JP5182287B2 - Active matrix substrate and manufacturing method thereof - Google Patents

Description

  The present invention relates to an active matrix substrate and a manufacturing method thereof.

  The active matrix substrate is a substrate in which pixel electrodes are arranged through thin film transistors (TFTs) at intersections of a plurality of gate signal lines and source signal lines arranged orthogonal to each other on the substrate. Such a substrate is used in an active matrix type flat display device. In an active matrix type flat display device, each display pixel is individually controlled by a TFT (switching element), so that crosstalk is less likely to occur than in a passive matrix type flat display device, which is suitable for high definition and large capacity. Yes.

  FIG. 6 is an explanatory diagram of an example of a conductor circuit on a conventional active matrix substrate. A TFT 14 as a switching element is arranged at the intersection of the gate signal line 12 and the source signal line 13 arranged orthogonally on the substrate. The amount of current flowing from the source electrode 16 to the drain electrode 17 changes according to the voltage applied to the gate electrode 15, and this change is transmitted to the pixel electrode 18 via the contact hole.

In a conventional active matrix substrate, a passivation film made of silicon nitride or the like is formed on the surface of an array substrate on which TFTs are formed by sputtering, vapor deposition, or CVD, and the surface is flattened by an interlayer insulating film. In many cases, the pixel electrode connected to the drain electrode of the TFT through the contact hole is provided on the insulating film. For example, Patent Document 1 discloses an active matrix substrate having a protective layer (passivation film) made of SiN _X or SiO ₂ and a planarization layer (interlayer insulating film) made of benzocyclobutene.

On the other hand, Patent Document 2 discloses a first organic interlayer insulating film made of a siloxane resin that directly covers a source electrode, a source wiring, a drain electrode, and a back channel between a pixel electrode and a wiring, and a first made of an acrylic resin. An active matrix substrate is disclosed in which two organic interlayer insulating films are formed and the lower organic interlayer insulating film is in direct contact with the channel portion of the TFT.
JP-A-10-96963 JP-A-11-307778

However, in the active matrix substrates described in these patent documents, although TFTs operate normally immediately after production, there is a problem that TFT characteristics deteriorate when used for a long time under wet heat.
Accordingly, an object of the present invention is to provide an active matrix substrate and a method for manufacturing the active matrix substrate that can stably manufacture TFT operations even when used for a long time under humid heat.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an adhesive layer made of a silane coupling agent and a protic polarity on a substrate surface on which a conductor circuit including a thin film transistor is formed. It has been found that the above problems can be solved by sequentially laminating an organic protective film made of a crosslinked product of a cyclic olefin polymer having a group to produce an active matrix substrate, and has completed the present invention.
That is, the present invention
[1] An active matrix substrate in which a conductor circuit including a thin film transistor is formed on a substrate, and an adhesive layer made of a silane coupling agent and a proton on the surface of the substrate on which the conductor circuit is formed an organic protective layer comprising a crosslinked product of the cyclic olefin polymer having a sex polar group, Ri Na by sequentially laminating an active matrix substrate in which a surface of the adhesion agent layer is silylated,
[2] The active matrix substrate according to [1], wherein the adhesive layer is made of a liquid silane coupling agent,
[3] The active matrix substrate according to [1] or [2], wherein the silane coupling agent has an epoxy group,
[4] A method for producing an active matrix substrate according to [1],
(1) A step of forming an adhesive layer made of a silane coupling agent on the substrate surface on which the conductor circuit is formed,
(1 ′) a step of silylating the surface of the adhesive layer by bringing the surface of the base material on which the adhesive layer is formed in the step (1) into contact with a silylating agent;
(2) Next, the process of forming the resin film which consists of a radiation sensitive resin composition containing the cyclic olefin type polymer which has a protic polar group on the adhesive agent layer silylated at the process ( 1 ' ). And (3) a step of crosslinking the resin film formed in step (2) to form an organic protective film,
A method of manufacturing an active matrix substrate having
[5] In the step (1), a liquid silane coupling agent is applied or printed on the surface of the base material on which the conductor circuit is formed, or the base material is dipped in the liquid silane coupling agent and then pulled up. The method for producing an active matrix substrate according to [4], wherein the adhesive layer is formed by heating and drying.
[6] The method for producing an active matrix substrate according to [4] or [5], wherein the step (2) is performed by a wet method.
[7] The method for producing an active matrix substrate according to any one of [4] to [6], wherein the radiation-sensitive resin composition further comprises a crosslinking agent, a radiation-sensitive compound, and a solvent. And a flat display device comprising the active matrix substrate according to any one of [8 ] [ 1] to [3],
Is to provide.

In the active matrix substrate of the present invention, the TFT can operate stably in a long-time use under wet heat. According to this substrate, an active matrix type flat display device having a long life, low power consumption and excellent high contrast can be obtained.
Moreover, according to the manufacturing method of the active matrix substrate of the present invention, the active matrix substrate can be efficiently manufactured by a simple operation.

It is the typical top view (1a) of 1 pixel unit of the one aspect | mode of the active matrix substrate of this invention, and the fragmentary sectional view (1b) containing a TFT part. 1 is a plan view of one embodiment of an active matrix liquid crystal display device that can be manufactured using an active matrix substrate of the present invention. FIG. 3 is an XY cross-sectional view of the active matrix liquid crystal display device of FIG. 2. The typical structural example of the organic EL element in the organic EL display apparatus of this invention is shown. It is explanatory drawing of an example of the circuit on the active matrix board | substrate of this invention used for an active matrix type organic electroluminescent display apparatus. It is explanatory drawing of an example of the circuit on the conventional active matrix board | substrate.

Explanation of symbols

1 Base Material 2 Gate Signal Line 3 Source Signal Line 4 Thin Film Transistor (TFT)
5 Gate electrode 6 Source electrode 7 Drain electrode 8 Adhesive layer 9 Organic protective film 10 Contact hole 11 Pixel electrode 12 Gate signal line 13 Source signal line 14 Thin film transistor (TFT)
DESCRIPTION OF SYMBOLS 15 Gate electrode 16 Source electrode 17 Drain electrode 18 Pixel electrode 101 Active matrix substrate 102 Color filter substrate 103 Seal material 105 Electrode pattern 108 Input terminal 110 Liquid crystal layer 111 Alignment film 201 Thin film transistor (TFT)
202 Pixel electrode 203 Gate signal line 204 Source signal line 206 Counter electrode 207 Color filter layer 208 Black matrix 301 Active matrix substrate 302 Luminescent material layer 303 Upper electrode layer (cathode)
304 Sealing film 401 Scan electrode 402 Thin film transistor (TFT)
403 Data electrode 404 Capacitor 405 Thin film transistor (TFT)
406 Organic EL device

The active matrix substrate of the present invention has an organic protective layer composed of an adhesive layer made of a silane coupling agent and a crosslinked product of a cyclic olefin polymer having a protic polar group on the surface of a base material on which a conductor circuit is formed. Films are sequentially laminated.
FIG. 1 is a schematic plan view (1a) of one pixel unit and a partial cross-sectional view (1b) including a TFT portion of one embodiment of the active matrix substrate of the present invention. In this embodiment, the gate signal line 2 and the source signal line 3 are arranged orthogonally on the surface of the substrate 1, and the TFT 4 is arranged at the intersection to form a conductor circuit. The TFT 4 has a gate electrode 5, a source electrode 6 and a drain electrode 7. An adhesive layer 8 made of a silane coupling agent is formed on the surface of the substrate 1 on which the conductor circuit including the TFT 4 is formed. On the adhesive layer 8, an organic protective film 9 made of a crosslinked product of a cyclic olefin polymer having a protic polar group is provided. The electrode 11 is connected. In this embodiment, one TFT is provided per pixel unit, but two or more TFTs may be formed as desired.

