selected from a carboxylic acid having an acrylic group, a carboxylic acid anhydride having an acrylic group, or an epoxy group-containing acrylate compound as an essential component. Or a copolymer is preferable.

Specific examples of the carboxylic acid having an acrylic group include (meth) acrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, glutaconic acid and the like;
Specific examples of the carboxylic acid anhydride having an acrylic group include maleic anhydride, citraconic anhydride and the like;
Specific examples of the epoxy group-containing acrylate compound include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylate 3,4. -Epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl; It is done.
Of these, (meth) acrylic acid, maleic anhydride, glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl and the like are preferable. In the present invention, “(meth)” means either methacryl or acryl.

  The acrylic resin is a copolymer of at least one selected from an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride and an epoxy group-containing unsaturated compound and another acrylate monomer or a copolymerizable monomer other than an acrylate. It may be a polymer. Other acrylate monomers include methyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, ethylhexyl (meth) acrylate, decyl (meth) acrylate, Alkyl (meth) acrylates such as dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate;

Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, etc .; phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl ( Phenoxyalkyl (meth) acrylates such as meth) acrylate; Alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate; Polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol ( Polyalkylene glycols such as (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and phenoxypolyethylene glycol (meth) acrylate Meth) acrylate; cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl (meth) Examples thereof include cycloalkyl (meth) acrylates such as acrylate, isobornyl (meth) acrylate, and tricyclodecanyl (meth) acrylate; benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like. Of these, butyl (meth) acrylate, ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and the like are preferable.

The copolymerizable monomer other than the acrylate is not particularly limited as long as it is a compound copolymerizable with the carboxylic acid having an acrylic group, a carboxylic acid anhydride having an acrylic group, or an epoxy group-containing acrylate compound. And vinyl group-containing radical polymerizable compounds such as vinyl benzyl methyl ether, vinyl glycidyl ether, styrene, α-methyl styrene, butadiene, and isoprene.
These compounds may be used alone or in combination of two or more.
The monomer polymerization method may be in accordance with a conventional method, for example, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method or the like is employed.

A cardo resin is a resin having a cardo structure, that is, a skeletal structure in which two cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure. A common cardo structure is a fluorene ring bonded to a benzene ring.
Specific examples of the skeleton structure in which two cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure include a fluorene skeleton, a bisphenol fluorene skeleton, a bisaminophenyl fluorene skeleton, a fluorene skeleton having an epoxy group, and an acrylic group. And a fluorene skeleton having the same.
The cardo resin used in the present invention is formed by polymerizing the skeleton having the cardo structure by a reaction between functional groups bonded thereto. The cardo resin has a structure in which a main chain and bulky side chains are connected by one element (cardo structure), and has a ring structure in a direction substantially perpendicular to the main chain.
An example of a cardo structure having an epoxy glycidyl ether structure is shown in Formula (III).

(In formula (III), n represents an integer of 0 to 10)

Monomers having a cardo structure include, for example, bis (glycidyloxyphenyl) fluorene type epoxy resin; condensate of bisphenol fluorene type epoxy resin and acrylic acid; 9,9-bis (4-hydroxyphenyl) fluorene, Cardio structure-containing bisphenols such as 9-bis (4-hydroxy-3-methylphenyl) fluorene; 9,9-bis (cyanoalkyl) fluorenes such as 9,9-bis (cyanomethyl) fluorene; -9,9-bis (aminoalkyl) fluorenes such as bis (3-aminopropyl) fluorene;
The cardo resin is a polymer obtained by polymerizing a monomer having a cardo structure, but may be a copolymer with other copolymerizable monomers.
The polymerization method of the monomer may be according to a conventional method, and for example, a ring-opening polymerization method or an addition polymerization method is employed.

  The structure of the polysiloxane used in the present invention is not particularly limited, but preferably includes a polysiloxane obtained by mixing and reacting at least one organosilane represented by the formula (IV).

R _{9 in} formula (IV) represents any one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and the plurality of R ₉ are the same. It can be different. In addition, these alkyl groups, alkenyl groups, and aryl groups may all have a substituent, or may be unsubstituted without a substituent, and are selected according to the characteristics of the composition. it can. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 2,2 , 2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-aminopropyl group, 3-mercaptopropyl Group, 3-isocyanatopropyl group. Specific examples of the alkenyl group include a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group. Specific examples of the aryl group include phenyl group, tolyl group, p-hydroxyphenyl group, 1- (p-hydroxyphenyl) ethyl group, 2- (p-hydroxyphenyl) ethyl group, 4-hydroxy-5- (p -Hydroxyphenylcarbonyloxy) pentyl group, naphthyl group.

R _{10 in} formula (IV) represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R ₁₀ may be the same. It may be different. In addition, these alkyl groups and acyl groups may have a substituent or may be an unsubstituted form having no substituent, and can be selected according to the characteristics of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Specific examples of the acyl group include an acetyl group. Specific examples of the aryl group may include a phenyl group.
N in the formula (IV) represents an integer of 0 to 3. A tetrafunctional silane when n = 0, a trifunctional silane when n = 1, a bifunctional silane when n = 2, and a monofunctional silane when n = 3.

  Specific examples of the organosilane represented by the formula (IV) include tetrafunctional silanes such as tetramethoxysilane and tetraethoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane Ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltri Methoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, p-hydroxyphenyltrimethoxysilane, 2- (p-hydroxy) Phenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -Trifunctional silanes such as glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxy And bifunctional silanes such as silane, di-n-butyldimethoxysilane and diphenyldimethoxysilane; monofunctional silanes such as trimethylmethoxysilane and tri-n-butylethoxysilane.

  Of these organosilanes, trifunctional silanes are preferably used from the viewpoint of crack resistance and hardness of the resin film obtained from the resin composition of the present invention. These organosilanes may be used alone or in combination of two or more.

  The polysiloxane in the present invention can be obtained by hydrolysis and partial condensation of the above organosilane. A general method can be used for hydrolysis and partial condensation. For example, a solvent, water, and a catalyst as necessary are added to the mixture, and the mixture is heated and stirred. During stirring, if necessary, hydrolysis by-products (alcohols such as methanol) and condensation by-products (water) may be distilled off by distillation.

The polyimide used by this invention can be obtained by heat-processing the polyimide precursor obtained by making tetracarboxylic anhydride and diamine react. Examples of the precursor for obtaining the polyimide resin include polyamic acid, polyamic acid ester, polyisoimide, and polyamic acid sulfonamide.
Specific examples of the acid dianhydride that can be used as a raw material for polyimide include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane Anhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) ) Methane dianhydride, bis (2 , 3-Dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6- Naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetra Aromatic tetracarboxylic dianhydrides such as carboxylic dianhydride and 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, butanetetracarboxylic dianhydride, 1,2, Examples thereof include aliphatic tetracarboxylic dianhydrides such as 3,4-cyclopentanetetracarboxylic dianhydride. These acid dianhydrides can be used alone or in combination of two or more.

