JPWO2011108533A1 - Manufacturing method of semiconductor element substrate - Google Patents

Abstract

A step of performing plasma treatment on a semiconductor element surface or a semiconductor layer surface included in the semiconductor element; and a step of forming a passivation film made of an organic material on the semiconductor element surface or the semiconductor layer surface subjected to the plasma treatment; Comprising.

Description

  The present invention relates to a method for manufacturing a semiconductor element substrate in which a hydrogen plasma treatment is performed on a semiconductor layer and a passivation film using an organic material is formed.

  Semiconductor element substrates are widely used in electronic products. For example, 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 element such as an active matrix liquid crystal display or an organic EL.

  In a conventional thin film transistor, a passivation film made of a silicon nitride film (SiNx film) is formed on the surface of a semiconductor element or a semiconductor layer included in the semiconductor element by sputtering, vapor deposition, or CVD. Further, the surface of the semiconductor layer has been treated for the purpose of improving the adhesion between the SiNx film and the semiconductor layer made of a-Si.

  For example, Patent Document 1 discloses that after a hydrogen plasma treatment is performed on a semiconductor layer, a nitrogen plasma treatment is performed to improve the adhesion between the semiconductor layer and the passivation film and reduce the off-leakage current. Yes. However, in the case of using an inorganic material for the passivation film as in Patent Document 1, it is necessary to form the film in a state where the material is plasmatized or ionized in a vacuum, the equipment becomes large-scale, and the operation is complicated. There was a problem of becoming.

  In this case, if the nitrogen plasma treatment is not performed after the hydrogen plasma treatment, there arises a problem that etching failure occurs. Therefore, it is necessary to perform the nitrogen plasma treatment after the hydrogen plasma treatment. Further, when an inorganic material is used for the passivation film, a resist is required when forming the contact hole, so that the number of processes is increased as compared with the case where an organic material is used for the passivation film. That is, a step of applying a resist and a step of removing the resist after dry etching are required. On the other hand, when an organic material is used for the passivation film, it is not necessary to use a resist, so that the number of steps can be reduced. When an inorganic material is used, the thickness of a passivation film that can be formed on a specific layer is limited, and it is difficult to form a flat passivation film.

  Non-Patent Document 1 discloses that an initial off-leakage current can be suppressed by performing plasma treatment using SiNx for a passivation film. However, when this semiconductor element substrate is used as an active matrix substrate of a display element, high reliability is required. That is, not only the initial off-leakage current but also the use of the device under severe conditions is required to suppress the off-leakage current and improve the TFT life.

  In addition, since SiNx has a function of terminating dangling bonds (see, for example, Patent Document 2), the plasma processing in Patent Document 1 and Non-Patent Document 1 does not mainly terminate dangling bonds. It is.

JP 2003-37269 A International Publication No. 2009/057444

Pei Ming Chen, Wan Yu Lo, Chuan Sheng Wei, Jing Jie Shih, Chih Hung Shih, Mao Song Chen, Feng Yuan Gen, and Tom Huang, “The effects of back-channel treatment on electrical characteristic of a-Si: H TFT device ”, International Display Workshop '07, p1951-1953

  An object of the present invention is to provide a method of manufacturing a semiconductor element substrate that can manufacture a highly reliable semiconductor element substrate.

  As a result of intensive studies to solve the above-mentioned object, the present inventors have conducted a dangling process by performing plasma treatment on the surface of the semiconductor element or the semiconductor layer included in the semiconductor element in the method of manufacturing a semiconductor element substrate. By forming a passivation film containing an organic material on the surface of the semiconductor element subjected to the plasma treatment or the semiconductor layer surface included in the semiconductor element surface by terminating the ring bond, an increase in off-leakage current can be achieved even under high temperature and high humidity. It was found that the device can be suppressed and is excellent in device reliability.

That is, according to the present invention,
(1) A step of performing plasma treatment on a semiconductor element surface or a semiconductor layer surface included in the semiconductor element, and forming a passivation film made of an organic material on the semiconductor element surface or the semiconductor layer surface subjected to the plasma treatment A process for producing a semiconductor element substrate comprising the steps of:
(2) The method of manufacturing a semiconductor element substrate according to (1), wherein the plasma treatment is a hydrogen plasma treatment,
(3) The semiconductor element or the semiconductor layer is manufactured by a process including a step of forming a gate electrode, a gate insulating film, a semiconductor layer, and a source / drain electrode on a substrate, and a step of forming a channel region. (1) or the method for producing a semiconductor element substrate according to (2), wherein
(4) The method for producing a semiconductor element substrate according to any one of (1) to (3), wherein the organic material is a resin composition containing a resin.
(5) The method for producing a semiconductor element substrate according to any one of (1) to (4), wherein the plasma treatment is performed for 1 to 10 minutes.