  Each component of the active matrix substrate of the present invention, that is, a base material, a conductor signal forming component such as a gate signal line, a source signal line and a TFT, and a pixel electrode are described in, for example, Patent Documents 1 and 2. The conventional active matrix substrate is similar to that of the conventional active matrix substrate, and is formed using the materials described in these known documents.

In the active matrix substrate of the present invention, the adhesive layer made of a silane coupling agent is usually formed on all or part of the substrate surface on which the conductor circuit is formed. As long as the effect of the present invention is not inhibited, a film made of a known material may exist between the base material and the adhesive layer. The thickness of the adhesive layer is not particularly limited, but is usually 0.1 to 50 nm, preferably 1 to 10 nm.
The adhesive agent layer only needs to be made of a silane coupling agent, and the property of the silane coupling agent to be used is not particularly limited, but from the viewpoint of forming the adhesive agent layer with a uniform thickness on the active matrix substrate surface, It is preferably formed using a liquid silane coupling agent, that is, a solution of a silane coupling agent using an organic solvent and / or water as a solvent. The liquid silane coupling agent will be described later.

As the silane coupling agent, usually, a silane compound having at least one active group (reactive organic functional group) selected from the group consisting of a vinyl group, an acrylic group, an epoxy group, an amino group, a mercapto group, and an alkoxy group is preferable. Used for.
Examples of the silane coupling agent used in the present invention include vinylsilanes such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyl-tri (β-methoxyethoxy) silane; γ-methacryloxypropyltrimethoxy Acrylic silanes such as silane; Epoxy silanes such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltri Aminosilanes such as ethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N- (dimethoxymethylsilylpropyl) ethylenediamine, N- (trimethoxysilylpropyl) ethylenediamine; γ-mercaptopropi Mercaptosilanes such as trimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyldimethoxy (methyl) silane, γ-mercaptopropyldiethoxy (methyl) silane; alkoxysilanes; And alkoxysilane partial hydrolysis products such as oligomers having an O—Si—O bond in the molecule, obtained by partial hydrolysis. The degree of polymerization of the oligomer is preferably about 2 to 10. Such a hydrolysis product is obtained by adding a predetermined amount of acid or alkali to an alcohol solution of 0.1 to 10% by weight of alkoxysilane, or a mixed solution of water and alcohol, and optionally at 10 to 50 ° C. It can be obtained by heating for about 1 to 60 minutes. Here, methanol, ethanol or isopropyl alcohol is preferably used as the alcohol.
These silane coupling agents can be used alone or in admixture of two or more.
Especially, since it is excellent in the reactivity with the cyclic olefin polymer which has a protic polar group used for formation of an organic protective film, as a silane coupling agent, what has an epoxy group is preferable, Usually, epoxy silanes Are preferably used.

In the active matrix substrate of the present invention, the surface of the substrate on which the adhesive layer is formed is further silylated from the viewpoint of further improving the stability of TFT operation when used for a long time under wet heat. It may be. Silylation is usually performed on the entire surface of the substrate on which the adhesive layer is formed.
In the present specification, silylation means that protons present on the surface of an object to be silylated such as a substrate on which an adhesive layer is formed are substituted with silyl groups.
There is no particular limitation on the silyl group used for silylation of the substrate surface on which the adhesive layer is formed. For example, dimethylsilyl group, trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, t-butyldimethylsilyl group, t -A butyl diphenylsilyl group, a triphenylsilyl group, etc. can be mentioned. Among these, a trimethylsilyl group can be preferably used.

  In the active matrix substrate of the present invention, the organic protective film made of a crosslinked product of a cyclic olefin polymer having a protic polar group is usually laminated on all or part of an adhesive layer made of a silane coupling agent. . As long as expression of the effect of the present invention is not inhibited, a film made of a known material may exist between the adhesive layer and the organic protective film. In this invention, the thickness of an organic protective film is 0.1-100 micrometers normally, Preferably it is 0.5-50 micrometers, More preferably, it is 0.5-30 micrometers.

In the cyclic olefin polymer having a protic polar group used in the present invention, the protic polar group means an atomic group in which a hydrogen atom is directly bonded to an atom other than a carbon atom. Here, the atoms other than carbon atoms are preferably atoms belonging to Groups 15 and 16 of the periodic table, more preferably atoms belonging to the first and second periods of Groups 15 and 16 of the periodic table, and more preferably Is an oxygen atom, a nitrogen atom and a sulfur atom, particularly preferably an oxygen atom.
Specific examples of the protic polar group include polar groups having an oxygen atom such as carboxy group (hydroxycarbonyl group), sulfonic acid group, phosphoric acid group, hydroxyl group; primary amino group, secondary amino group, A polar group having a nitrogen atom such as a primary 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 contained in the cyclic olefin polymer having a protic polar group is not particularly limited, and different types of protic polar groups may be contained.

In the present invention, the cyclic olefin polymer is a homopolymer or copolymer of a cyclic olefin monomer having a cyclic structure (alicyclic ring or aromatic ring) and a carbon-carbon double bond. The cyclic olefin polymer may have a monomer unit other than the cyclic olefin monomer. The ratio of the cyclic olefin monomer unit in the total structural unit of the cyclic olefin polymer is usually 30 to 100% by weight, preferably 50 to 100% by weight, and more preferably 70 to 100% by weight.
In the present invention, 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 unit. It is desirable that they are combined.
In the cyclic olefin polymer having a protic polar group used in the present invention, the ratio between the monomer unit having a protic polar group and the other monomer unit (monomer unit having a protic polar group) / Monomer units other than this) are generally in the range of 100/0 to 10/90, preferably 90/10 to 20/80, more preferably 80/20 to 30/70, in weight ratio. Selected.