  Specific examples of diamines that can be used as raw materials for polyimide include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4 '-Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m- Phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl , Screw {4 (4-Aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4,4′- Diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-diethyl-4,4′-diaminobiphenyl, 2,2 ′, 3,3′-tetramethyl-4,4 ′ -Diaminobiphenyl, 3,3 ', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl, or aromatics thereof Examples include compounds substituted on the ring with an alkyl group or a halogen atom, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and the like. These diamines can be used alone or in combination of two or more.

  The polyimide used in the present invention is synthesized by a known method. That is, a tetracarboxylic dianhydride and a diamine are selectively combined, and these are combined with N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphorotriamide, It is synthesized by a known method such as reacting in a polar solvent such as γ-butyrolactone or cyclopentanone.

The weight average molecular weight (Mw) of the resin (A) used in the present invention is usually 1,000 to 1,000,000, preferably 1,500 to 100,000, more preferably 2,000 to 10,000. 000 range.
The molecular weight distribution of the resin (A) is a weight average molecular weight / number average molecular weight (Mw / Mn) ratio, and is usually 4 or less, preferably 3 or less, more preferably 2.5 or less.
The weight average molecular weight (Mw) and molecular weight distribution of the resin (A) can be measured using gel permeation chromatography. For example, it can be determined as a molecular weight in terms of polystyrene using a solvent such as tetrahydrofuran as an eluent.

The organic solvent (B) used in the present invention is not particularly limited. Specific examples thereof include alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol; ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene Alkylene glycol monoethers such as glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol di Alkylene glycol dialkyl ethers such as chill ether and dipropylene glycol ethyl methyl ether; alkylene glycol monoalkyl ether esters such as propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; methyl ethyl ketone and cyclohexanone Ketones such as 2-heptanone, 4-hydroxy-4-methyl-2-pentanone, cyclohexanone, cyclopentanone; alcohols such as methanol, ethanol, propanol, butanol, 3-methoxy-3-methylbutanol; tetrahydrofuran, Cyclic ethers such as dioxane; methyl cellosolve acetate, ethyl cellosolve acetate Cellosolve esters; aromatic hydrocarbons such as benzene, toluene, xylene; ethyl acetate, butyl acetate, ethyl lactate, methyl 2-hydroxy-2-methylpropionate, ethyl 3-ethoxypropionate, 3-ethoxypropionic acid Esters such as methyl and γ-butyrolactone; Amides such as N-methylformamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-methylacetamide and N, N-dimethylacetamide; Sulfoxides; and the like.
Among these, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, cyclopentanone, and N-methyl-2-pyrrolidone are preferable.

  These organic solvents (B) may be used alone or in combination of two or more. The amount of the organic solvent (B) used is usually in the range of 20 to 10,000 parts by weight, preferably 50 to 5,000 parts by weight, more preferably 100 to 1,000 parts by weight with respect to 100 parts by weight of the resin. It is.

In the resin composition of this invention, it is preferable to contain the compound (C) which has an acidic group further. The compound (C) having an acidic group is not particularly limited, but is preferably an aliphatic compound, an aromatic compound, or a heterocyclic compound, and more preferably an aromatic compound or a heterocyclic compound.
These compounds (C) can be used alone or in combination of two or more.

The number of acidic groups is not particularly limited, but those having two or more acidic groups are preferable, and those having two acidic groups are particularly preferable. The acidic groups may be the same as or different from each other.
The acidic group may be an acidic functional group, and specific examples thereof include strong acidic groups such as sulfonic acid group and phosphoric acid group; weak acidic groups such as carboxy group, thiol group and carboxymethylenethio group. It is done. Among these, a carboxy group, a thiol group, or a carboxymethylenethio group is preferable, and a carboxy group is particularly preferable. Among these acidic groups, those having an acid dissociation constant pKa in the range of 3.5 to 5.0 are preferred. When there are two or more acidic groups, the first dissociation constant pKa1 is defined as the acid dissociation constant. Note that pKa is an acid dissociation constant Ka = [H ₃ O +] [B −] / [BH] under dilute aqueous solution conditions. Here, BH represents an organic acid, and B − represents a conjugate base of the organic acid. pKa is pKa = −logKa.
Moreover, the measuring method of pKa can calculate hydrogen ion concentration, for example using a pH meter, and can calculate from the density | concentration of a applicable substance, and hydrogen ion concentration.
In this invention, the passivation film formed from the resin composition of this invention is excellent in the reliability improvement of a thin-film transistor by using the compound (C) which has these acidic groups.

In the present invention, the compound (C) may have a substituent other than an acidic group.
As such substituents, in addition to hydrocarbon groups such as alkyl groups and aryl groups, halogen atoms; alkoxy groups, aryloxy groups, acyloxy groups, heterocyclic oxy groups; substituted with alkyl groups, aryl groups, or heterocyclic groups Polar groups having no proton such as amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group; alkylthio group, arylthio group, heterocyclic thio group; Examples thereof include a hydrocarbon group substituted with a polar group having no proton.

  Specific examples of the compound (B) include methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, glycolic acid, glycerin. Acid, ethanedioic acid (also referred to as “oxalic acid”), propanedioic acid (also referred to as “malonic acid”), butanedioic acid (also referred to as “succinic acid”), pentanedioic acid, hexanedioic acid (“ Adipic acid "), 1,2-cyclohexanedicarboxylic acid, 2-oxopropanoic acid, 2-hydroxybutanedioic acid, 2-hydroxypropanetricarboxylic acid, mercaptosuccinic acid, dimercaptosuccinic acid, 2,3-dimercapto- 1-propanol, 1,2,3-trimercaptopropane, 2,3,4-trimercapto-1-butanol, 2,4-dimercapto 1,3-butanediol, 1,3,4-trimercapto-2-butanol, 3,4-dimercapto-1,2-butanediol, aliphatic compounds such as 1,5-dimercapto-3-Chiapentan;