  According to the semiconductor element substrate manufacturing method of the present invention, a highly reliable semiconductor element substrate can be manufactured.

It is a figure which shows the process of the manufacturing method of the semiconductor element substrate which concerns on embodiment of this invention. It is a figure which shows the process of the manufacturing method of the semiconductor element substrate which concerns on embodiment of this invention. It is a figure which shows the passivation film which concerns on embodiment of this invention.

  Hereinafter, a method for manufacturing a semiconductor device substrate according to the present invention will be described with reference to the drawings. 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, it is understood that the present invention can be variously replaced, modified and changed within the scope of the technical idea of the present invention described in the claims. It is obvious to those who have

  First, as shown in FIG. 1A, a gate electrode 22 is formed on an insulating substrate 21 such as a glass substrate by a sputtering method. Next, using a photoresist (not shown) as a mask, the gate electrode 22 is patterned by dry etching or wet etching as shown in FIG. Next, as shown in FIG. 1C, a gate insulating film 23, a semiconductor layer 24 made of amorphous silicon, and an impurity-added semiconductor layer 25 are sequentially deposited by CVD. Next, as shown in FIG. 1D, by patterning the semiconductor layer 24 and the impurity-added semiconductor layer 25 by dry etching or wet etching using a photoresist (not shown) as a mask, the semiconductor layer 24 and impurities An island-shaped semiconductor structure composed of the additional semiconductor layer 25 is formed.

(Ohmic layer)
Next, as shown in FIG. 2A, source / drain electrodes 26 are formed by sputtering. Next, using the photoresist (not shown) as a mask, the source / drain electrode 26 is patterned by etching as shown in FIG. 2B to form the source electrode 27 and the 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 a photoresist (not shown) reduced by patterning of the source / drain electrode 26 as a mask. A channel region as shown in FIG. 2C is formed. 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 sandwiched between 31 and the gate electrode side end. In other words, the semiconductor layer in the portion indicated by the arrow between the dotted lines in FIG.

Next, the photoresist (not shown) used for 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 in which N ₂ or the like is mixed, and an ashing process using the generated oxygen radicals or a combination process thereof can be appropriately incorporated.

  Next, hydrogen plasma treatment is performed on the channel region 29 to terminate dangling bonds. The hydrogen plasma treatment is preferably performed for 1 to 10 minutes, and a bias of several hundred W or less, preferably 200 W or less may be applied when performing the hydrogen plasma treatment. In addition, it is preferable to include a step of surface-treating the plasma-treated surface with hydrofluoric acid after the step of performing the plasma treatment because the reliability of the thin film transistor may be further improved.

  Next, a passivation film made of an organic material is formed. 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 formed easily and efficiently, and a coating method is more preferable.

  When a passivation film made of an organic material is formed by a coating method, a highly reliable thin film transistor can be formed in a simple and short process. Moreover, it is preferable to form a film | membrane with the resin composition containing resin and an organic solvent.

  The coating method is a method in which a solvent is removed after a resin composition is coated on a substrate over which a thin film transistor is formed after the step of removing the oxide film on the surface of the semiconductor layer in the channel region. 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 case of a passivation film made of an inorganic material, the film thickness is limited to 200 to 400 nm. Accordingly, as shown in FIG. 3A, the passivation film 32 made of an organic material can be flattened compared to the passivation film 33 made of an inorganic material shown in FIG.

  The passivation film made of an organic material used in the present invention is preferably formed from a resin composition containing a resin (A) and an organic solvent (B).

In the present invention, the resin (A) is not particularly limited. For example, the cyclic olefin resin, acrylic resin, acrylamide resin, polysiloxane, epoxy resin, phenol resin, cardo resin, polyimide, polyamideimide, polycarbonate, polyethylene terephthalate, the following Examples thereof include a resin containing a monomer unit represented by the general formula (1). 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 preferably, the cyclic olefin resin is particularly preferably a cyclic olefin resin having a protic polar group or a resin containing the monomer unit (e) represented by the general formula (1).