The cyclic olefin polymer having a protic polar group used in the present invention may be composed only of the cyclic olefin monomer (a) having a protic polar group, but usually has a protic polar group. In addition to the cyclic olefin monomer (a), as a monomer copolymerizable with the cyclic olefin monomer (a) having a protic polar group, the cyclic olefin monomer having a polar group other than the protic polar group It is preferable to prepare by arbitrarily using (b), a cyclic olefin monomer (c) having no polar group, and a monomer (d) other than the cyclic olefin. These monomers are hereinafter simply referred to as monomers (a) to (d), respectively.
In the present invention, it is more preferable to use the monomer (a) and the monomer (b) and / or the monomer (c), and the monomer (a) and the monomer ( More preferably, b) is used.

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-exo-6-endo-dihydroxycarbonylbicyclo [2.2.1] hept-2-ene, 8 -Hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-exo-9-endo-dihydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . Carboxy group-containing cyclic olefins such as ^{17, 10} ] dodec-3-ene; 5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5- (4-hydroxy Phenyl) bicyclo [2.2.1] hept-2-ene, 8- (4-hydroxyphenyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (4-hydroxyphenyl) tetracyclo [4.4.0.1 ^2,5 . Hydroxy group-containing cyclic olefins such as ^{17, 10} ] dodec-3-ene, and the like, among which carboxy group-containing cyclic olefins are preferable. These cyclic olefin monomers 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 include ester groups (referred to generically as alkoxycarbonyl groups and aryloxycarbonyl groups), N-substituted imide groups, epoxy groups, halogen atoms, cyano groups, carbonyloxycarbonyls. Group (acid anhydride residue of dicarboxylic acid), alkoxy group, carbonyl group, tertiary amino group, sulfone group, halogen atom, acryloyl group and the like. 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.
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, 8-acetoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.

Examples of the cyclic olefin having an N-substituted imide group include N- (4-phenyl)-(5-norbornene-2,3-dicarboximide).
Examples of the cyclic olefin having a cyano group include 8-cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5-cyanobicyclo [2.2.1] hept-2-ene, and the like.
Examples of the cyclic olefin having a halogen atom include 8-chlorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-chlorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.
These cyclic olefin monomers having polar groups other than protic polar groups may be used alone or in combination of two or more.

Specific examples of the monomer (c) include bicyclo [2.2.1] hept-2-ene (common name: 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 [4.3.0.1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene) , tetracyclo ^{[8.4.0.1 11,14.} 0 ^3,7 ] pentadeca-3,5,7,12,11-pentaene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dec-3-ene (common name: tetracyclododecene), 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene, cyclopentene, cyclopentadiene, 1,4-methano -1,4,4a, 5,10,10a hexa hydro anthracene, 8-phenyl - tetracyclo [4.4. 0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), pentacyclo [7.4.0.1 ^{3 , 6} . 1 ^10,13 . 0 ^2,7] pentadeca-4,11-diene, pentacyclo [9.2.1.1 ^4,7. 0 ^2,10 . 0 ^3,8 ] pentadeca-5,12-diene and the like. These cyclic olefin monomers having no polar group can be used alone or in combination of two or more.

  A typical example of the monomer (d) is 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. These monomers other than cyclic olefins can be used alone or in combination of two or more.

  The cyclic olefin polymer having a protic polar group used in the present invention is usually obtained by polymerizing the monomer (a). If necessary, the obtained polymer may be further hydrogenated. A hydrogenated polymer is also included in the cyclic olefin polymer used in the present invention. In the polymerization, the monomer (a) and a monomer copolymerizable with the monomer (a) [monomer (b), (c) or (d)] are optionally co-polymerized. Polymerization may be performed.

In addition, the cyclic olefin polymer having a protic polar group used in the present invention is obtained by introducing a protic polar group into the cyclic olefin polymer having no protic polar group using a known modifier A. If desired, it can also be obtained by a method of hydrogenation. Hydrogenation may be performed on the polymer before introduction of the protic polar group.
As the modifier A, 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 acid and cinnamic acid; allyl alcohol, methyl vinyl methanol, crotyl alcohol, methallyl alcohol, 1-phenylethen-1-ol, 2-propen-1-ol, 3-butene- 1-ol, 3-buten-2-ol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2- Such as methyl-3-buten-1-ol, 4-penten-1-ol, 4-methyl-4-penten-1-ol, 2-hexen-1-ol, etc. It sat alcohol; and the like.
The modification reaction of the cyclic olefin polymer using the modifier A may be carried out in accordance with a conventional method, and is usually performed in the presence of a radical generator.

The polymerization method of each monomer may be in accordance with a conventional method, for example, a 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, Ziegler type homogeneous catalysts, noble metal complex catalysts, supported noble metal catalysts and the like can be used. Among these hydrogenation catalysts, side reactions such as functional group modification do not occur, and noble metal complex catalysts such as rhodium and ruthenium can be used because carbon-carbon unsaturated bonds in the polymer can be selectively hydrogenated. A nitrogen-containing heterocyclic carbene compound or a ruthenium catalyst coordinated with a phosphine having a high electron donating property is particularly preferable.

  In the present invention, as the cyclic olefin polymer having a protic polar group, those having a structural unit represented by the formula (I) as shown below are particularly preferred, and represented by the formula (I): Those having a structural unit represented by formula (II) and a structural unit represented by formula (II) are more preferred. The structural unit represented by formula (I) and the structural unit represented by formula (II) are both cyclic olefin monomer units.

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

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

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

In the general formula (II), R ^{5 to} R ⁸ are formed together with two carbon atoms to which they are bonded together to form an oxygen atom or a nitrogen atom which may have a substituent. Examples of the heterocyclic structure include an epoxy structure. In addition, as the 5-membered heterocyclic structure formed by including R ^{5 to} R ⁸ together with two carbon atoms to which they are bonded, and optionally having a substituent, including an oxygen atom or a nitrogen atom, Examples thereof include a dicarboxylic anhydride structure [—C (O) —O—C (O) —] and a dicarboximide structure [—C (O) —N—C (O) —]. Examples of the substituent for the oxygen atom or nitrogen atom include a phenyl group, a naphthyl group, and an anthracenyl group.

  The weight average molecular weight (Mw) of the cyclic olefin polymer having a protic polar group used in the present invention is usually 1,000 to 1,000,000, preferably 1,500 to 100,000, more preferably. Is in the range of 2,000 to 10,000. The molecular weight distribution of the cyclic olefin polymer 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. Further, the iodine value of the cyclic olefin polymer containing a protic polar group is usually 200 or less, preferably 50 or less, more preferably 10 or less. When the iodine value is in this range, the heat resistance is particularly excellent and suitable.

  The organic protective film in the present invention is formed by further crosslinking a resin film made of a cyclic olefin-based polymer having a protic polar group as described above. Excellent process compatibility.

The active matrix substrate of the present invention can be manufactured, for example, according to a known method described in Patent Documents 1 and 2, but (1) a silane cup on the surface of a substrate on which a conductor circuit is formed. Forming an adhesive layer comprising a ring agent;
(2) forming a resin film made of a radiation-sensitive resin composition containing a cyclic olefin polymer having a protic polar group on the adhesive layer formed in step (1); and (3 And a step of forming an organic protective film by crosslinking the resin film formed in the step (2).