Benzoic acid, p-hydroxybenzenecarboxylic acid, o-hydroxybenzenecarboxylic acid, 2-naphthalenecarboxylic acid, methylbenzoic acid, dimethylbenzoic acid, trimethylbenzoic acid, 3-phenylpropanoic acid, 2-hydroxybenzoic acid, dihydroxybenzoic acid , Dimethoxybenzoic acid, benzene-1,2-dicarboxylic acid (also referred to as “phthalic acid”), benzene-1,3-dicarboxylic acid (also referred to as “isophthalic acid”), benzene-1,4-dicarboxylic acid ( Also referred to as “terephthalic acid”), benzene-1,2,3-tricarboxylic acid, benzene-1,2,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, benzenehexacarboxylic acid, biphenyl-2 , 2'-dicarboxylic acid, 2- (carboxymethyl) benzoic acid, 3- (carboxymethyl) benzoic acid 4- (carboxymethyl) benzoic acid, 2- (carboxycarbonyl) benzoic acid, 3- (carboxycarbonyl) benzoic acid, 4- (carboxycarbonyl) benzoic acid, 2-mercaptobenzoic acid, 4-mercaptobenzoic acid, 2- Mercapto-6-naphthalenecarboxylic acid, 2-mercapto-7-naphthalenecarboxylic acid, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,4-naphthalenedithiol, 1 , 5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercapto) Chill) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris Aromatic compounds such as (mercaptoethyl) benzene;

Nicotinic acid, isonicotinic acid, 2-furoic acid, pyrrole-2,3-dicarboxylic acid, pyrrole-2,4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dicarboxylic acid, imidazole Five-membered nitrogen atoms such as 2,4-dicarboxylic acid, imidazole-2,5-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, pyrazole-3,5-dicarboxylic acid Heterocyclic compounds; thiophene-2,3-dicarboxylic acid, thiophene-2,4-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, thiazole-2,4-dicarboxylic acid, thiazole -2,5-dicarboxylic acid, thiazole-4,5-dicarboxylic acid, isothiazole-3,4-dicarboxylic acid, isothiazole -3,5-dicarboxylic acid, 1,2,4-thiadiazole-2,5-dicarboxylic acid, 1,3,4-thiadiazole-2,5-dicarboxylic acid, 3-amino-5-mercapto-1,2, 4-thiadiazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 3,5-dimercapto-1,2,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole, 3- (5-mercapto-1,2,4-thiadiazol-3-ylsulfanyl) succinic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylsulfanyl) succinic acid, (5-mercapto-1 , 2,4-thiadiazol-3-ylthio) acetic acid, (5-mercapto-1,3,4-thiadiazol-2-ylthio) acetic acid, 3- (5-mercapto-1,2,4) Thiadiazol-3-ylthio) propionic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylthio) propionic acid, 3- (5-mercapto-1,2,4-thiadiazol-3-ylthio) Succinic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylthio) succinic acid, 4- (3-mercapto-1,2,4-thiadiazol-5-yl) thiobutanesulfonic acid, 4 -5-membered heterocyclic compound containing a nitrogen atom and a sulfur atom such as (2-mercapto-1,3,4-thiadiazol-5-yl) thiobutanesulfonic acid;

Pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine-3,5 -Dicarboxylic acid, pyridazine-3,4-dicarboxylic acid, pyridazine-3,5-dicarboxylic acid, pyridazine-3,6-dicarboxylic acid, pyridazine-4,5-dicarboxylic acid, pyrimidine-2,4-dicarboxylic acid, pyrimidine -2,5-dicarboxylic acid, pyrimidine-4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, pyrazine-2,5-dicarboxylic acid, pyridine-2,6- Dicarboxylic acid, triazine-2,4-dicarboxylic acid, 2-diethylamino-4,6-dimercapto-s-triazine, 2-dipropyl Mino-4,6-dimercapto-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, 2-anilino-4,6-dimercapto-s-triazine, 2,4,6-trimercapto- 6-membered heterocyclic compounds containing a nitrogen atom such as s-triazine.
Among these, from the viewpoint of further improving the stability of the thin film transistor, the number of acidic groups is preferably 2 or more, and particularly preferably 2.
The compounds having two acidic groups include ethanedioic acid, propanedioic acid, butanedioic acid, pentanedioic acid, hexanedioic acid, 1,2-cyclohexanedicarboxylic acid, benzene-1,2-dicarboxylic acid (“phthalic acid”). ), Benzene-1,3-dicarboxylic acid (also referred to as “isophthalic acid”), benzene-1,4-dicarboxylic acid (also referred to as “terephthalic acid”), biphenyl-2,2′-dicarboxylic acid. 2- (carboxymethyl) benzoic acid, 3- (carboxymethyl) benzoic acid, 4- (carboxymethyl) benzoic acid, 2-mercaptobenzoic acid, 4-mercaptobenzoic acid, 2-mercapto-6-naphthalenecarboxylic acid, 2-mercapto-7-naphthalenecarboxylic acid, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, Aromatic compounds having two acidic groups of 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, and 2,7-naphthalenedithiol; pyrrole-2,3-dicarboxylic acid, pyrrole-2 , 4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dicarboxylic acid, imidazole-2,4-dicarboxylic acid-, imidazole-2,5-dicarboxylic acid, imidazole-4,5-dicarboxylic acid Acid, pyrazole-3,4-dicarboxylic acid, pyrazole-3,5-dicarboxylic acid, thiophene-2,3-dicarboxylic acid, thiophene-2,4-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, thiophene-3, 4-dicarboxylic acid, thiazole-2,4-dicarboxylic acid, thiazole-2,5-dicarboxylic acid, thiazo -4,5-dicarboxylic acid, isothiazole-3,4-dicarboxylic acid, isothiazole-3,5-dicarboxylic acid, 1,2,4-thiadiazole-2,5-dicarboxylic acid, 1,3,4 -Thiadiazole-2,5-dicarboxylic acid, (5-mercapto-1,2,4-thiadiazol-3-ylthio) acetic acid, (5-mercapto-1,3,4-thiadiazol-2-ylthio) acetic acid, pyridine- 2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine-3,5-dicarboxylic acid Acid, pyridazine-3,4-dicarboxylic acid, pyridazine-3,5-dicarboxylic acid, pyridazine-3,6-dicarboxylic acid, pyridazine-4,5-dicarboxylic acid, Midine-2,4-dicarboxylic acid, pyrimidine-2,5-dicarboxylic acid, pyrimidine-4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, pyrazine-2,5 -A heterocyclic compound having two acidic groups of dicarboxylic acid, pyridine-2,6-dicarboxylic acid, and triazine-2,4-dicarboxylic acid.
By using these compounds, the effect of further improving the stability of the thin film transistor having an organic passivation film formed from the resin composition can be obtained.

  In the present invention, the content of the compound (C) having an acidic group in the resin composition to be used is usually 5 to 45 parts by weight, preferably 7 to 40 parts by weight with respect to 100 parts by weight of the resin (A). More preferably, it is the range of 10-30 weight part. If the amount of the compound (C) having an acidic group is within this range, even if the resin composition is stored after production, the properties of the resin composition change due to changes in the physical properties of the resin composition. There can be obtained a resin composition excellent in liquid stability.