(In the above formula (1), R ₁ represents a branched alkyl group having 5 to 16 carbon atoms.)
These resins may be used alone or in combination of two or more.

  A protic 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 an alicyclic structure 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.

As the cyclic olefin resin having a protic polar group in the present invention, a resin having a structural unit represented by the formula (2) as shown below is particularly suitable, and a structure represented by the formula (2). What has a unit and the structural unit represented by Formula (3) is more suitable.

Wherein ^(2), 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 (3), R < ⁵ > -R < ⁸ > is a 3-5 membered heterocyclic ring which contains an oxygen atom or a nitrogen atom as a ring-constituting atom with two carbon atoms with 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 (2), 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 (3), 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 it is a single weight 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 a monomer. A blend or copolymer is preferred.

  Specific examples of the carboxylic acid having an acrylic group include (meth) acrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, glutaconic acid, etc .; specific examples of the carboxylic acid anhydride having an acrylic group include maleic anhydride Acid, citraconic anhydride, etc .; specific examples of epoxy group-containing acrylate compounds include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α-n-butyl acrylic acid Glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6 7-epoxyheptyl; and the like.

  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 copolymerizable monomer other than at least one monomer selected from unsaturated carboxylic acid, unsaturated carboxylic acid anhydride and epoxy group-containing unsaturated compound, and other acrylate monomers or acrylates. It may be a copolymer with the body. Other acrylate monomers include methyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl ( Alkyl (meth) acrylates such as meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, etc. Hydroxyalkyl (meth) acrylates; phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate; Alkoxyalkyl (meth) acrylates such as xylethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxy polyethylene glycol Polyalkylene glycol (meth) acrylates such as (meth) acrylate; cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopenta Dienyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meta Cycloalkyl (meth) acrylates such as acrylate; benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate. 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 (4).

(In formula (4), 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.

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 (5).

R _{9 in} Formula (5) 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 (5) 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 include a phenyl group. N in the formula (5) 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 (5) 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 Enyl) 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 hydrolyzing and partially condensing the above organosilane. A general method can be used for hydrolysis and partial condensation. For example, a solvent, water and, if necessary, a catalyst 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) ) No methane 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-perylenetetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride such as 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, butanetetracarboxylic dianhydride And aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-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 resin containing the monomer unit (e) represented by the general formula (1) used in the present invention is a unit obtained by polymerizing a monomer represented by the following general formula (1) ( It is a cyclic olefin resin comprising e).

(In the above formula (1), R ₁ represents a branched alkyl group having 5 to 16 carbon atoms.)
In the general formula (1), R ₁ is a branched alkyl group having 5 to 16 carbon atoms, for example, 1-methylbutyl group, 2-methylbutyl group, 1-methylpentyl group, 1-ethylbutyl group, 2-methyl. Examples include hexyl group, 2-ethylhexyl group, 4-methylheptyl group, 1-methylnonyl group, 1-methyltridecyl group, 1-methyltetradecyl group and the like. Among these, a branched alkyl group having 6 to 14 carbon atoms is preferable, and a branched alkyl group having 7 to 10 carbon atoms is more preferable because of excellent heat resistance and solubility in an organic solvent. When the carbon number is 4 or less, the solubility in an organic solvent is inferior, when the carbon number is 17 or more, the heat resistance is inferior, and the patterned resin film is melted by heat and the pattern disappears. There is.