(Process 1)
In step (1) of the method for producing an active matrix substrate of the present invention, an adhesive layer made of a silane coupling agent is formed on the surface of the base material on which the conductor circuit is formed.
As the silane coupling agent used for forming the adhesive layer, a liquid silane coupling agent is suitable. The liquid silane coupling agent can be prepared by dissolving one or more silane coupling agents in an organic solvent and / or water. The content of the silane coupling agent in the liquid silane coupling agent is usually 0.01 to 5% by weight, preferably 0.05 to 0.5% by weight.
The organic solvent used for the preparation of the liquid silane coupling agent is not particularly limited. For example, alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as methyl isobutyl ketone, methyl ethyl ketone, acetone and cyclohexanone; diethyl ether, dimethyl ether, And ethers such as tetrahydrofuran, dioxane, ethylene glycol, and ethylene glycol monobutyl ether; esters such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; These solvents can be used alone or in combination of two or more.
Among them, a liquid silane coupling agent obtained by dissolving an epoxy group-containing silane coupling agent in an organic solvent and / or water, preferably an organic solvent, more preferably a mixture of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate is The composition for forming an adhesive layer of an active matrix substrate of the present invention is very useful.
The ratio of propylene glycol monomethyl ether to propylene glycol monomethyl ether acetate is preferably 99/1 to 50/50 by weight ratio (propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate).

  There is no particular limitation on the method for forming an adhesive layer made of a silane coupling agent on the substrate surface on which the conductor circuit is formed, but the substrate surface on which the conductor circuit is formed using a liquid silane coupling agent It is efficient and preferable to apply or print a liquid silane coupling agent on top of it, or to immerse the substrate in the liquid silane coupling agent and pull it up, and then heat and dry to form the adhesive layer.

  Examples of a method for applying the liquid silane coupling agent on the surface of the substrate on which the conductor circuit is formed include an application method used for forming an organic protective film described later.

  Examples of the method for printing the liquid silane coupling agent on the surface of the substrate on which the conductor circuit is formed include a screen printing method using a screen printer as described below. That is, the surface of the base material on which the conductor circuit is formed is covered with a mask having a predetermined pattern of openings, and a liquid silane coupling agent is put into a squeegee portion installed in a screen printer. Next, the liquid silane coupling agent is filled in the opening of the masking member by moving the squeegee and moving the mask over the mask while applying pressure to the liquid silane coupling agent (filling step). Next, the mask is removed. Thus, a liquid silane coupling agent pattern is formed on the surface of the substrate. Thereby, the thin film which consists of a silane coupling agent partially on the surface of a base material is formed.

  As a method of immersing and pulling up a substrate on which a conductor circuit is formed in a liquid silane coupling agent, for example, a method of immersing and pulling up a substrate in a liquid silane coupling agent at 10 to 50 ° C. for about 1 to 60 minutes Is mentioned.

  By the above method, a thin film of a liquid silane coupling agent is formed on all or part of the substrate surface. Then, if desired, after drying in an inert gas stream such as nitrogen, the adhesive layer is further formed by heating and drying at 50 to 150 ° C. for about 1 to 30 minutes in the same stream. If desired, it may be further cured (post-cured) at a high temperature of 200 to 350 ° C.

In the method for producing an active matrix substrate of the present invention, a base material on which an adhesive layer is formed after forming an adhesive layer on the surface of the base material on which the conductor circuit is formed (hereinafter referred to as “adhesive layer forming base material”). The step of contacting the surface of silylation with a silylating agent [step (1 ′)] may be added as appropriate.
Examples of the silylating agent used for silylating the adhesive layer-forming substrate include hexamethyldisilazane, dimethyldichlorosilane, trimethylchlorosilane, N-trimethylsilylacetamide, N, O-bis (trimethylsilyl) acetamide, N-methyl-N-trimethylsilylacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, N-trimethylsilyldimethylamine, N-trimethylsilyldiethylamine, N, O-bis (trimethylsilyl) trifluoroacetamide, N-trimethylsilylimidazole, tetramethyl Disilazane, t-butyldimethylchlorosilane, N-methyl-N- (t-butyldimethylsilyl) trifluoroacetamide, dichloromethyltetramethyldisilazane, chlorome Didimethylchlorosilane, bromomethyldimethylchlorosilane, octadecyltrichlorosilane, N, N′-bis (trimethylsilyl) urea, N-trimethylsilyl-N, N′-diphenylurea, N, O-bis (trimethylsilyl) carbamate, N, O— Bis (trimethylsilyl) sulfamate, trimethylsilyltrifluoromethanesulfonic acid and the like can be mentioned. Among these, hexamethyldisilazane can be particularly preferably used because it is excellent in the effect of preventing moisture from entering the active matrix substrate of the present invention and the effect of improving the adhesion at the interface. These silylating agents can be used alone or in admixture of two or more.

  There is no restriction | limiting in particular in the method of making an adhesion agent layer formation base-material surface contact with a silylating agent, and silylating. For example, the adhesive layer forming base material is carried away from the hot plate into the silylation processing chamber equipped with a hot plate, the silylating agent vapor is introduced under reduced pressure in the processing chamber, and the hot plate is heated to form the base material. The silylating agent vapor is uniformly diffused at 50 ° C. or less, the introduction and exhaustion of the silylating agent vapor is stopped, and the substrate is brought into contact with the hot plate at a temperature of 80 to 90 ° C. And a method of stopping the silylation reaction by substituting the vapor of the silylating agent with nitrogen. Silylation proceeds while contact is made between the surface of the base material for forming the adhesive layer and the vapor of the silylating agent. In that case, the concentration of the silylating agent is preferably 0.1 to 5% by volume. According to the said method, the whole adhesive agent layer formation base-material surface can be silylated. The contact may usually be performed for 1 minute or longer.

(Process 2)
Next, a resin film is formed using a radiation sensitive resin composition containing a cyclic olefin polymer having a protic polar group on the adhesive layer formed in the step (1).

