JP5083566B2 - Method for producing transparent cured film using positive photosensitive resin layer for half exposure - Google Patents

Description

The present invention relates to a method for producing a transparent cured film obtained by using a positive photosensitive resin layer.
More specifically, the present invention relates to a method for producing a transparent cured film by exposing two positive photosensitive resin layers having different exposure sensitivities formed on a substrate and finally performing a post-baking step.
In particular, the photosensitive resin layer having the above structure is half-exposed to be applicable to a method for producing a reflection layer, a flat transmission layer, and a contact hole with an arbitrary shape with high accuracy. The present invention relates to application to the manufacture of liquid crystal display elements.

  In general, a thin film transistor (TFT) type liquid crystal display element has a reflection type, a semi-transmission type, a transmission type structure, and the like, and is appropriately selected depending on a device used. Among these, a transflective type capable of high-definition display both indoors and outdoors both day and night is often used. In such a transflective liquid crystal display element, a flattening film is used for the purpose of flattening the TFT and widening the aperture ratio. On such a flattened film, irregular irregularities are produced on the surface in order to provide the light scattering property of the reflecting portion and increase the reflection efficiency. A metal such as aluminum or molybdenum is formed on the irregularities as a reflector and a pixel electrode. On the other hand, a transparent electrode such as ITO is used as a pixel electrode in the transmission part. A contact hole is formed in the planarizing film to make these pixel electrodes conductive with the common electrode.

As a method for producing such irregularities and contact holes, a thick film protrusion is formed on a substrate using a photosensitive material, and a photosensitive material is further applied thereon to flatten the protrusion to some extent for reflection. A method of forming a contact hole after forming the irregularities is often used.
However, in such a method, it is necessary to perform pattern formation using a photosensitive material twice, so that the throughput (production efficiency) of device manufacturing does not increase, and therefore this throughput improvement has been demanded.

Therefore, in recent years, a method of simultaneously producing contact holes and reflection irregularities by applying a photosensitive material and then exposing through a halftone mask (half exposure) has been proposed and adopted.
The photosensitive material used here has excellent process resistance such as heat resistance and solvent resistance, good adhesion to the substrate, and highly accurate patterning under various process conditions according to the purpose of use. In addition, various characteristics such as having a wide process margin capable of forming a film, high sensitivity and high transparency, and little film unevenness after development are required.
Therefore, from the viewpoint of such required characteristics, a photosensitive resin composition containing a naphthoquinonediazide compound has been widely used as the photosensitive material.

  By the way, sensitivity and a process margin are mentioned as important characteristics among the required characteristics of such a photosensitive resin material. The improvement in sensitivity makes it possible to greatly reduce the production time in industrial production of display elements and the like. In the current situation where the demand for liquid crystal displays is significantly increasing, the sensitivity is This is one of the most important properties required for this type of photosensitive resin material. In addition, the process margin is important for forming a highly accurate reflective layer as designed. In recent years, with the enlargement of the substrate, a wide exposure margin and development margin are required to improve the yield. .

  However, the conventional photosensitive resin material containing the above-mentioned naphthoquinone diazide compound has not been sufficiently satisfactory in terms of sensitivity. Although it is possible to improve the sensitivity by increasing the solubility of the polymer in the material in an alkaline developer, this method has limitations, and dissolution of unexposed areas also occurs, resulting in a decrease in the remaining film ratio. However, this has the disadvantage that it causes film unevenness for large display substrates.

So far, several proposals have been made for the purpose of increasing the sensitivity of the photosensitive resin material.
For example, a radiation-sensitive resin composition containing an alkali-soluble resin and at least one of a specific polyhydroxy compound and a derivative thereof has been proposed (see, for example, Patent Document 1), but a conventional photosensitive resin containing a naphthoquinone diazide compound is proposed. In the case of the photosensitive resin material, the exposure margin in the half exposure region tends to decrease as the sensitivity is increased in the exposure through the halftone mask, and it is impossible to achieve both high sensitivity and improvement in the exposure margin.
On the other hand, a chemically amplified resist has been developed as a photosensitive material with high sensitivity and high resolution, and the conventional chemically amplified resist developed as a resist for semiconductors has a light source (KrF) having a wavelength shorter than that of i-line. , ArF), and it has been proposed that finer pattern formation is possible (see, for example, Patent Document 2).