  In the present invention, the resin composition used further has one atom selected from a silicon atom, a titanium atom, an aluminum atom, and a zirconium atom, and has a hydrocarbyloxy group or a hydroxy group bonded to the atom. It is preferable to contain a compound (D).

Further, among the compounds (D), a compound having a hydrocarbyloxy group bonded to a silicon atom or a titanium atom is preferable.
Moreover, it is preferable that the said hydrocarbyloxy group is a C1-C18 hydrocarbyloxy group.

Moreover, it is especially preferable that the compound (D) has a functional group capable of reacting with the protic polar group when the resin (A) has a protic polar group.
The functional group capable of reacting with the protic polar group is preferably an isocyanate group, a mercapto group, an epoxy group, or an amino group, and more preferably an epoxy group.

Specific examples of the compound (D) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane,
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n- Butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, n-decyltrimethoxysilane, p-styryl Trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyl Nyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyl Limethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyl Triethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-ethyl (trimethoxysilylpropoxymethyl) oxetane, 3-ethyl (triethoxysilylpropoxymethyl) Kisetan, 3-triethoxysilyl-N-(1,3-dimethyl - butylidene) propylamine, trialkoxysilanes such as bis (triethoxysilylpropyl) tetrasulfide,
Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxy Silane, di-n-butyldimethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyl Dimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, Diphenyldie Xysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldiethoxysilane In addition to dialkoxysilanes such as N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane,
Silicon atoms such as methyltriacetyloxysilane, dimethyldiacetyloxysilane, trade names X-12-414, KBP-44 (manufactured by Shin-Etsu Chemical Co., Ltd.), 217FLAKE, 220FLAKE, 233FLAKE, z6018 (manufactured by Toray Dow Corning Co., Ltd.) Containing compounds;

(Tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, titanium-i-propoxyoctylene glycolate, di-i-propoxybis (acetylacetonato) titanium, propanedi Oxytitanium bis (ethylacetoacetate), tri-n-butoxytitanium monostearate, di-i-propoxytitanium distearate, titanium stearate, di-i-propoxytitanium diisostearate, (2-n-butoxycarbonyl Titanium atom-containing compounds such as benzoyloxy) tributoxytitanium, di-n-butoxy bis (triethanolaminato) titanium, as well as the preneact series (manufactured by Ajinomoto Fine Techno Co., Ltd.);
Aluminum atom-containing compounds such as (acetoalkoxyaluminum diisopropylate);
(Tetranormal propoxyzirconium, tetranormalbutoxyzirconium, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium butoxyacetylacetonate bis (ethylacetoacetate), zirconium dibutoxybis (ethylacetoacetate), zirconium tetraacetyl Zirconium atom-containing compounds such as acetonate and zirconium tributoxy systemate).

Among these, as said compound (D), a silicon atom containing compound and a titanium atom containing compound are preferable, and it is especially preferable to have a functional group which can react with a protic polar group. By having the functional group, the stability of the thin film transistor is further improved.
Examples of the compound having a functional group capable of reacting with the protic polar group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, n-2- (aminoethyl) -3-aminopropyltrimethoxysilane, n-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycid Xylpropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-ureidopropyl Particularly preferred are limethoxysilane, 3-ureidopropyltriethoxysilane, 3-triethoxysilyl-n- (1,3-dimethyl-butylidene) propylamine, n-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane. preferable.
These compounds (D) can be used alone or in combination of two or more.

  Content of the compound (D) in the resin composition used for this invention is 1-40 weight part with respect to 100 weight part of binder resin (A), Preferably it is 3-30 weight part, More preferably, it is 5-25 weight. Part range. If the amount of the compound (D) used is within this range, the stability of the thin film transistor can be further improved.

The resin composition used in the present invention preferably further contains a radiation sensitive compound (E).
The radiation sensitive compound (E) used in the present invention is a compound capable of causing a chemical reaction by irradiation with radiation such as ultraviolet rays and electron beams. In the present invention, the radiation sensitive compound (E) is preferably one capable of controlling the alkali solubility of the resin film formed from the resin composition.
In the present invention, it is preferable to use a photoacid generator as the radiation-sensitive compound (E).

  Examples of the radiation-sensitive compound (E) include azide compounds such as acetophenone compounds, triarylsulfonium salts, and quinonediazide compounds, with azide compounds being preferred, and quinonediazide compounds being particularly preferred.

As the quinonediazide compound, for example, an ester compound of a quinonediazidesulfonic acid halide and a compound having a phenolic hydroxyl group can be used. Specific examples of the quinone diazide sulfonic acid halide include 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-benzoquinone diazide-5-sulfonic acid chloride, and the like. Can be mentioned. Typical examples of the compound having a phenolic hydroxyl group include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1. -[4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and the like. Other compounds having a phenolic hydroxyl group include 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2-bis (4-hydroxyphenyl) propane, tris (4- Hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, novolac resin oligomer, phenolic hydroxyl group Examples thereof include oligomers obtained by copolymerizing one or more compounds and dicyclopentadiene.
Among these, a condensate of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and a compound having a phenolic hydroxyl group is preferable, and 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl)- A condensate of 3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.5 mol) is more preferred.

Photoacid generators include quinonediazide compounds, onium salts, halogenated organic compounds, α, α′-bis (sulfonyl) diazomethane compounds, α-carbonyl-α′-sulfonyldiazomethane compounds, sulfone compounds, organic acids Known compounds such as ester compounds, organic acid amide compounds, and organic acid imide compounds can be used.
These radiation-sensitive compounds can be used alone or in combination of two or more.

  Content of the radiation sensitive compound (E) in the resin composition used for this invention is 1-100 weight part with respect to 100 weight part of resin (A), Preferably it is 5-50 weight part, More preferably, it is 10-40. The range is parts by weight. When the amount of the radiation sensitive compound (E) is within this range, when patterning a resin film made of a resin composition formed on an arbitrary substrate, the developer is applied to the radiation irradiated portion and the radiation non-irradiated portion. This is preferable because the difference in solubility between the two is large, patterning by development is easy, and radiation sensitivity is high.

In this invention, it is preferable to further contain a crosslinking agent (F) as a component of a resin composition.
As the crosslinking agent (F), one having two or more, preferably three or more functional groups capable of reacting with the resin (A) in the molecule is used. The functional group possessed by the cross-linking agent (F) is not particularly limited as long as it can react with the functional group or unsaturated bond in the binder resin, but is preferably capable of reacting with a protic polar group.
Examples of such a functional group include an amino group, a hydroxyl group, an epoxy group, and an isocyanate group, more preferably an amino group, an epoxy group, and an isocyanate group, and still more preferably an epoxy group.