  Specific examples of the monomer represented by the general formula (1) include N- (1-methylbutyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N -(2-Methylbutyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methylpentyl) -bicyclo [2.2.1] hept-5 Ene-2,3-dicarboximide, N- (2-methylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-ethylbutyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (2-ethylbutyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide , N- (1-methylhexyl) -bicyclo [2.2.1 Hept-5-ene-2,3-dicarboximide, N- (2-methylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3- Methylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-butylpentyl) -bicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N- (2-butylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methylheptyl) -bicyclo [2 2.1] hept-5-ene-2,3-dicarboximide, N- (2-methylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-methylheptyl) -bicyclo [2. .1] Hept-5-ene-2,3-dicarboximide, N- (4-methylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N -(1-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene -2,3-dicarboximide, N- (3-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-propylpentyl) -bicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximide, N- (2-propylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide N- (1-methyloctyl) -bisic [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (2-methyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-di Carboximide, N- (3-methyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-methyloctyl) -bicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide, N- (1-ethylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2 -Ethylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-ethylheptyl) -bicyclo [2.2.1] hept-5-ene- 2,3-dicarboximide, N- (4-ethylheptyl)- Cyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-propylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-di Carboximide, N- (2-propylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-propylhexyl) -bicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide, N- (1-methylnonyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2- Methylnonyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-methylnonyl) -bicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N- (4-methylnonyl) -Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (5-methylnonyl) -bicyclo [2.2.1] hept-5-ene-2,3-di Carboximide, N- (1-ethyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-ethyloctyl) -bicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide, N- (3-ethyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4 -Ethyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methyldecyl) -bicyclo [2.2.1] hept-5-ene-2 , 3-Dicarboximide, N- (1-methyldodecyl) ) -Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methylundecyl) -bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (1-methyldodecyl) -bicyclo [2.2.1] hept-5-ene 2,3-dicarboximide, N- (1-methyltridecyl) -bicyclo [2. 2.1] hept-5-ene-2,3-dicarboximide, N- (1-methyltetradecyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methylpentadecyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide and the like can be mentioned. These may be used alone or in combination of two or more.

  Although it does not specifically limit as a manufacturing method of the monomer represented by the said General formula (1), For example, it obtains by the amidation reaction of a corresponding amine and 5-norbornene-2,3-dicarboxylic anhydride. be able to. The obtained monomer can be efficiently isolated by separating and purifying the reaction solution of the amidation reaction by a known method.

  The content ratio of the monomer unit (e) represented by the general formula (1) in the resin (A) is preferably 10 to 90 mol% with respect to the total monomer units. When the content ratio of the unit (e) of the monomer represented by the general formula (1) is too small, the solubility of the resin (A) in the organic solvent may be insufficient. There is a possibility that the radiation sensitivity of the resin composition is lowered, or dissolution residue is generated during development.

  In addition, the more preferable range of the content rate of the monomer unit (e) represented by the general formula (1) varies depending on the type of the passivation film constituted by the resin composition used in the present invention. Specifically, when the passivation film is a passivation film formed of a resin composition containing a radiation-sensitive compound and patterned by photolithography, a single amount represented by the above general formula (1) As for the content rate of the unit (e) of a body, it is more preferable that it is 30-60 mol%, and it is especially preferable that it is 40-50 mol%. On the other hand, when the passivation film is a passivation film that is not patterned by photolithography, the content ratio of the monomer unit (e) represented by the general formula (1) is 20 to 80 mol. % Is more preferable, and 30 to 70 mol% is particularly preferable.

  It is preferable that the monomer unit copolymerizable with the monomer represented by the general formula (1) is copolymerized. Examples of the copolymerizable monomer include the above-mentioned cyclic olefin monomer having a protic polar group (a) and polar groups other than the protic polar group excluding the monomer represented by the general formula (1). And a cyclic olefin monomer (b) having no polar group, and a monomer (d) other than a cyclic olefin.

  A ring-opening polymer obtained by ring-opening polymerization of at least one of the monomers represented by the general formula (1) and a copolymerizable monomer used as necessary may be used.

  As the polymerization catalyst, for example, the above-described 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.