However, even in the above-mentioned chemically amplified resist, the protective group bond portion and the ether bond thermal crosslinking portion are easily decomposed at a high temperature used for film curing or in the presence of a resist stripping solution. The heat resistance and chemical resistance are extremely low, making it almost impossible to use as a permanent film.
In addition, in order to enable thermosetting, even if an epoxy or aminoplast crosslinking system is introduced into the chemically amplified resist, it is generated from a photoacid generator (hereinafter also referred to as PAG) in the resist by exposure. Due to the influence of the acid, the crosslinking of the exposed part proceeds and a new problem arises such as the disappearance of the dissolution contrast with the unexposed part. Therefore, it was difficult to introduce such a crosslinked system into the chemically amplified resist.

Under such circumstances, in the manufacture of a transflective liquid crystal display element, particularly in the manufacture of a flattened film, exposure is performed by adjusting the aperture and interval of the mask pattern opening for half exposure, and contact holes and An uneven pattern for reflection is formed. However, there is a limit to the amount of adjustment of the mask, and in order to form a concavo-convex pattern with high accuracy, it is necessary to reduce the exposure sensitivity of the planarization film. For this reason, it is necessary to increase the exposure amount for forming the contact hole, and as a result, it is difficult to improve the throughput of device manufacturing.
JP-A-4-21255 US Pat. No. 5,075,199

  In order to overcome the above problems, an object of the present invention is to provide a method for producing a transparent cured film having a wide exposure margin while maintaining high sensitivity. In particular, the present invention provides a method for producing a transparent cured film that can be applied to the production of a TFT flattening film in a transflective liquid crystal display element, particularly for forming contact holes and reflective irregularities simultaneously by half exposure. With the goal.

That is, as a first aspect, two positive photosensitive resin layers having different exposure sensitivities are formed on a substrate, and a low-sensitivity positive photosensitive resin layer is disposed between the substrate and a high-sensitivity positive photosensitive resin layer. A step of laminating the two layers, a step of exposing the two layers of the positive photosensitive resin layer, a step of heating the two layers of the positive photosensitive resin layer after exposure, and a step of exposing the two layers of the positive photosensitive resin layer. A method for producing a transparent cured film comprising a step of developing a photosensitive resin layer and a step of post-baking the two positive photosensitive resin layers, wherein the low-sensitivity positive photosensitive resin layer comprises the following ( A method for producing a transparent cured film, which is a positive photosensitive resin layer containing component A), component (B), component (C) and component (D).
(A) Component: Alkali-soluble resin (B) Component: Compound having two or more vinyl ether groups in the molecule (C) Component: Compound that crosslinks with (A) component by post-baking (D) Component: Photoacid generation Agent As a second aspect, the method for producing a transparent cured film according to the first aspect, wherein the exposure is half exposure.
As a third aspect, the method for producing a transparent cured film according to the first aspect or the second aspect, wherein the post-exposure heating is performed at a temperature of 80 ° C. to 140 ° C. and the post-baking is performed at a temperature of 150 ° C. to 270 ° C.
As a fourth aspect, the high-sensitivity positive photosensitive resin layer is a positive photosensitive resin layer containing the following component (A), component (B), component (C), and component (D), respectively. The manufacturing method of the transparent cured film as described in any one of a 1st viewpoint thru | or a 3rd viewpoint.
(A) Component: Alkali-soluble resin (B) Component: Compound having two or more vinyl ether groups in the molecule (C) Component: Compound that crosslinks with (A) component by post-baking (D) Component: Photoacid generation Agent As a fifth aspect, in the low-sensitivity positive photosensitive resin layer, based on 100 parts by mass of component (A), 1 to 80 parts by mass of component (B), 1 to 70 parts by mass of (C ) Component, and the manufacturing method of the transparent cured film as described in any one of 1st viewpoint thru | or 4th viewpoint containing 0.5 thru | or 50 mass parts said (D) component.
The manufacturing method of the transparent cured film as described in any one of the 1st viewpoint thru | or a 5th viewpoint which is a base material in which the base material formed the TFT element as a 6th viewpoint.
As a seventh aspect, a TFT array planarizing film comprising a transparent cured film obtained by the manufacturing method according to any one of the first aspect to the fifth aspect.
As an eighth aspect, a display element having a transparent cured film obtained by the production method according to any one of the first aspect to the fifth aspect.
As a ninth aspect, a liquid crystal display element having a transparent cured film obtained by the manufacturing method according to any one of the first aspect to the fifth aspect.