  Specific examples of the crosslinking agent (F) include aliphatic polyamines such as hexamethylenediamine; aromatic polyamines such as 4,4′-diaminodiphenyl ether and diaminodiphenylsulfone; 2,6-bis (4′-azidobenzal) Azides such as cyclohexanone and 4,4′-diazidodiphenylsulfone; polyamides such as nylon, polyhexamethylenediamine terephthalamide and polyhexamethyleneisophthalamide; N, N, N ′, N ′, N ″, N Melamines such as "-(hexaalkoxymethyl) melamine; N, N ', N", N "'-(tetraalkoxymethyl) glycolurils such as glycoluril; Acrylate compounds such as ethylene glycol di (meth) acrylate; Hexamethylene diisocyanate polyisocyanate Isocyanate compounds such as isophorone diisocyanate polyisocyanate, tolylene diisocyanate polyisocyanate, hydrogenated diphenylmethane diisocyanate; 1,4-di- (hydroxymethyl) cyclohexane, 1,4-di- (hydroxymethyl) norbornane; 1,3 , 4-trihydroxycyclohexane; bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, polyphenol type epoxy resin, cyclic aliphatic epoxy resin, aliphatic glycidyl ether, epoxy acrylate heavy And epoxy compounds such as coalescence;

  Specific examples of such an epoxy compound include a trifunctional epoxy compound having a dicyclopentadiene skeleton (trade name “XD-1000” manufactured by Nippon Kayaku Co., Ltd.), [2,2-bis (hydroxymethyl) 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 1-butanol (a 15-functional alicyclic epoxy resin having a cyclohexane skeleton and a terminal epoxy group. Trade name “EHPE3150”, manufactured by Daicel Chemical Industries, Ltd. ), Epoxidized 3-cyclohexene-1,2-dicarboxylic acid bis (3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic trifunctional epoxy resin, trade name “Epolide GT301”, manufactured by Daicel Chemical Industries, Ltd.) Epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-capro Epoxy compounds having an alicyclic structure such as lactone (aliphatic cyclic tetrafunctional epoxy resin, trade name “Epolide GT401”, manufactured by Daicel Chemical Industries);

Aromatic amine type polyfunctional epoxy compound (trade name “H-434”, manufactured by Tohto Kasei Kogyo Co., Ltd.), cresol novolac type polyfunctional epoxy compound (trade name “EOCN-1020”, manufactured by Nippon Kayaku Co., Ltd.), phenol novolac type Polyfunctional epoxy compounds (Epicoat 152, 154, manufactured by Japan Epoxy Resin Co., Ltd.), polyfunctional epoxy compounds having a naphthalene skeleton (trade name EXA-4700, manufactured by Dainippon Ink & Chemicals, Inc.), chain alkyl polyfunctional epoxy compounds (products) Name “SR-TMP”, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., multifunctional epoxy polybutadiene (trade name “Epolide PB3600”, manufactured by Daicel Chemical Industries, Ltd.), glycerin glycidyl polyether compound (trade name “SR-GLG”, Sakamoto Yakuhin) Kogyo Co., Ltd.), diglycerin polyglycidyl ether compound ( Product name “SR-DGE”, Sakamoto Yakuhin Kogyo Co., Ltd., polyglycerol polyglycidyl ether compound (trade name “SR-4GL”, Sakamoto Yakuhin Kogyo Co., Ltd.) and other epoxy compounds having no alicyclic structure; be able to.
Among these, an epoxy compound is preferable, and an epoxy compound having an alicyclic structure is more preferable in order to further improve the stability of a thin film transistor having an organic passivation film formed from the present resin composition.

Although the molecular weight of a crosslinking agent (F) is not specifically limited, Usually, it is 100-100,000, Preferably it is 500-50,000, More preferably, it is 1,000-10,000. A crosslinking agent can be used individually or in combination of 2 types or more, respectively.
The content of the crosslinking agent (F) in the resin composition of the present invention is usually 0.1 to 200 parts by weight, preferably 1 to 150 parts by weight, and more preferably 5 parts per 100 parts by weight of the resin (A). It is in the range of ˜100 parts by weight. If the usage-amount of a crosslinking agent exists in this range, sufficient heat resistance will be acquired and it is preferable.

  If desired, the resin composition used in the present invention is a sensitizer, a surfactant, a latent acid generator, an antioxidant, a light stabilizer, and an antifoaming agent as long as the effects of the present invention are not inhibited. , Other compounding agents such as pigments and dyes;

  Specific examples of the sensitizer include 2H-pyrido- (3,2-b) -1,4-oxazin-3 (4H) -ones, 10H-pyrido- (3,2-b) -1,4. -Benzothiazines, urazoles, hydantoins, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxans, maleimides and the like.

In this invention, it is preferable to contain surfactant as a component of a resin composition.
The surfactant is used for the purpose of preventing striation (after application stripes) and improving developability. Specific examples thereof include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. Aryl ethers; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Fluorine surfactants; Silicone surfactants; Methacrylic acid copolymer surfactants Agents; acrylic acid copolymer surfactants; and the like.

  The latent acid generator is used for the purpose of improving the heat resistance and chemical resistance of the resin composition of the present invention. Specific examples thereof include sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts, which are cationic polymerization catalysts that generate an acid upon heating. Of these, sulfonium salts and benzothiazolium salts are preferred.

  As the antioxidant, there can be used phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, lactone antioxidants and the like used in ordinary polymers. For example, as phenols, 2,6-di-t-butyl-4-methylphenol, p-methoxyphenol, styrenated phenol, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4 '-Hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-5'-methyl-2' -Hydroxybenzyl) -4-methylphenyl acrylate, 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol), 4,4'-thio-bis (3-methyl-6-tert-butylphenol) ), Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], alkylated bisphenols, etc. Can. Examples of the phosphorus-based antioxidant include triphenyl phosphite and tris (nonylphenyl) phosphite. Examples of the sulfur-based antioxidant include dilauryl thiodipropionate.

In the present invention, it is preferable to contain a light stabilizer as a component of the resin composition.
Light stabilizers include benzophenone-based, salicylic acid ester-based, benzotriazole-based, cyanoacrylate-based, metal complex salt-based ultraviolet absorbers, hindered amine-based (HALS), etc. that capture radicals generated by light, etc. But you can. Among these, HALS is a compound having a piperidine structure and is preferable because it is less colored and has good stability with respect to the composition of the present invention. Specific compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl 1,2,3,4 -Butanetetracarboxylate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.

The method for preparing the resin composition used in the present invention is not particularly limited, and each component of the resin composition, that is, the resin (A) and the organic solvent (B), and other components used as desired are known. What is necessary is just to mix by the method.
The mixing method is not particularly limited, but it is preferable to mix a solution or dispersion obtained by dissolving or dispersing each component of the resin composition in the organic solvent (B). Thereby, the resin composition of this invention is obtained with the form of a solution or a dispersion liquid.