Although it does not specifically limit as a radiation sensitive resin composition, Usually, what contains a crosslinking agent, a radiation sensitive compound, and a solvent other than the cyclic olefin polymer which has a protic polar group normally Are preferably used.
Preferable examples of the cyclic olefin polymer having a protic polar group include a cyclic olefin polymer having a structural unit represented by the formula (I) and a structural unit represented by the formula (II). Preferred examples of the crosslinking agent include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, polyphenol type epoxy having two or more, more preferably three or more epoxy groups. Examples thereof include polyfunctional epoxy compounds such as resins, cycloaliphatic epoxy resins, aliphatic glycidyl ethers, and epoxy acrylate polymers.
Preferred examples of radiation sensitive compounds (compounds that can cause a chemical reaction upon irradiation with radiation such as ultraviolet rays and electron beams) include 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-naphthoquinonediazide- Quinonediazidesulfonic acid halides such as 4-sulfonic acid chloride and 1,2-benzoquinonediazide-5-sulfonic acid chloride, and 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane , 4,4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and other photoacid generators such as ester compounds with compounds having a phenolic hydroxyl group Is mentioned.
In the present invention, the radiation-sensitive resin composition may contain, for example, colloidal silica as inorganic fine particles in addition to other components commonly used in known radiation-sensitive resin compositions. Examples of the solvent include a monoalkylene glycol solvent; a polyalkylene glycol solvent; a monoalkylene glycol alkyl ester solvent; a polyalkylene glycol alkyl ester solvent; a monoalkylene glycol diester solvent; a polyalkylene glycol diester solvent;
The radiation-sensitive resin composition used in the present invention is usually 1 to 200 parts by weight of a crosslinking agent and usually 5 to 5 parts of a radiation-sensitive compound with respect to 100 parts by weight of a cyclic olefin polymer having a protic polar group. Contains ~ 50 parts by weight.

So far, as an example, a positive type was described as an example of the radiation sensitive resin composition, but the radiation sensitive resin composition may be a negative type. The radiation sensitive resin composition can be produced according to a known method. The solid content concentration of the radiation-sensitive resin composition can be appropriately selected in consideration of the necessary thickness of the organic protective film, the coating method, etc., but is preferably 5 to 40% by weight.
The prepared radiation-sensitive resin composition is usually preferably applied after removing foreign substances using a filter having a pore size of 0.1 to 5 μm.

  When a radiation-sensitive resin composition in a solution state is used, the resin film forming operation is simple and the production efficiency is excellent. Therefore, step (2) is usually performed by a wet method. In the wet method, a solution is obtained by dissolving an organic polymer constituting a resin film and other components to be blended as required in a solvent, and the solution is cast to remove the solvent to form a resin film. Is the method. Specific examples of the method include a coating method and a film lamination method.

The coating method is a method in which the radiation-sensitive resin composition is coated on the adhesive layer on the surface of the substrate on which the conductor circuit is formed, and then dried by heating to remove the solvent. Examples of the method for applying the radiation-sensitive resin composition on the adhesive layer 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. Can be mentioned. The heating and drying temperature can be appropriately selected according to the type and blending ratio of each component, but is usually 30 to 150 ° C. The heating and drying time can be appropriately selected according to the type and mixing ratio of each component, but is usually 0.5 to 90 minutes.
In addition, the film laminating method applies a radiation-sensitive resin composition onto a B-stage film-forming substrate such as a resin film or a metal film, and then removes the solvent by heat drying to obtain a B-stage film. In this method, the B-stage film is laminated on the adhesive layer. The heating and drying conditions can be appropriately selected according to the type and mixing ratio of each component, but the heating temperature is usually 30 to 150 ° C., and the heating time is usually 0.5 to 90 minutes. . Film lamination can be performed using a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator or the like.

  In this way, a resin film made of the radiation sensitive resin composition is formed on the adhesive layer. Usually, the resin film is irradiated with actinic radiation to form a latent image pattern in the resin film, and then the latent image pattern is exposed and patterned by bringing a developer into contact therewith. By such an operation, a hole pattern to be a contact hole can be easily formed.

  The actinic radiation is not particularly limited as long as it activates the radiation-sensitive compound and can change the alkali solubility of the radiation-sensitive resin composition. For example, the active radiation has a single wavelength such as ultraviolet ray, g-line or i-line. UV rays, KrF excimer laser light, ArF excimer laser light, etc .; particle beams such as electron beams; As a method of selectively irradiating these actinic radiations in a pattern to form a latent image pattern, for example, using a reduction projection exposure apparatus or the like, ultraviolet rays, g-line, i-line, KrF excimer laser light, ArF excimer laser light For example, a method of irradiating a light beam such as through a mask pattern, a method of drawing with a particle beam such as an electron beam, and the like. After irradiation with actinic radiation, the organic protective film may be heat-treated at 60 to 130 ° C. for 1 to 2 minutes, if desired.

  An aqueous solution of an alkaline compound can be used as a developer for developing and exposing the latent image pattern formed by actinic radiation. As the alkaline compound, any of inorganic compounds such as sodium hydroxide and potassium hydroxide; organic compounds such as tetramethylammonium hydroxide and tetraethylammonium hydroxide can be used. As an aqueous medium of the alkaline aqueous solution, water and a water-soluble organic solvent such as methanol and ethanol can be used. The alkaline aqueous solution may have a surfactant added in an appropriate amount.

Examples of the method for bringing the developer into contact with the resin film having the latent image pattern include a paddle method, a spray method, and a dipping method. The development temperature is usually 5 to 55 ° C., and the development time is usually 30 to 180 seconds.
After forming the patterned resin film in this way, if necessary, the substrate is rinsed with a rinsing liquid such as ultrapure water in order to remove development residues on the substrate, the back surface of the substrate, and the edge of the substrate. May be used for rinsing.
Furthermore, if desired, in order to deactivate the radiation-sensitive compound, the entire surface of the substrate having the patterned resin film may be irradiated with active radiation, or the resin film may be heated at the same time or after irradiation. Examples of the heating method include a method of heating the substrate in a hot plate or an oven. The heating temperature is usually 100 to 300 ° C.

(Process 3)
In step (3), the resin film formed from the radiation-sensitive resin composition formed in step (2) is crosslinked to form an organic protective film.
The method of crosslinking the resin film formed on the substrate can be appropriately selected according to the type of the crosslinking agent used, but is usually performed by heating. Heating can be performed using, for example, a hot plate or an oven. The heating temperature is usually preferably 180 to 250 ° C., and the heating time can be appropriately selected according to the size, thickness, equipment used, etc. of the resin film. For example, when a hot plate is used, it is usually preferably 5 to 60 minutes, and when an oven is used, it is usually preferably 30 to 90 minutes.
If desired, heating can be performed in an inert gas atmosphere such as nitrogen, argon, helium, neon, xenon, krypton, or the like.
As described above, an organic protective film made of a crosslinked product of a cyclic olefin polymer having a protic polar group is laminated on the adhesive layer made of a silane coupling agent on the surface of the substrate on which the conductor circuit is formed. Will be.

  If a hole pattern to be a contact hole is formed in the organic protective film, a pixel electrode made of ITO (Indium Tin Oxide) is formed on the organic protective film by sputtering, for example, and patterned. The drain electrode of the TFT and the pixel electrode are connected through the contact hole. At this time, an electrode pattern is simultaneously formed by ITO constituting the pixel electrode. Thereafter, an alignment film is formed and an alignment process such as a rubbing process is performed to obtain a desired active matrix substrate.

  The flat display device of the present invention comprises the active matrix substrate of the present invention. The flat display device of the present invention is a flat display device with long life, low power consumption, and high contrast. Specific examples of the flat display device include an active matrix liquid crystal display device and an active matrix organic electroluminescence (EL) display device.