  The transparent cured film obtained by the present invention has the effects of high sensitivity at the time of half exposure and a wide exposure margin. It can be suitably used for manufacturing a transmissive liquid crystal display element.

The present invention provides two positive photosensitive resin layers having different exposure sensitivities on a substrate, and the low-sensitivity positive photosensitive resin layer is positioned between the substrate and the high-sensitivity positive photosensitive resin layer. Transparent curing, comprising the steps of: exposing the positive photosensitive resin layer composed of the two layers, post-exposure heating (Post Exposure Bake: PEB), developing, and post-baking It is a manufacturing method of a film | membrane.
Specifically, a low-sensitivity positive photosensitive resin layer is formed on a base material, and a high-sensitivity positive photosensitive resin layer is further laminated on the low-sensitivity layer, so that the exposure sensitivity differs on the base material. A step of laminating two positive photosensitive resin layers, a step of exposing the laminated two positive photosensitive resin layers, a step of heating the two positive photosensitive resin layers after exposure, A method for producing a transparent cured film comprising a step of developing two positive photosensitive resin layers and a step of post-baking the two positive photosensitive resin layers, the positive photosensitive resin having low sensitivity. The resin layer is a positive photosensitive resin layer containing the following component (A), component (B), component (C) and component (D): a method for producing a transparent cured film .
(A) Component: Alkali-soluble resin (B) Component: Compound having two or more vinyl ether groups in the molecule (C) Component: Compound that crosslinks with (A) component by post-baking (D) Component: Photoacid generation Agent

  According to the production method of the present invention, two layers of positive photosensitive resin layers having different exposure sensitivities are laminated on a substrate, so that when exposed through a halftone mask, a high sensitivity positive photosensitive property is obtained. Different pattern shapes can be formed between a resin layer (hereinafter referred to as a high sensitivity layer) and a low sensitivity positive photosensitive resin layer (hereinafter referred to as a low sensitivity layer). In other words, according to the manufacturing method of the present invention, different image shapes can be formed in one exposure by using a halftone mask in the high-sensitivity layer and the low-sensitivity layer.

In the present invention, since the low-sensitivity layer is laminated so as to be positioned between the substrate and the high-sensitivity layer, the high-sensitivity layer and the low sensitivity remain as unexposed portions during development, and the half-exposed portion has a high sensitivity. The layer is removed and the low-sensitivity layer remains, and in the completely exposed portion, the positive photosensitive resin layer (high-sensitivity layer and low-sensitivity layer) is completely removed, and the substrate is exposed.
The half-exposure portion referred to here is a portion that can be developed with an exposure amount smaller than that of the complete exposure portion and can form a desired image.

In order to obtain a desired image, it is required to suppress intermixing between the low-sensitivity layer and the high-sensitivity layer to be laminated. If the suppression of intermixing is insufficient in the two layers, the interface between the low-sensitivity layer and the high-sensitivity layer becomes unclear, and it is difficult to obtain a desired image during half exposure.
In the present invention, when the low-sensitivity layer is formed, the components contained in the resin composition are preliminarily dried (heat treatment) after applying a positive photosensitive resin composition solution for forming the layer. They are cross-linked with each other, whereby a film hardly soluble in an organic solvent is formed on the substrate. Therefore, when a high-sensitivity layer is subsequently formed on the low-sensitivity layer, the low-sensitivity layer and the high-sensitivity layer may intermix even if a positive photosensitive resin composition solution that forms the layer is applied. There is no.