  The method for dissolving or dispersing each component of the resin composition of the present invention in the organic solvent (B) may be in accordance with a conventional method. Specifically, stirring using a stirrer and a magnetic stirrer, a high-speed homogenizer, a disper, a planetary stirrer, a twin-screw stirrer, a ball mill, a three-roll, etc. can be used. Further, after each component is dissolved or dispersed in the organic solvent (B), it may be filtered using, for example, a filter having a pore size of about 0.5 μm.

  The solid content concentration when each component of the resin composition of the present invention is dissolved or dispersed in the organic solvent (B) is usually 1 to 70% by weight, preferably 5 to 60% by weight, more preferably 10 to 50%. % By weight. If the solid content concentration is in this range, the dissolution stability, the coating property on the substrate, the film thickness uniformity of the formed resin film, the flatness, etc. can be highly balanced.

In the present invention, after forming a passivation film on a substrate having a thin film transistor that has undergone a step of removing the oxide film on the surface of the semiconductor layer in the channel region, the passivation film can be crosslinked.
The passivation film formed on the substrate can be crosslinked by a crosslinking reaction of the resin (A), and preferably a crosslinking agent is used. The crosslinking may be appropriately selected depending on the type of the crosslinking agent, but is usually performed by heating. The heating method can be performed using, for example, a hot plate or an oven. The heating temperature is usually 180 to 250 ° C., and the heating time is appropriately selected depending on the size and thickness of the passivation film and the equipment used. For example, when using a hot plate, the oven is usually run for 5 to 90 minutes. When used, it is usually in the range of 30 to 120 minutes. Heating may be performed in an inert gas atmosphere as necessary. Any inert gas may be used as long as it does not contain oxygen and does not oxidize the passivation film. Examples thereof include nitrogen, argon, helium, neon, xenon, and krypton. Among these, nitrogen and argon are preferable, and nitrogen is particularly preferable. In particular, an inert gas having an oxygen content of 0.1% by volume or less, preferably 0.01% by volume or less, particularly nitrogen is suitable. These inert gases can be used alone or in combination of two or more.

In the present invention, the passivation film may be patterned.
The patterning of the passivation film formed on the substrate is, for example, a method of dry etching using a photoresist as a mask, or a resin film formed by using a resin composition containing a radiation-sensitive substance and the resin composition. In addition, a latent image pattern can be formed using actinic radiation, and a latent image pattern can be revealed using a developer.

The actinic radiation is not particularly limited as long as it can activate the photoacid generator and change the alkali solubility of the crosslinkable composition containing the photoacid generator. Specifically, ultraviolet rays, ultraviolet rays having a single wavelength such as g-line or i-line, light rays such as KrF excimer laser light and ArF excimer laser light; particle beams such as electron beams; As a method for selectively irradiating these actinic radiations in a pattern to form a latent image pattern, a conventional method may be used. For example, ultraviolet, g-line, i-line, KrF excimer is used by a reduction projection exposure apparatus or the like. A method of irradiating a light beam such as a laser beam or an ArF excimer laser beam through a desired mask pattern, a method of drawing with a particle beam such as an electron beam, or the like can be used. When light is used as the active radiation, it may be single wavelength light or mixed wavelength light. Irradiation conditions may be appropriately selected depending on the active radiation to be used, for example, when using a light beam of wavelength 200 to 450 nm, the amount of irradiation is usually 10~1,000mJ / cm ^2, preferably 50 to 500 mJ / It is a range of cm ² and is determined according to irradiation time and illuminance. After irradiation with actinic radiation in this manner, the resin film is heat-treated at a temperature of about 60 to 130 ° C. for about 1 to 2 minutes as necessary.

  Next, the latent image pattern formed on the passivation film is developed and made visible. In the present invention, such a process is referred to as “patterning”, and the patterned passivation film is referred to as “patterned passivation film”. As the developer, an aqueous solution of an alkaline compound is usually used. As the alkaline compound, for example, an alkali metal salt, an amine, or an ammonium salt can be used. The alkaline compound may be an inorganic compound or an organic compound. Specific examples of these compounds include alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate and sodium metasilicate; ammonia water; primary amines such as ethylamine and n-propylamine; diethylamine Secondary amines such as di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and choline Alcohol alcohols such as dimethylethanolamine and triethanolamine; pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona-5 -En, N-Me Cyclic amines such as Rupiroridon; and the like. These alkaline compounds can be used alone or in combination of two or more.

As an aqueous medium of the alkaline aqueous solution, water; a water-soluble organic solvent such as methanol or ethanol can be used. The alkaline aqueous solution may have a surfactant added in an appropriate amount.
As a method of bringing a developer into contact with a passivation film having a latent image pattern, for example, a paddle method, a spray method, a dipping method, or the like is used. The development is usually appropriately selected in the range of 0 to 100 ° C, preferably 5 to 55 ° C, more preferably 10 to 30 ° C, and usually 30 to 180 seconds.

After the target patterned passivation film is formed in this way, the substrate can be rinsed with a rinsing liquid as necessary to remove development residues on the substrate, the back surface of the substrate, and the edge of the substrate. After the rinse treatment, the remaining rinse liquid is removed with compressed air or compressed nitrogen.
Further, if necessary, in order to deactivate the photoacid generator, the entire surface of the substrate having the patterned passivation film can be irradiated with actinic radiation. For irradiation with actinic radiation, the method exemplified in the formation of the latent image pattern can be used. The passivation film may be heated simultaneously with irradiation or after irradiation. Examples of the heating method include a method of heating the substrate in a hot plate or an oven. The temperature is usually in the range of 100 to 300 ° C, preferably 120 to 200 ° C.

In this invention, after forming patterned resin on a board | substrate, the crosslinking reaction of patterned resin can be performed.
The cross-linking may be performed in the same manner as the above-described cross-linking of the passivation film formed on the substrate.

  The thin film transistor obtained by the production method of the present invention can be used for a display device such as an active matrix type liquid crystal display or an active matrix type organic EL.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In this example, “parts” and “%” are “parts by weight” and “% by weight”, respectively, unless otherwise specified.