  Moreover, you may hydrogenate with respect to the polymer obtained by superposing | polymerizing each monomer using a hydrogenation catalyst. As the hydrogenation catalyst, for example, those generally used for hydrogenation of olefin compounds can be used as described above. 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 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 used by 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. 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 (C) 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 Aliphatic compounds such as 1,3-butanediol, 1,3,4-trimercapto-2-butanol, 3,4-dimercapto-1,2-butanediol, 1,5-dimercapto-3-thiapentane; 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, dimethoxy Benzoic 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 (“terephthalic acid”) Also referred to as “acid”), benzene-1,2,3-tricarboxylic acid, benzene-1,2,4-trica Boronic 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 (Mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5 -Aromatic compounds such as tris (mercaptoethyl) benzene; nicotinic acid, isonicotinic acid, 2-furoic acid, pyrrole-2,3-dicarboxylic acid, pyrrole-2,4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid Acid, pyrrole-3,4-dicarboxylic acid, imidazole-2,4-dicarboxylic acid, imidazole-2,5-dicarboxylic acid, imidazole 5-membered heterocyclic compounds containing nitrogen atoms such as 4,5-dicarboxylic 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, thiazole-4,5-dicarboxylic acid, iso Thiazole-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-dimerca To-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) propion Acid, 3- (5-mercapto-1,2,4-thiadiazol-3-ylthio) succinic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-yl) Thio) succinic acid, 4- (3-mercapto-1,2,4-thiadiazol-5-yl) thiobutanesulfonic acid, 4- (2-mercapto-1,3,4-thiadiazol-5-yl) thiobutane 5-membered heterocyclic compounds containing nitrogen and sulfur atoms such as sulfonic 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-dipropylamino-4,6-dimercapto-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, 2-anilino-4,6-dimercapto-s- 6-membered heterocyclic compounds containing nitrogen atoms such as triazine and 2,4,6-trimercapto-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, thia -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, Limidine-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 1 to 45 parts by weight, preferably 1.5 to 30 parts per 100 parts by weight of the resin (A). Part by weight, more preferably in the range of 2 to 15 parts by weight. 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-styryltrimethoxysilane Run, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltri Ethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- ( Aminoethyl) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 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) acryloxypropyltriethoxysila , 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-ethyl (trimethoxysilylpropoxymethyl) oxetane, 3-ethyl (triethoxysilylpropoxymethyl) oxetane, 3-triethoxysilyl-N- ( 1,3-dimethyl-butylidene) propylamine, trialkoxysilanes such as bis (triethoxysilylpropyl) tetrasulfide, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyl Dimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-pentyldimethoxysilane, di -N-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane , Di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryl Oxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropi In addition to dialkoxysilanes such as methyldimethoxysilane, methyltriacetyloxysilane, dimethyldiacetyloxysilane, trade names X-12-414, KBP-44 (manufactured by Shin-Etsu Chemical Co., Ltd.), 217FLAKE, 220FLAKE, 233FLAKE, z6018 Silicon atom-containing compounds such as Toray Dow Corning Co., Ltd .; (tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, titanium-i-propoxyoctylene glycolate, di -I-propoxy bis (acetylacetonato) titanium, propanedioxytitanium bis (ethylacetoacetate), tri-n-butoxytitanium monostearate, di-i-propoxytitanium distearate, titanium stearate , Di-i-propoxytitanium diisostearate, (2-n-butoxycarbonylbenzoyloxy) tributoxytitanium, di-n-butoxybis (triethanolaminato) titanium, as well as the preneact series (Ajinomoto) Titanium atom-containing compounds such as fine techno)); aluminum atom-containing compounds such as (acetoalkoxyaluminum diisopropylate); (tetranormal propoxyzirconium, tetranormalbutoxyzirconium, zirconium tetraacetylacetonate, zirconium tributoxyacetyl) Acetonate, zirconium monobutoxyacetylacetonate bis (ethyl acetoacetate), zirconium dibutoxybis (ethyl acetoacetate), zirconium tetraacetylacetonate , Zirconium tributoxy system A rate) zirconium atom containing compounds such as, and the like.

  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, polyhexamethylenediamineterephthalamide and polyhexamethyleneisophthalamide; N, N, N ′, N ′, N ″, Melamines such as N ″-(hexaalkoxymethyl) melamine; Glycolurils such as N, N ′, N ″, N ′ ″-(tetraalkoxymethyl) glycoluril; Ethylene glycol di (meth) acrylate Acrylate compound: hexamethylene diisocyanate polyisocyanate 1, 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 And epoxy compounds such as acrylate polymers.

  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 (15-functional alicyclic epoxy resin having a cyclohexane skeleton and a terminal epoxy group, trade name “EHPE3150”, manufactured by Daicel Chemical Industries, Ltd. ), Epoxy-cyclohexene-1,2-dicarboxylate bis (3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic trifunctional epoxy resin, trade name “Epolide GT301”, manufactured by Daicel Chemical Industries), epoxy Butanetetracarboxylate Tetrakis (3-cyclohexenylmethyl) Modified ε-Caprolac Ton (aliphatic cyclic tetrafunctional epoxy resin, trade name “Epolide GT401”, manufactured by Daicel Chemical Industries), 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate (trade name “Celoxide” 2021P ", manufactured by Daicel Chemical Industries, Ltd.) and the like; 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 compound (Epicoat 152, 154, manufactured by Japan Epoxy Resin Co., Ltd.), polyfunctional epoxy compound having a naphthalene skeleton (trade name EXA-4700 , Manufactured by Dainippon Ink Chemical Co., Ltd.) Xyoxy compound (trade name “SR-TMP”, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), polyfunctional 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 (trade name" SR-DGE ", Sakamoto Yakuhin Kogyo Co., Ltd., polyglycerin polyglycidyl ether compound (brand name" SR-4GL ", Sakamoto Yakuhin Kogyo) And epoxy compounds having no alicyclic structure, such as those manufactured by KK).