  The high-sensitivity layer and the low-sensitivity layer are each exposed to an amount of light that is less than the exposure amount necessary for starting development. It is desired that development is performed rapidly (high accuracy and high sensitivity) after irradiation of an amount of light.

  Here, in the half exposure portion, at the time of development, the difference between the exposure amount at which dissolution of the low-sensitivity layer ends and the exposure amount at which dissolution of the high-sensitivity layer starts becomes the half exposure margin. This is closely related to the sensitivity difference between the high-sensitivity layer and the low-sensitivity layer, and the half exposure margin increases as the sensitivity difference between these two layers increases. That is, the higher the sensitivity of the high sensitivity layer, the wider the exposure margin the lower the sensitivity of the low sensitivity layer. In order to obtain a highly accurate image, the half exposure margin is preferably 10 mJ or more.

On the other hand, in order to improve the throughput of device manufacturing, it is important that the low sensitivity layer has a certain degree of sensitivity. For the purpose of increasing the half-exposure margin, if the amount of exposure required to start development of the low-sensitivity layer is too large, the sensitivity of the low-sensitivity layer will be reduced, leading to a decrease in throughput. by.
For this reason, the low-sensitivity layer is preferably, for example, a highly sensitive chemical amplification type photosensitive layer.
Therefore, the high-sensitivity layer is required to be a photosensitive layer with higher sensitivity than the high-sensitivity low-sensitivity layer, and a chemically amplified photosensitive layer with higher sensitivity is preferable.

The positive photosensitive resin layer used in the present invention is as described above, and a transparent cured film can be obtained by post-baking after forming a desired image.
A more preferred positive photosensitive resin layer will be described below.

<Low-sensitivity positive photosensitive resin layer (low-sensitivity layer)>
The low-sensitivity layer used in the present invention comprises (A) an alkali-soluble resin, (B) a compound having two or more vinyl ether groups in one molecule, and (C) component post-baking to (A) component. It consists of a positive photosensitive resin composition containing a reacting compound and a photoacid generator as component (D).
Usually, the low-sensitivity layer can be formed by dissolving the positive photosensitive resin composition described above in (E) solvent to form a solution, applying the solution to a substrate, and drying. Below, each component is described.

[(A) component]
The component (A) is an alkali-soluble resin, and as a preferred one, a functional group for allowing a thermal crosslinking reaction with the compound having a vinyl ether group as the component (B) in the resin structure, and (C) It has a functional group for film curing that can undergo a thermosetting reaction between the component (A) and a compound that undergoes a crosslinking reaction by post-baking of the component, and has a number average molecular weight of 2,000 to 50, An alkali-soluble resin that is 000 can be mentioned.
In other words, the component (A) is an alkali-soluble resin, and it is preferable that a thermal crosslinking reaction can be performed with the compound having a vinyl ether group of the component (B) by pre-baking in the resin structure. Alkali having a functional group and a functional group for film curing that can undergo a crosslinking reaction with component (C) by post-baking to form a thermosetting reaction, and has a number average molecular weight of 2,000 to 50,000 A soluble resin can be mentioned.

  The functional group for the thermal crosslinking reaction reacts with the vinyl ether group in the compound of the component (B) under an elevated temperature (prebake temperature), and performs thermal crosslinking with the compound of the component (B). The typical functional group is at least one selected from the group consisting of a carboxyl group and a phenolic hydroxy group.