  An active matrix type liquid crystal display device is composed of a pair of substrates disposed opposite to each other with a liquid crystal material, a film-like liquid crystal or the like sandwiched therebetween, and one of the pair of substrates is the active matrix of the present invention. This is a flat display device composed of a substrate. Examples of the substrate disposed opposite to the active matrix substrate (hereinafter referred to as “counter substrate”) include a color filter substrate, a microlens substrate, and the like.

  Further, as a modification of the liquid crystal display device composed of an active matrix substrate and a color filter substrate, a mode in which a color filter material layer is directly provided on a pixel electrode in an active matrix substrate and a color filter is not provided on a counter substrate. Examples include a liquid crystal display device and a liquid crystal display device in which a pixel electrode of an active matrix substrate is formed using a conductive color filter material and a color filter is not provided on a counter substrate.

FIG. 2 is a plan view of an embodiment of an active matrix liquid crystal display device that can be manufactured using the active matrix substrate of the present invention, and FIG. 3 is a cross-sectional view taken along the line XY. In this embodiment, the active matrix substrate 101 including the pixel electrode 202 and the color filter substrate 102 including the counter electrode 206 are disposed to face each other with the liquid crystal layer 110 interposed therebetween. The opposite portion is a pixel. A sealing material 103 is provided on the outer periphery of the display area composed of pixels, and an electrode pattern 105 exists in an area between the display area and the sealing material 103. In the color filter substrate 102, a counter electrode 206 is provided on a color filter layer 207 having a black matrix 208, and an alignment film 111 is provided thereon. On the substrate, the active matrix substrate 101 is provided with a gate signal line 203 for supplying a gate signal for driving the TFT 201 as a switching element and a source signal line 204 for supplying a source signal to the TFT 201 orthogonal to each other. A TFT 201 is provided in the vicinity of the intersection of both signal lines, and a pixel electrode 202 is provided thereon so as to partially overlap both signal lines via the organic protective film 104. Note that the pixel electrode 202 and the drain electrode of the TFT 201 are connected in a contact hole (not shown) of the organic protective film 104. An alignment film 111 is disposed on the organic protective film 104 so as to face the organic protective film 104.
On the other hand, the gate signal line 203 and the source signal line 204 are formed so as to extend beyond the frame region, and the gate signal line 203 is connected to the gate signal line 203 for driving the TFT 201 via the input terminal 108 provided in the outer terminal region. A signal voltage is input, and a signal voltage of display data can be input to the source signal line 204. The electrode pattern 105 is formed on the outer peripheral region of the organic protective film 104 and further extended to the terminal region, and a signal from the drive circuit is input. The above liquid crystal display device can be manufactured according to a known method, for example, a method described in JP-A-2003-005215.

In the active matrix organic EL display device, each pixel formed in a matrix arrangement on the active matrix substrate of the present invention includes at least one organic EL element and at least two TFTs for driving the organic EL element. It is what has.
The organic EL element is not particularly limited. For example, a structure in which a hole transport layer and a light emitting material layer are formed between a hole injection electrode serving as an anode and an electron injection electrode serving as a cathode (SH-A structure). A structure in which a light emitting material layer and an electron transport layer are formed between a hole injection electrode and an electron injection electrode (SH-B structure), or between a hole injection electrode and an electron injection electrode And those having a structure (DH structure) in which a hole transport layer, a light emitting material layer, and an electron transport layer are formed. Regardless of the structure, the organic EL element has a light emitting material layer and a hole (or electron) transport layer in which holes injected from a hole injection electrode (anode) and electrons injected from an electron injection electrode (cathode) are used. It operates on the principle that light is emitted by recombination within the interface and the light emitting material layer.

  FIG. 4 shows a typical configuration example of the organic EL element in the organic EL display device of the present invention. The organic EL element shown in FIG. 4 includes an active matrix substrate (including a pixel electrode as a lower electrode layer (anode)) 301, a light emitting material layer 302, and an upper electrode layer (cathode) 303. A sealing film 304 is provided as the outermost layer. As a configuration for one pixel of the organic EL display device, normally, at least two TFTs for driving the EL element are required for at least one organic EL element, that is, a driving transistor and a writing transistor. In the configuration example of FIG. 4, both transistors are omitted. These transistors are present in the active matrix substrate of the present invention.

  In the active matrix substrate of the present invention, the pixel electrode as the anode and the drain electrode of the TFT are connected. FIG. 5 shows an example of a circuit on the active matrix substrate of the present invention. In this circuit, the TFT 402 (write transistor) is turned on by a voltage sequentially applied to the scan electrode 401 connected to the horizontal drive circuit. The amount of charge corresponding to the display signal from the data electrode 403 connected to the vertical drive circuit is accumulated in the capacitor 404. The TFT 405 (driving transistor) operates according to the amount of electric charge accumulated in the capacitor 404, current is supplied to the organic EL element 406, and the organic EL element is turned on. This lighting state is maintained until a voltage is applied to the scan electrode 401. The above organic EL display device can be manufactured according to a known method, for example, a method described in JP-A-2002-333846.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[Production Example 1] (Production of cyclic olefin polymer having a protic polar group)
8-carboxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene 60 parts by weight, N-phenyl- (5-norbornene-2,3-dicarboximide) 40 parts by weight, 1,5-hexadiene 2.8 parts by weight, (1,3 -Dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride 0.05 parts by weight and diethylene glycol ethyl methyl ether 400 parts by weight were charged into a nitrogen-substituted pressure-resistant glass reactor and stirred at 80 ° C. A polymerization reaction was carried out for 2 hours to obtain a polymerization reaction solution containing the ring-opening metathesis polymer 1A. The polymerization conversion rate was 99.9% or more. The polymer 1A had a weight average molecular weight of 3,200, a number average molecular weight of 1,900, and a molecular weight distribution of 1.68.

Next, 0.1 part by weight of bis (tricyclohexylphosphine) ethoxymethylene ruthenium dichloride as a hydrogenation catalyst is added to the polymerization reaction solution, hydrogen is dissolved at a pressure of 4 MPa for 5 hours, and the hydrogenation reaction proceeds. 1 part by weight of powder was added, and the mixture was placed in an autoclave and stirred, and hydrogen was dissolved at 150 ° C. under a pressure of 4 MPa for 3 hours. Next, the solution was taken out and filtered through a fluororesin filter having a pore size of 0.2 μm to separate the activated carbon to obtain 476 parts by weight of a hydrogenation reaction solution containing the hydride 1B of the ring-opening metathesis polymer 1A. Filtration could be performed without any delay. The hydrogenation reaction solution containing hydride 1B obtained here had a solid content concentration of 20.6% by weight, and the yield of hydride 1B was 98.1 parts by weight. The obtained hydride 1B had a weight average molecular weight of 4,430, a number average molecular weight of 2,570, and a molecular weight distribution of 1.72. The hydrogenation rate was 99.9%.
The weight average molecular weight and number average molecular weight of the polymer and hydride were determined as polyisoprene equivalent molecular weight using gel permeation chromatography (product name: HLC-8020, manufactured by Tosoh Corporation) using tetrahydrofuran as an eluent. The hydrogenation rate was calculated | required as a ratio with respect to the carbon-carbon double bond mole number before hydrogenation of the hydrogenated carbon-carbon double bond mole number by < ¹ > H-NMR spectrum.