  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 used in the present invention is usually 0.1 to 200 parts by weight, preferably 1 to 150 parts by weight, more preferably 100 parts by weight of the resin (A). It is in the range of 5 to 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 used in 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 used in 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 10% by weight. 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.

  According to the semiconductor element substrate manufacturing method of the present invention, a highly reliable semiconductor element substrate can be manufactured.

  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. In addition, since a semiconductor element manufactured by the manufacturing method according to the present invention has a flat passivation film, luminance can be improved in a display device. In addition, power consumption can be reduced. In addition, the lifetime of the thin film transistor can be improved.

  In addition, since a passivation film containing an organic material has a low dielectric constant, RC delay can be suppressed.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. “Parts” and “%” in each example 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. A voltage of 10 V was applied between the source electrode and the drain electrode, and the minimum value of the source-drain current when the gate voltage was changed in the range of −10 V to 15 V in increments of 0.2 V was observed as the off-leakage current value. 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 off-leakage current value is measured by the above method every 20 hours up to 100 hours and every 100 hours after exceeding 100 hours, and the time when the off-leakage current value reaches 1.0 × 10 ⁻¹¹ A is measured. Observed as thin film transistor characteristics. According to this analysis, the longer the thin film transistor characteristics, the higher the reliability of the thin film transistor.

(Production Example 1)
N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NEHI) 40 mol% and 8-hydroxycarbonyltetracyclo [4.4.0. 1 ^2,5 . 1 ^7,10 ] Dodeca-3-ene (TCDC) 60 parts by mole monomer mixture 100 parts, 1,5-hexadiene 2 parts, (1,3-dimethylimidazoline-2-ylidene) (tricyclohexylphosphine) A glass pressure-resistant reactor in which 0.02 part of benzylidene ruthenium chloride (synthesized by the method described in Org. Lett., Vol. 1, page 953, 1999) and 400 parts of diethylene glycol methyl ethyl ether were replaced with nitrogen. The polymerization reaction liquid was obtained by charging and stirring at 80 ° C. for 4 hours while stirring. And the obtained polymerization reaction liquid was put into the autoclave, and it stirred at 150 degreeC and the hydrogen pressure of 4 MPa for 5 hours, and obtained the solution of cyclic olefin resin by performing a hydrogenation reaction. The polymerization conversion rate of the cyclic olefin resin in the obtained solution was 99.7%, the weight average molecular weight was 7150, the number average molecular weight was 4690, the molecular weight distribution was 1.52, and the hydrogenation rate was 99.7%.
Next, 2 parts of pyrazine-2,3-dicarboxylic acid as a compound having an acidic group in the solution of the cyclic olefin resin obtained as described above (in an amount such that the cyclic olefin resin in the solution becomes 100 parts), As radiation-sensitive compounds, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2 mol) 30 parts of a condensate (Toyo Gosei Co., Ltd., “TS200”), 30 parts of a methyl ether melamine resin (Cytech Industries, “Cymel 370”) as a crosslinking agent, 3,4-epoxycyclohexenylmethyl- 30 parts of 3 ′, 4′-epoxycyclohexene carboxylate (manufactured by Daicel Chemical Industries, “Celoxide 2021P”), and epoxy 10 parts of butanetetracarboxylic acid tetrakis- (3-cyclohexenylmethyl) modified ε-caprolactone (manufactured by Daicel Chemical Industries, “Epolide GT401”), as an antioxidant, pentaerythritol tetrakis [3- (3,5- 1 part of (di-t-butyl-4-hydroxyphenyl) propionate] (Ciba Specialty Chemicals, "Irganox 1010"), and as a surfactant, a silicone-based interface in a concentration of 300 ppm in the solution An activator (manufactured by Shin-Etsu Silicone, “KP-341”) was added, and 100 parts of diethylene glycol methyl ethyl ether was further added, followed by stirring. After stirring for 30 minutes, the solution was filtered through a polytetrafluoroethylene filter having a pore diameter of 0.45 μm to prepare a resin composition (α) containing a cyclic olefin resin and having radiation sensitivity.