In addition, the functional group for film curing is higher in the thermal cross-linked product of the components (A) and (B) (in the exposed part, in the de-cross-linked product in which the thermal cross-linked product is further dissociated). It is a group capable of causing a film to cure by causing a crosslinking reaction with the compound of component (C) under a given temperature (post-bake temperature).
As will be described later, when the component (C) is a compound having two or more blocked isocyanate groups, the functional group for film curing that the component (A) has is a block moiety with the compound of the component (C). A cross-linking reaction is carried out through the isocyanate group dissociated to harden the film.
A representative functional group as a functional group for film curing is at least one selected from the group of hydroxy groups other than phenolic hydroxy groups and amino groups having active hydrogen.
Here, the amino group having active hydrogen means a primary or secondary amino group capable of releasing a proton by reaction. Therefore, the amide group does not correspond to an amino group having active hydrogen because it does not have active hydrogen.

  The alkali-soluble resin as the component (A) may be any alkali-soluble resin having such a structure, and is not particularly limited with respect to the main chain skeleton and side chain type of the polymer constituting the resin.

  However, the resin of component (A) has a number average molecular weight in the range of 2,000 to 50,000. If the number average molecular weight is excessively larger than 50,000, a development residue is easily generated, and the sensitivity is greatly reduced. On the other hand, if the number average molecular weight is less than 2,000 and is too small, a considerable amount of film loss in the exposed area may occur during development, resulting in insufficient curing.

  Examples of the alkali-soluble resin (A) include acrylic resins, polyhydroxystyrene resins, polyimide precursors, and polyimides.

  In the present invention, an alkali-soluble resin composed of a copolymer obtained by polymerizing plural kinds of monomers (hereinafter referred to as a specific copolymer) can also be used as the component (A). In this case, the alkali-soluble resin as the component (A) may be a blend of a plurality of types of specific copolymers.

That is, the specific copolymer includes a monomer that exhibits alkali solubility, that is, at least one monomer appropriately selected from the group of monomers having at least one of a carboxyl group and a phenolic hydroxy group, and a functional group for film curing. A copolymer formed as an essential constituent unit with a monomer having a group, that is, at least one monomer appropriately selected from the group of monomers having at least one of a hydroxy group other than a phenolic hydroxy group and an amino group having an active hydrogen. A polymer having a number average molecular weight (in terms of polystyrene) of 2,000 to 50,000.
The number average molecular weight and the weight average molecular weight of the specific copolymer are, for example, using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation and the elution solvent tetrahydrofuran at a flow rate of 1 ml / min. The measurement can be performed under the condition that the column is eluted (column temperature: 40 ° C.).

  The above “monomer having at least one of carboxyl group and phenolic hydroxy group” includes a monomer having a carboxyl group, a monomer having a phenolic hydroxy group, and a monomer having both a carboxyl group and a phenolic hydroxy group. included. These monomers are not limited to those having one carboxyl group or one phenolic hydroxy group, and may have a plurality of monomers.

Further, the above-mentioned “monomer having at least one of a hydroxy group other than a phenolic hydroxy group and an amino group having an active hydrogen” has a monomer having a hydroxy group other than a phenolic hydroxy group and an amino group having an active hydrogen. Monomers and monomers having both hydroxy groups other than phenolic hydroxy groups and amino groups having active hydrogen are included. These monomers are not limited to those having one amino group having a hydroxy group or active hydrogen other than the phenolic hydroxy group, and may have a plurality thereof.
Hereinafter, although the specific example of the said monomer is given, it is not limited to these.

  Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl). ) Maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.

  Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide and the like.

  Examples of the monomer having a hydroxy group other than the phenolic hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxyl-6-lactone, 2-hydroxy Examples include ethyl methacrylate, 2-hydroxypropyl methacrylate, and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxyl-6-lactone.

Further, examples of the monomer having an amino group having active hydrogen include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.

  The specific copolymer was also formed with a monomer having a functional group for thermal crosslinking reaction and a monomer other than the monomer having a functional group for film curing (hereinafter referred to as other monomer) as a structural unit. A copolymer may also be used.

  The other monomer specifically includes a monomer having at least one of a carboxyl group and a phenolic hydroxy group, and a monomer having at least one of a hydroxy group other than the phenolic hydroxy group and an amino group having active hydrogen. As long as it can be copolymerized with the component (A), it is not particularly limited as long as the properties of the component (A) are not impaired.