Each characteristic was evaluated by the following methods.
(1) Thin Film Transistor Characteristics Using a semiconductor parameter analyzer (Agilent 4156A), the change in the source-drain current with respect to the change in the gate voltage of the measurement sample (substrate having the thin film transistor) immediately after the production was measured. The ratio between the value of the source-drain current when the gate voltage was −3 V and the value of the source-drain current when the gate voltage was 10 V was observed as the ON / OFF ratio. Subsequently, the measurement sample was placed in a constant temperature and humidity chamber (Platinus PR-2KP manufactured by Espec Corp.) set at a temperature of 60 ° C. and a humidity of 90%. After installation, the ON / OFF ratio was measured by the above method every 5 hours. Thereafter, the time when the ON / OFF ratio was reduced to 1/10 from the initial value was observed as the thin film transistor characteristics. Evaluation criteria were as follows. According to this analysis, the longer the thin film transistor characteristics, the higher the reliability of the thin film transistor.
A +: 400 hours or more A: 300 hours or more and less than 400 hours B: 200 hours or more and less than 300 hours C: 100 hours or more and less than 200 hours D: Less than 100 hours (2) Transmittance Measurement sample immediately after preparation (substrate having thin film transistors ) Was measured using a spectrophotometer (manufactured by JASCO Corporation, “UV-visible spectrophotometer V-560 (product name)”). The portion of the measurement sample substrate on which the glass substrate, the gate insulating film, and the passivation film are stacked and does not include the gate electrode, the source electrode, the drain electrode, the semiconductor layer, and the impurity-added semiconductor layer is used. According to this analysis, the higher the transmittance, the lower the transmittance. The transparency of the film transistor substrate is increased.

[Production Example 1]
(Production of cyclic olefin polymer having a protic polar group)
As a cyclic olefin monomer having a protic polar group, 9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene as a cyclic olefin monomer having no protic polar group as tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene (also referred to as “tetracyclododecene”) 40 parts, 2.8 parts 1,5-hexadiene, and (1,3-dimesitylimidazolidine-2- Iridene) (tricyclohexylphosphine) benzylidene ruthenium dichloride 0.05 part and 400 parts of diethylene glycol ethyl methyl ether as a solvent were charged into a nitrogen-substituted pressure-resistant glass reactor and subjected to polymerization at 80 ° C. for 2 hours with stirring to open the ring. A polymerization reaction solution containing the metathesis polymer a1 was obtained. The polymerization conversion rate was 99.9% or more. The polymer a1 had a weight average molecular weight of 3,200, a number average molecular weight of 1,900, and a molecular weight distribution of 1.68.

  Next, 0.1 part of bis (tricyclohexylphosphine) ethoxymethylene ruthenium dichloride as a hydrogenation catalyst was added to the polymerization reaction solution, and hydrogen was dissolved at a pressure of 4 MPa for 5 hours to proceed the hydrogenation reaction. 1 part was added, hydrogen was dissolved at 150 ° C. under a pressure of 4 MPa for 3 hours while stirring in an autoclave. Subsequently, the solution was taken out and filtered through a fluororesin filter having a pore size of 0.2 μm to separate the activated carbon to obtain 476 parts of a hydrogenation reaction solution containing a hydride a2 of the ring-opening metathesis polymer a1. Filtration could be performed without any delay. The hydrogenation reaction solution containing the hydride a2 obtained here had a solid content concentration of 20.6%, and the yield of the hydride a2 was 98.1 parts. The obtained hydride a2 had a weight average molecular weight of 4,430, a number average molecular weight of 2,570, and a molecular weight distribution of 1.72. The hydrogenation rate was 99.9%.

  The obtained hydrogenation reaction solution of hydride a2 was concentrated with a rotary evaporator, the solid content concentration was adjusted to 35%, and a solution of hydride a3 (a cyclic olefin polymer having a carboxyl group as a protic polar group) was prepared. Obtained. There was no change in yield, hydride weight average molecular weight, number average molecular weight, and molecular weight distribution before and after concentration.

[Example 1]
Resin (A) (hydride a3 obtained in Production Example 1) 100 parts by weight (in terms of solid content), silicone surfactant [manufactured by Shin-Etsu Chemical Co., Ltd., KP341 (trade name)] 0.05 part by weight and solvent (B) (diethylene glycol ethyl methyl ether) was added in an amount of the solvent (B) so that the solid content concentration would be 24%, and the mixture was mixed and stirred to obtain a mixture solution. The mixture became a homogeneous solution within 5 minutes. This solution was filtered through a polytetrafluoroethylene filter having a pore diameter of 0.45 μm to prepare a resin composition a4.

A 200 nm-thick chromium film to be a gate electrode was formed on a glass substrate (Corning, product name Corning 1737) by a sputtering method. Next, in order to pattern the chromium film to form a gate electrode, a positive photoresist (ZPP-1800U3 manufactured by Nippon Zeon Co., Ltd.) used as an etching mask is applied onto the chromium film by a spin coating method, and a hot plate is formed. A 1.5 μm resist film was formed by removing the solvent. Next, an exposure process and a development process were performed, and the resist film was patterned. Next, the chrome film was patterned by wet etching using diammonium cerium nitrate as an etchant to form a gate electrode. Next, the resist film was removed using a stripping solution of a mixed solution of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO) (MEA / DMSO = 7/3).
Next, a 450-nm-thick silicon nitride film serving as a gate insulating film covering the gate electrode, a 250-nm-thick a-Si layer (amorphous silicon layer) serving as a semiconductor layer, and a 50-nm-thick n + Si layer serving as an impurity-added semiconductor layer, respectively. It formed in order by CVD method. Next, in order to pattern the semiconductor layer and the impurity-doped semiconductor layer in an island shape, a positive photoresist (ZPP-1800U3 manufactured by Nippon Zeon Co., Ltd.) used as an etching mask is applied on the impurity-doped semiconductor layer by spin coating. Then, a 1.5 μm resist film was formed by removing the solvent using a hot plate. Next, the resist film was patterned through an exposure process and a development process. Next, the impurity-added semiconductor layer and the semiconductor layer were patterned in an island shape by dry etching. Next, the resist film was removed with a stripping solution of a mixed solution (MEA / DMSO = 7/3) of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO). Next, a 200 nm thick chromium film serving as a source / drain electrode was formed on the gate insulating film and the doped semiconductor layer by a sputtering method. Next, in order to form the source electrode and the drain electrode by patterning the source / drain electrode, a positive photoresist (ZPP-1800U3 manufactured by Nippon Zeon Co., Ltd.) used as an etching mask is spin coated on the source / drain electrode. And a 1.5 μm resist film was formed by removing the solvent using a hot plate. Next, the resist film was patterned through an exposure process and a development process. Subsequently, the source / drain electrodes were patterned by wet etching using diammonium cerium nitrate as an etching solution. Next, dry etching was performed on the n + Si layer using sulfur hexafluoride gas using the photoresist used for patterning the source / drain electrodes. Next, the resist film was removed using a stripping solution of a mixed solution of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO) (MEA / DMSO = 7/3). Next, the gate electrode side end portion of the impurity-added semiconductor layer in the region where the source electrode and the source electrode are present is immersed in a 0.5% hydrofluoric acid solution at 25 ° C. for 3 minutes by passing through the above-described steps, The oxide film on the surface of the semiconductor layer in the channel region formed between the drain electrode and the impurity-added semiconductor layer in the region where the drain electrode exists and the end on the gate electrode side was removed. Next, the substrate having been subjected to the above steps was rinsed with ultrapure water for 30 seconds, and the ultrapure water adhering at the time of rinsing was removed from the substrate surface using nitrogen. Next, the resin composition a4 to be a passivation film containing an organic material is applied onto the substrate that has undergone the above steps by a spin coat method, and is heated and dried (prebaked) at 90 ° C. for 2 minutes using a hot plate. A resin film having a thickness of 2.5 μm was formed. Subsequently, it heated at 230 degreeC for 60 minute (s). As a result, a thin film transistor having an organic passivation film formed thereon was obtained.
Next, characteristics of the obtained thin film transistor were evaluated. The results are shown in Table 1.