(Production Example 2)
Glass substituted with nitrogen for 20 parts of styrene, 25 parts of butyl methacrylate, 25 parts of 2-ethylhexyl acrylate, 30 parts of methacrylic acid, 0.5 part of 2,2-azobisisobutyronitrile, and 300 parts of propylene glycol monomethyl ether acetate A pressure-resistant reactor was prepared and reacted at 80 ° C. for 4 hours with stirring in a nitrogen stream. Then, the obtained reaction solution was concentrated by a rotary evaporator to obtain an acrylic resin solution with a solid content concentration of 35%. The polymerization conversion rate of the acrylic resin in the obtained solution was 99% or more, the weight average molecular weight was 15000, the number average molecular weight was 6500, and the molecular weight distribution was 2.31.
Next, the solution of the acrylic resin obtained as described above (in an amount such that the acrylic resin in the solution becomes 100 parts) was treated with 3-glycidoxypropyltrimethyl as a compound having a hydrocarbyloxy group bonded to a silicon atom. 10 parts of methoxysilane (manufactured by Toray Dow Corning, “SH-6040”), 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane (1 Mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2 moles) (Toyo Gosei Kogyo Co., Ltd., “TS200”), 30 parts as a crosslinking agent, methyl etherified melamine resin (Cytech Industries) "Cymel 350"), 50 parts, as an antioxidant, pentaerythritol tetrakis [3- (3,5-di-t (Butyl-4-hydroxyphenyl) propionate] (Ciba Specialty Chemicals, "Irganox 1010") 1 part, and as a surfactant, a silicone surfactant in an amount of 300 ppm by weight in the solution (Manufactured by Shin-Etsu Silicone Co., “KP-341”) was added, and 100 parts of propylene glycol monomethyl ether acetate was further added and mixed and stirred. After stirring for 30 minutes, this solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.45 μm to prepare a resin composition (β) containing an acrylic resin and having radiation sensitivity.

Example 1
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, hydrogen plasma treatment was performed for 5 minutes in a state where a bias of 100 W was applied using a hydrogen plasma treatment apparatus (an apparatus in which Dipole Ring Magnet [manufactured by Tokyo Electron Ltd.] was improved so that plasma treatment was possible). 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 (α) to be a passivation film containing an organic material is applied onto the substrate that has undergone the above process by a spin coating method, and is heated and dried (prebaked) at 90 ° C. for 2 minutes using a hot plate. Thus, a resin film having a thickness of 2.5 μm was formed. Next, the resin film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5 mW / cm ² in the air for 40 seconds through a 10 μm × 10 μm hole pattern mask. Next, after developing for 90 seconds at 23 ° C. using a 0.4 wt% tetramethylammonium hydroxide aqueous solution, rinsing with ultrapure water for 30 seconds to form a contact hole pattern, 230 ° C. For 60 minutes (post-bake). Thereby, a thin film transistor in which a patterned organic passivation film was formed was obtained.

(Example 2)
A thin film transistor was obtained in which a patterned organic passivation film was formed by the same method as in Example 1 except that the bias was set to 0 W in the hydrogen plasma treatment.
(Example 3)
A thin film transistor was obtained in which a patterned organic passivation film was formed by the same method as in Example 2 except that the resin composition (β) was used instead of the resin composition (α).

(Comparative Example 1)
A thin film transistor on which a patterned organic passivation film was formed was prepared and evaluated in the same manner as in Example 1 except that the hydrogen plasma treatment was not performed.

(Comparative Example 2)
A thin film transistor was fabricated 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 a CVD method using silane gas and ammonium gas as raw materials.

(Comparative Example 3)
A thin film transistor was fabricated and evaluated in the same manner as in Comparative Example 2 except that the hydrogen plasma treatment was not performed.
(Comparative Example 4)
A thin film transistor on which a patterned organic passivation film was formed was prepared and evaluated in the same manner as in Example 3 except that the hydrogen plasma treatment was not performed.
Table 1 also shows the results of evaluating the following characteristics.

(2) Aperture Ratio The ratio of the area of the portion that allows light to pass except the wiring portion and the transistor portion to the area of the manufactured thin film transistor substrate was determined as the aperture ratio. The higher the aperture ratio, the better the brightness.

(3) Number of Passivation Film Fabrication Steps After Fabrication of TFTs The number of steps required to obtain a thin film transistor having a patterned passivation film after fabrication of the thin film transistors by the steps shown in FIGS. A comparison was made.