  Specific examples of other monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.

  Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, and tert-butyl. Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and , Etc. 8-ethyl-8-tricyclodecyl acrylate.

  Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl. Methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- Propyl-2-adamantyl methacrylate, 8-methyl 8 tricyclodecyl methacrylate, and, 8-ethyl-8-tricyclodecyl methacrylate.

  Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

  Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.

  Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

The method for obtaining the specific copolymer used in the present invention is not particularly limited. For example, at least one monomer appropriately selected from the group of monomers having at least one of a carboxyl group and a phenolic hydroxy group, and other than the phenolic hydroxy group In a solvent, at least one monomer appropriately selected from the group of monomers having at least one of hydroxy groups and amino groups having active hydrogen, a monomer other than the above monomers, and a polymerization initiator, if desired, in a solvent. It can be obtained by carrying out the polymerization reaction at a temperature of 110 ° C. to 110 ° C. In that case, the solvent used will not be specifically limited if the monomer which comprises a specific copolymer, and a specific copolymer are melt | dissolved. As a specific example, the solvent described in (E) solvent mentioned later is mentioned.
The specific copolymer thus obtained is usually in the form of a solution in which the specific copolymer is dissolved in a solvent.
In addition, the solution of the specific copolymer obtained as described above is re-precipitated by stirring with stirring such as diethyl ether or water, and the generated precipitate is filtered and washed, and then under normal pressure or reduced pressure. Thus, the powder of the specific copolymer can be obtained by drying at room temperature or by heating. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If sufficient purification cannot be achieved by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
In the present invention, the powder of the specific copolymer may be used as it is, or the powder may be redissolved in a solvent (E) described later and used as a solution.

In addition, as the alkali-soluble resin of component (A), polyimide precursors such as polyamic acid, polyamic acid ester, partially imidized polyamic acid, and polyimide such as carboxylic acid group-containing polyimide can be used. If it is soluble, the kind can be used without particular limitation.
The polyimide precursor and polyimide are those having a number average molecular weight (in terms of polyethylene oxide and polyethylene glycol) of 2,000 to 50,000 in terms of developability and solubility in the solvent used.
The number average molecular weight and weight average molecular weight of the polyimide precursor and polyimide are, for example, using a GPC apparatus (Shodex (registered trademark) columns KD802, KD803, and KD804) manufactured by JASCO Corporation, and 0.1 mol% of elution solvent. The measurement can be performed under the condition that a lithium bromide N, N-dimethylformamide solution is eluted by flowing through a column (column temperature: 40 ° C.) at a flow rate of 1 ml / min.

  The polyamic acid, which is a polyimide precursor, can generally be obtained by polycondensation of (a) a tetracarboxylic dianhydride compound and (b) a diamine compound.

(A) The tetracarboxylic dianhydride compound is not particularly limited, and specific examples include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3. ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride Aromatic tetracarboxylic acid such as 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2 , 3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexane Tetracarbo Alicyclic tetracarboxylic dianhydrides such as acid dianhydrides, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1,2,3,4 Mention may be made of aliphatic tetracarboxylic dianhydrides such as -butanetetracarboxylic dianhydride.
These can be used alone or in combination of two or more compounds.