  The obtained hydrogenation reaction solution of hydride 1B was concentrated with a rotary evaporator, the solid content concentration was adjusted to 35% by weight, and hydride 1C (cyclic olefin polymer having a carboxy group as a protic polar group) was obtained. A solution was obtained. There was no change in yield, weight average molecular weight, number average molecular weight and molecular weight distribution of hydride before and after concentration.

  In Examples and Comparative Examples described below, predetermined characteristics were evaluated according to the following evaluation methods.

(Adhesion evaluation)
The adhesion of the resin film to the surface of the glass base material on which the adhesive layer was formed was evaluated by a pull-off method of JISK5600-5-7 using a substrate for adhesion evaluation described later. The evaluation was performed twice immediately after the substrate was manufactured (initial value) and after the substrate was maintained in an atmosphere of 90% RH at 60 ° C. for 400 hours. The evaluation criteria are as follows.
〔Evaluation criteria〕
○ Adhesion force exceeds 6 MPa.
Δ: Adhesive strength is in the range of 6-3 MPa.
X The adhesion is less than 3 MPa.

(Evaluation of TFT drive characteristics)
A voltage of 20 V is applied between the source electrode and the drain electrode of the active matrix substrate, the voltage applied to the gate electrode is changed to -20 to 30 V, and the current flowing between the source electrode and the drain electrode is changed to a manual prober. Measurement was performed using a semiconductor parameter analyzer (product name: 4156C, manufactured by Agilent). The evaluation was performed twice immediately after the substrate was manufactured (initial value) and after the substrate was maintained in an atmosphere of 90% RH at 60 ° C. for 400 hours. The measurement was performed at room temperature (25 ° C.).

[Example 1]
100 parts by weight of a solution of hydride 1C obtained in Production Example 1 (solid content 35% by weight), polyfunctional epoxy compound having an alicyclic structure as a crosslinking agent [manufactured by Daicel Chemical Industries, EHPE3150 (product name), molecular weight About 2,700, epoxy group number 15] 25 parts by weight, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane (1 mol) and 1,2- 25 parts by weight of a condensate with naphthoquinonediazide-5-sulfonic acid chloride (2.5 mol), (1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2, 3,4-butanetetracarboxylate 5 parts by weight, γ-glycidoxypropyltrimethoxysilane 5 parts by weight as an adhesion aid and silicone surfactant [Shin-Etsu Chemical Co., Ltd. Company Ltd., KP341 (product name)] 0.05 parts by weight, was mixed and stirred with further addition of 92 parts by weight of diethylene glycol ethyl methyl ether and N- methyl-2-pyrrolidone 8 parts by weight. The mixture became a homogeneous solution within 5 minutes. This solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.45 μm to prepare a radiation sensitive resin composition 1D.

(Preparation of adhesion evaluation substrate)
A silicon nitride film having a thickness of 450 nm was formed on a glass substrate using a CVD apparatus.
Thereafter, the glass substrate was mixed with 1 part by weight of 3-glycidoxytrimethoxysilane and a solvent having a mixing ratio (volume ratio) of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 70/30 (hereinafter referred to as “solvent X”). .) Was immersed in a liquid silane coupling agent obtained by mixing 20 parts by weight, 79 parts by weight of ultrapure water and 2 parts by weight of acetic acid at 23 ° C. for 10 minutes. After immersion, the glass substrate was blown with nitrogen and then heated in an oven at 120 ° C. for 30 minutes. After heating, the glass substrate was immersed in ultrapure water for 1 minute for rinsing.
The above-mentioned radiation sensitive composition 1D is spin-coated on a glass base material on which a silicon nitride film and an adhesive layer are formed, and then prebaked at 90 ° C. for 2 minutes using a hot plate, to give a resin having a film thickness of 2.5 μm. A film was formed. After film formation, ultraviolet rays having a light intensity at 365 nm of 5 mW / cm ² were irradiated for 120 seconds. Further, post-baking treatment was performed using an oven at 230 ° C. for 60 minutes to produce an adhesion evaluation substrate.
(Evaluation of adhesion)
Table 2 shows the evaluation results of the adhesion immediately after the substrate production (initial value) and after maintaining the substrate in an atmosphere of 90% RH at 60 ° C. for 400 hours.

(Preparation of array substrate for active matrix substrate)
On a glass substrate [Corning, Corning 1737 (product name)], a sputtering apparatus is used to form chromium with a film thickness of 200 nm, patterning is performed by photolithography, and a gate electrode, a gate signal line, and a gate terminal Part was formed. Next, the CVD apparatus covers the gate electrode and the gate wiring, the silicon nitride film serving as the gate insulating film is 450 nm thick, the a-Si layer serving as the semiconductor layer is 250 nm thick, and n + Si serving as the ohmic contact layer The layer was continuously formed with a thickness of 50 nm, and the n + Si layer and the a-Si layer were patterned into an island shape. Further, chromium is formed to a thickness of 200 nm on the gate insulating film and the n + Si layer by a sputtering apparatus, and a source electrode, a source signal line, a drain electrode, and a data terminal portion are formed by photolithography, and the source electrode and the drain electrode are formed. An unnecessary n + Si layer between the layers was removed to form a back channel, and an array substrate in which TFTs were formed on a glass substrate was obtained.
(Production of active matrix substrate)
Thereafter, 1 part by weight of 3-glycidoxytrimethoxysilane, 20 parts by weight of solvent X having a mixing ratio of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 70/30, 79 parts by weight of ultrapure water, and 2 parts of acetic acid The array substrate was immersed in a liquid silane coupling agent obtained by mixing at a weight part ratio at 23 ° C. for 10 minutes. After immersion, the array substrate was blown with nitrogen and then heated in an oven at 120 ° C. for 30 minutes. After heating, the array substrate was immersed in ultrapure water for 1 minute for rinsing.
The obtained array substrate on which the silane coupling agent layer is formed is put into a silylation treatment chamber equipped with a hot plate, and after degassing the inside of the treatment chamber, hexamethyldisilazane (HMDS) is introduced as a silylation agent. Then, the vapor of hexamethyldisilazane was uniformly diffused into the processing chamber at 50 ° C., and then the array substrate was heated to 85 ° C. with a hot plate to effect silylation for 1 minute. Next, hexamethyldisilazane in the processing chamber was replaced with nitrogen and cooled to room temperature to obtain an array substrate whose surface was silylated (trimethylsilylated).
The obtained array substrate having a silylated surface was spin-coated with the above radiation sensitive resin composition 1D and then pre-baked at 90 ° C. for 2 minutes using a hot plate to obtain a resin film having a thickness of 1.2 μm. Formed. 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 25 ° C. using a 0.4 wt% tetramethylammonium hydroxide aqueous solution, the contact hole pattern was formed by rinsing with ultrapure water for 30 seconds. A good pattern of 90% or more was obtained. After development, ultraviolet rays were irradiated at 5 mW / cm ² for 120 seconds. Furthermore, the organic protective film (1) was formed by performing post-baking (crosslinking treatment) by heating at 230 ° C. for 60 minutes using an oven.
The array substrate on which the organic protective film (1) is formed is transferred to a vacuum chamber, a mixed gas of argon and oxygen (volume ratio: 100: 4) is used as a sputtering gas, the pressure is 0.3 Pa, the DC output is 400 W, and the DC is passed through the mask. By sputtering, an In—Sn—O-based amorphous transparent conductive layer (pixel electrode) having a thickness of 200 nm was formed so as to be in contact with the drain electrode, whereby an active matrix substrate (1) was obtained.
With respect to the obtained active matrix substrate (1), the current flowing between the source electrode and the drain electrode was measured according to the above “Evaluation of TFT driving characteristics”, and the leakage current was obtained. The leakage current was 1 × 10 ⁻¹³ A / cm ² and the threshold voltage was 4V.
Further, the active matrix substrate (1) was maintained in an atmosphere of 60 ° C. and 90% RH for 400 hours, and then the same measurement was performed. The leakage current was 8 × 10 ⁻¹³ A / cm ² , the threshold voltage was 3 V, and there was no substantial change.