[Example 2]
In Example 1, using a diammonium cerium nitrate etching solution and patterning the source / drain electrodes by wet etching, and then using the photoresist used for patterning the source / drain electrodes, the n + Si layer Is dry-etched using sulfur hexafluoride gas, and then the resist film is removed using a stripping solution of a mixed solution of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO) (MEA / DMSO = 7/3) And the step of removing the oxide film on the surface of the semiconductor layer using a 0.5% hydrofluoric acid solution, and the source / drain by wet etching using diammonium cerium nitrate as an etchant. Pattern the electrode and then apply the resist film to the monoethanol (MEA) and dimethyl sulfoxide (DMSO) mixed solution (MEA / DMSO = 7/3) was removed using a stripping solution, and then the substrate was removed from a room temperature nitric acid aqueous solution (61% nitric acid aqueous solution) and hydrofluoric acid (50% Wet etching is performed by immersing in a mixed solution (aqueous solution of hydrogen fluoride) (a solution in which nitric acid and hydrofluoric acid are mixed at a volume ratio of 100: 0.5) for 5 seconds. At the same time, a thin film transistor was fabricated and evaluated in the same manner as in Example 1 except that the process was changed to the step of removing the oxide film on the semiconductor layer surface. The results are shown in Table 1.

Example 3
In Example 1, as the resin composition, the resin composition a5 prepared by adding 10 parts by weight of phthalic acid as the acidic compound (C) to the resin composition a4 to adjust the solid content concentration to 24% is used. A thin film transistor was prepared and evaluated in the same manner as in Example 1 except that an organic passivation film was formed. The results are shown in Table 1.

Example 4
In Example 3, as a resin composition, a hydrocarbyloxy group or a hydroxy group having one atom selected from a silicon atom, a titanium atom, an aluminum atom, and a zirconium atom in the resin composition a5 and bonded to the atom. Organic passivation using resin composition a6 prepared by adding 10 parts by weight of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as the compound (D) having a group to adjust the solid content concentration to 24% A thin film transistor was prepared and evaluated in the same manner as in Example 3 except that a film was formed. The results are shown in Table 1.

[Comparative Example 1]
In Example 1, a thin film transistor was prepared and evaluated in the same manner as in Example 1 except that the passivation film was changed to a silicon nitride film (SiNx film) formed by CVD using silane gas and ammonium gas as raw materials. It was. The results are shown in Table 1.

[Comparative Example 2]
In Example 1, a thin film transistor was prepared and evaluated in the same manner as in Example 1 except that the step of removing the oxide film using hydrofluoric acid was not performed. The results are shown in Table 1.

  Whether or not the oxide film was removed was confirmed by performing surface analysis on the substrate before and after the hydrofluoric acid treatment using an X-ray photoelectron spectrometer (ESCA). Note that the measurement was performed using a portion having a sufficient area for performing surface analysis in the measurement sample. In the examples and comparative examples, it was confirmed from the surface analysis that the substrate subjected to the step of removing the oxide film surely had the oxide film removed.

Moreover, in the reliability evaluation of the thin film transistor of each Example and Comparative Example, all the measurement samples immediately after the production had a good ON / OFF ratio of 10 ⁶ or more.

  From the results shown in Table 1, the thin film transistor that had been subjected to the process of removing the oxide film was very reliable without deterioration of the characteristics even in a harsh atmosphere. In addition, a thin film transistor substrate using a passivation film containing an organic material can be easily manufactured without complicated processes than those using a passivation film made of an inorganic film. Furthermore, a thin film transistor substrate using a passivation film containing an organic material has high transparency.

  When the thin film transistor manufactured in the example is used, it is excellent in reliability, can be manufactured simply and efficiently, and a bright display device can be obtained.

Claims (11)

Forming a gate electrode, a gate insulating film, a semiconductor layer, and source / drain electrodes on a substrate;
Forming a channel region;
Removing the oxide film on the surface of the semiconductor layer in the channel region;
And a step of forming a passivation film containing an organic material after the step of removing the oxide film. Forming a gate electrode on the substrate;
Forming a gate insulating film covering the gate electrode;
Forming a semiconductor layer on the gate insulating film;
Forming a source electrode and a drain electrode on the semiconductor layer;
Forming a channel region that is a region exposing the semiconductor layer between the source electrode and the drain electrode;
Removing an oxide film formed on the surface of the semiconductor layer in the channel region;
Forming an organic passivation film comprising an organic material so as to cover at least the source electrode, the drain electrode, and the channel region formed on the substrate;
Method of manufacturing a thin film tiger Njisuta comprising.   3. The method for manufacturing a thin film transistor according to claim 1, wherein the step of forming the channel region is a step of forming the channel region by wet etching.   The method for producing a thin film transistor according to claim 1, wherein the step of removing the oxide film uses a solution containing hydrofluoric acid.   4. The method of manufacturing a thin film transistor according to claim 3, wherein the step of forming the channel region by wet etching uses a solution containing hydrofluoric acid.   The method for producing a thin film transistor according to claim 1, wherein the passivation film is a film formed of a resin composition containing a resin (A) and an organic solvent (B).   The method for producing a thin film transistor according to claim 6, wherein the resin composition further contains a compound (C) having an acidic group.   The resin composition further comprises a compound (D) having one atom selected from a silicon atom, a titanium atom, an aluminum atom and a zirconium atom, and having a hydrocarbyloxy group or a hydroxy group bonded to the atom, The method for producing a thin film transistor according to claim 6 or 7, wherein the thin film transistor is contained.   The production of a thin film transistor according to any one of claims 6 to 8, wherein the resin (A) contains at least one selected from the group consisting of a cyclic olefin resin, an acrylic resin, a cardo resin, a polysiloxane resin and a polyimide resin. Method.   A thin film transistor obtained by the production method according to claim 1.   A display device comprising the thin film transistor according to claim 10.

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