The (b) diamine compound is not particularly limited, and for example, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1,3 Benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis (4-amino-3-carboxyphenyl) ether, bis (4-amino-3,5-dicarboxyphenyl) ether, bis ( 4-amino-3-carboxyphenyl) sulfone, bis (4-amino-3,5-dicarboxyphenyl) sulfone, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′-diamino- 3,3′-dicarboxy-5,5′-dimethylbiphenyl, 4,4′-diamino-3,3′-dicarboxy-5,5′-dimethoxybiphenyl, 1,4-bis (4- Mino-3-carboxyphenoxy) benzene, 1,3-bis (4-amino-3-carboxyphenoxy) benzene, bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone, bis [4- (4 -Amino-3-carboxyphenoxy) phenyl] propane, 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] hexafluoropropane, 2,4-diaminophenol, 3,5-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis (3-amino-4-hydroxyphenyl) ether, bis (4-amino-3-hydroxyphenyl) ether, bis (4 -Amino-3,5-dihydroxyphenyl) ether, bis (3-amino-4) -Hydroxyphenyl) methane, bis (4-amino-3-hydroxyphenyl) methane, bis (4-amino-3,5-dihydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4 -Amino-3-hydroxyphenyl) sulfone, bis (4-amino-3,5-dihydroxyphenyl) sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis ( 4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3,5-dihydroxyphenyl) hexafluoropropane, 4,4′-diamino-3,3′-dihydroxybiphenyl, 4, , 4'-diamino-3,3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4'-diamino- , 3′-dihydroxy-5,5′-dimethoxybiphenyl, 1,4-bis (3-amino-4-hydroxyphenoxy) benzene, 1,3-bis (3-amino-4-hydroxyphenoxy) benzene, 1, 4-bis (4-amino-3-hydroxyphenoxy) benzene, 1,3-bis (4-amino-3-hydroxyphenoxy) benzene, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] sulfone, Diamine compounds having a phenolic hydroxy group such as bis [4- (3-amino-4-hydroxyphenoxy) phenyl] propane, 2,2-bis [4- (3-amino-4-hydroxyphenoxy) phenyl] hexafluoropropane 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, Diamine compounds having a thiophenol group such as 1,4-diamino-2-mercaptobenzene, bis (4-amino-3-mercaptophenyl) ether, 2,2-bis (3-amino-4-mercaptophenyl) hexafluoropropane, 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis (4-aminobenzene-3-sulfonic acid) ether, Examples thereof include diamine compounds having a sulfonic acid group such as 4,4′-diaminobiphenyl-3,3′-disulfonic acid and 4,4′-diamino-3,3′-dimethylbiphenyl-6,6′-disulfonic acid. P-phenylenediamine, m-phenylenediamine, 4,4′-methylene-bis (2,6-ethylaniline), 4,4′-methylene-bis (2-isopropyl-6-methylaniline), 4, 4'-methylene-bis (2,6-diisopropylaniline), 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, o- Tolidine, m-tolidine, 3,3 ′, 5,5′-tetramethylbenzidine, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] Propane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 4,4 ′ Diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 2,2-bis (4-anilino) hexafluoropropane, 2,2-bis (3-anilino) hexafluoropropane, 2,2- Bis (3-amino-4-toluyl) hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) And diamine compounds such as phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane. .
These can be used alone or in combination of two or more compounds.

  When the polyamic acid used in the present invention is produced from (a) a tetracarboxylic dianhydride compound and (b) a diamine compound, the compounding ratio of both compounds, that is, <(b) the total number of moles of the diamine compound / (a ) The total number of moles of tetracarboxylic dianhydride compound is preferably 0.7 to 1.2. As in the normal polycondensation reaction, the closer the molar ratio is to 1, the higher the degree of polymerization of the polyamic acid produced and the higher the molecular weight.

Moreover, when it superposes | polymerizes using a diamine compound excessively, a carboxylic anhydride can be made to react with the terminal amino group of the remaining polyamic acid, and a terminal amino group can also be protected.
Examples of such carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid There may be mentioned anhydrides, itaconic anhydride, tetrahydrophthalic anhydride and the like.

In the production of polyamic acid, the reaction temperature of the reaction between the diamine compound and the tetracarboxylic dianhydride compound can be selected from -20 to 150 ° C, preferably -5 to 100 ° C. In order to obtain a high molecular weight polyamic acid, the reaction temperature is appropriately selected within the range of 5 to 40 ° C. and the reaction time of 1 to 48 hours. In order to obtain a partially imidized polyamic acid having a low molecular weight and high storage stability, it is more preferable to select from a reaction temperature of 40 ° C. to 90 ° C. and a reaction time of 10 hours or more.
The reaction temperature for protecting the terminal amino group with an acid anhydride can be selected from -20 to 150 ° C, preferably -5 to 100 ° C.