[Examples 2 to 4, Reference Examples 1 to 3 ]
The adhesive evaluation substrate and the active matrix substrate were prepared in the same manner as in Example 1 except that the composition of the liquid silane coupling agent, the adhesive layer forming method, and the presence or absence of silylation by HMDS were changed as shown in Table 1. The same evaluation as in Example 1 was performed. The results are shown in Table 2.
In Table 1, “spin” in the terms “adhesive layer forming method” and “rinsing method” means that the liquid silane coupling agent is placed on the substrate while rotating the glass substrate or the active matrix substrate, respectively. An operation of applying and an operation of rinsing the substrate with ultrapure water.

[Comparative Examples 1-2]
An adhesive evaluation substrate and an active matrix substrate were prepared in the same manner as in Example 1 except that the composition of the liquid silane coupling agent, the method of forming the adhesive layer, and the organic protective film material were changed as shown in Table 1. The same evaluation as in Example 1 was performed. The results are shown in Table 2.

(1) Production of acrylic resin 20 parts by weight of styrene, 25 parts by weight of butyl methacrylate, 25 parts by weight of 2-ethylhexyl acrylate, 30 parts by weight of methacrylic acid, 0.5 part by weight of 2,2-azobisisobutyronitrile and propylene glycol 300 parts by weight of monomethyl ether acetate was heated at 80 ° C. for 5 hours with stirring in a nitrogen stream. The obtained resin solution was concentrated by a rotary evaporator to obtain an acrylic resin solution having a solid content concentration of 35% by weight.

(2) Production of polyimide resin Under a dry air stream, 9.61 g (0.048 mol) of 4,4′-diaminodiphenyl ether and bis [4- (4-aminophenoxy) phenyl] in a 1-liter four-necked flask 17.3 g (0.04 mol) of sulfone and 1.24 g (0.005 mol) of bis (3-aminopropyl) tetramethyldisiloxane were dissolved in 102.5 g of cyclopentanone at 40 ° C. Thereafter, pyromellitic anhydride 6.54 g (0.03 mol), 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride 9.67 g (0.03 mol), 3,3 ′, 4, 12.41 g (0.04 mol) of 4′-diphenyl ether tetracarboxylic dianhydride and 30 g of cyclopentanone were added and reacted at 50 ° C. for 3 hours. This solution was concentrated by a rotary evaporator to obtain a polyimide resin solution having a solid concentration of 35% by weight.

From the results of Table 2, Examples 1 to 1 are formed by laminating an adhesive layer composed of a silane coupling agent and an organic protective film composed of a crosslinked cyclic olefin polymer having a carboxy group on a glass substrate. 4 and the active matrix substrates of Reference Examples 1 to 3 , unlike the active matrix substrate of Comparative Example 1 in which the organic protective film forming material is changed to acrylic resin and Comparative Example 2 in which the material is changed to polyimide resin, has excellent adhesion, It can be seen that the TFT can operate stably without increasing the leakage current and the threshold voltage even if it is maintained in the atmosphere of 60% at 90% RH under the wet heat condition of 400 hours. From the comparison between Example 1 and Reference Example 1 , Example 2 and Reference Example 2, and Example 3 and Reference Example 3 , it was found that the surface of the adhesive layer was silylated after formation of the adhesive layer. It can be seen that the stability is improved.

Claims (8)

An active matrix substrate in which a conductor circuit including a thin film transistor is formed on a base material, and an adhesive layer made of a silane coupling agent and a protic polar group on the surface of the base material on which the conductor circuit is formed an active matrix substrate in which an organic protection film made of a crosslinked product of the cyclic olefin polymer, Ri name by sequentially laminating, surface of the adhesion agent layer is silylated with. The active matrix substrate according to claim 1 , wherein the adhesive layer is made of a liquid silane coupling agent. The active matrix substrate according to claim 1 , wherein the silane coupling agent has an epoxy group. A method of manufacturing an active matrix substrate according to claim 1 ,
(1) A step of forming an adhesive layer made of a silane coupling agent on the substrate surface on which the conductor circuit is formed,
(1 ′) a step of silylating the surface of the adhesive layer by bringing the surface of the base material on which the adhesive layer is formed in the step (1) into contact with a silylating agent;
(2) Next, the process of forming the resin film which consists of a radiation sensitive resin composition containing the cyclic olefin type polymer which has a protic polar group on the adhesive agent layer silylated at the process ( 1 ' ). And (3) a step of crosslinking the resin film formed in step (2) to form an organic protective film,
A method for manufacturing an active matrix substrate. In step (1), a liquid silane coupling agent is applied or printed on the surface of the substrate on which the conductor circuit is formed, or the substrate is dipped in the liquid silane coupling agent and pulled up, and then dried by heating. The manufacturing method of the active-matrix board | substrate of Claim 4 which forms an adhesive agent layer by doing. The method for manufacturing an active matrix substrate according to claim 4 or 5 , wherein the step (2) is performed by a wet method. The method for producing an active matrix substrate according to any one of claims 4 to 6 , wherein the radiation-sensitive resin composition further comprises a crosslinking agent, a radiation-sensitive compound, and a solvent. A flat display device comprising the active matrix substrate according to claim 1 .

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