  That is, in Examples 1 to 3, six steps of (i) hydrogen plasma treatment, (ii) cleaning, (iii) coating, (iv) exposure, (v) development, and (vi) baking are required. In Comparative Examples 1 and 4, five steps of (i) cleaning, (ii) coating, (iii) exposure, (iv) development, and (v) baking are required. In Comparative Example 2, (i) cleaning, (ii) formation of SiNx film by CVD method, (iii) cleaning, (iv) coating, (v) exposure, (vi) development, (vii) baking, ( viii) Eight steps of dry etching are required. In Comparative Example 3, (i) hydrogen plasma treatment, (ii) cleaning, (iii) formation of SiNx film by CVD method, (iv) cleaning, (v) coating, (vi) exposure, (vii) development (Viii) Nine steps of baking and (ix) dry etching are required.

(4) Relative permittivity and RC delay After the resin composition containing the organic material produced in Production Examples 1 and 2 is applied on a silicon wafer by spin coating, it is heated at 90 ° C. for 2 minutes using a hot plate. Drying (prebaking) was performed to form a resin film having a thickness of 2.5 μm. Subsequently, it heated at 230 degreeC for 60 minute (s), and the test sample which consists of a silicon wafer in which the resin film containing an organic material was formed was obtained.

  Further, a silicon nitride film (SiNx film) formed by a CVD method using silane gas and ammonium gas as raw materials is formed on a silicon wafer, and is heated and dried (prebaked) at 90 ° C. for 2 minutes using a hot plate. A resin film having a thickness of 120 nm was formed. Subsequently, it heated at 230 degreeC for 60 minute (s), and the test sample which consists of a silicon wafer in which the SiNx film | membrane was formed was obtained. Then, using the obtained test sample, the relative dielectric constant of the resin film and the SiNx film was measured at 10 kHz (room temperature) according to JIS C6481. The lower the dielectric constant, the better.

The RC delay was calculated as the RC delay time (DT) by calculating the time required for 97% voltage to reach the end of the data wiring when the input signal was 10 V in 65 inch full high vision.
V (t) = V (1-exp [t / RC])
V: input voltage, t: time, R: resistance of data wiring, C: parasitic capacitance of data wiring

  From the results shown in Table 1, it was found that the thin film transistor using an organic material for the passivation film after hydrogen plasma treatment does not deteriorate in characteristics even in a harsh atmosphere and is very reliable. In addition, the thin film transistor substrate using the passivation film containing an organic material has a smaller number of processes than the one using the passivation film containing SiNx, which is an inorganic material, and can be easily manufactured. Furthermore, the passivation film containing an organic material has a high aperture ratio and thus has excellent luminance, and further has a low relative dielectric constant and can suppress RC delay.

DESCRIPTION OF SYMBOLS 21 ... Substrate, 22 ... Gate electrode, 23 ... Gate insulating film, 24 ... Semiconductor layer, 25 ... Impurity added semiconductor layer, 26 ... Source / drain electrode, 27 ... Source electrode, 28 ... Drain electrode, 29 ... Channel region, 30 ... impurity-doped semiconductor layer in the region where the source electrode exists, 31 ... impurity-added semiconductor layer in the region where the drain electrode exists, 32 ... passivation film containing an organic material, 33 ... passivation film containing an inorganic material

Claims (5)

Performing a plasma treatment on a semiconductor element surface or a semiconductor layer surface included in the semiconductor element;
Forming a passivation film made of an organic material on the surface of the semiconductor element or the surface of the semiconductor layer that has been subjected to the plasma treatment.   2. The method of manufacturing a semiconductor element substrate according to claim 1, wherein the plasma treatment is a hydrogen plasma treatment. The semiconductor element or the semiconductor layer is
Forming a gate electrode, a gate insulating film, a semiconductor layer, and source / drain electrodes on a substrate;
3. The method of manufacturing a semiconductor element substrate according to claim 1, wherein the semiconductor element substrate is manufactured by a process including a step of forming a channel region.   The said organic material is a resin composition containing resin, The manufacturing method of the semiconductor element substrate as described in any one of Claims 1-3 characterized by the above-mentioned.   The said plasma processing is the processing time for 1 to 10 minutes, The manufacturing method of the semiconductor element substrate as described in any one of Claims 1-4 characterized by the above-mentioned.

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