  The reaction of the diamine compound and the tetracarboxylic dianhydride compound can be performed in a solvent. Examples of solvents that can be used in this case include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethylsulfone, Hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, 3 -Ethyl ethoxypropionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ester Ter, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene Examples include glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. These may be used alone or in combination. Furthermore, even if it is a solvent which does not melt | dissolve a polyamic acid, you may mix and use it for the said solvent in the range which does not precipitate the polyamic acid produced | generated by the polymerization reaction.

The solution containing the polyamic acid thus obtained can be used as it is for preparing a positive photosensitive resin composition solution. Alternatively, the polyamic acid can be used after being precipitated and isolated in a poor solvent such as water, methanol, ethanol, and recovered.
The polyamic acid thus obtained can be esterified with a carboxyl group and used as a polyamic acid ester.
The polyamic acid thus obtained may be used alone or at the same time as the alkali-soluble resin described above.

In the present invention, any polyimide can be used. The polyimide used in the present invention is obtained by chemically or thermally imidizing 50% or more of a polyimide precursor such as polyamic acid. These polyimides include copolymers such as polyamideimide and polyetherimide.
The polyimide in the positive photosensitive resin composition used in the present invention has a carboxyl group or a phenolic hydroxy group to give alkali solubility, or has a carboxylic acid or a phenolic hydroxy group by the action of heat or acid. It preferably has a group to be generated.
The method of introducing a carboxyl group or a phenolic hydroxy group into polyimide is a method using a monomer having a carboxyl group or a phenolic hydroxy group, a method of sealing an amine terminal with an acid anhydride having a carboxyl group or a phenolic hydroxy group, Or the method etc. which make imidation rate 99% or less when imidating a polyimide precursor are used.
Moreover, the introduction method of the group which produces | generates carboxylic acid or a phenolic hydroxy group by the effect | action of a heat | fever or an acid to a polyimide is the method using the monomer which produces | generates a carboxyl group or a phenolic hydroxy group by the effect | action of a heat | fever or an acid, and introduce | transduced beforehand. There is a method in which a carboxyl group, a phenolic hydroxy group, or a carboxylic acid residue after imidization is reacted with a group that is dissociated by the action of heat or acid.
Such a polyimide can be obtained by synthesizing the above polyimide precursor and then performing chemical imidization or thermal imidization.
As a method of chemical imidization, generally, a method of adding excess acetic anhydride and pyridine to a polyimide precursor solution and reacting at room temperature to 100 ° C. is used. As a method for thermal imidization, generally, a method in which a polyimide precursor solution is heated while being dehydrated at a temperature of 180 ° C. to 250 ° C. is used.

  The polyimide thus obtained may be used alone or at the same time as other alkali-soluble resins (for example, specific copolymers) described above.

[Component (B)]
Component (B) is a compound having two or more vinyl ether groups in one molecule. This may be a compound having two or more vinyl ether groups in one molecule that can be thermally cross-linked with the alkali-soluble resin (A) at a conventional pre-baking temperature, and the type and structure are particularly limited. Not a thing.

  The compound of component (B) is separated from the alkali-soluble resin of component (A) by acid generated by exposure in the presence of a photoacid generator after thermal crosslinking with the alkali-soluble resin of component (A). (Decrosslinking), and thereafter development using an alkaline developer removes both the alkali-soluble resin of component (A). Accordingly, as this type of compound, a vinyl ether compound generally used as a component of a vinyl ether type chemically amplified resist can be applied. The use of such a compound has an advantage that the formed image can be controlled by adjusting the thermal crosslinking density by changing the compounding amount of the compound.

  And as a compound of (B) component, the compound represented by Formula (1) and Formula (2) especially among the said vinyl ether type compounds is preferable at the point developed without a residual film and a residue in an exposure part. .

(In the formula, n is an integer of 2 to 10, k is an integer of 1 to 10, and R ¹ represents an n-valent organic group.)

(In the formula, m represents an integer of 2 to 10.)

  N in the formula (1) represents the number of vinyl ether groups in one molecule, and n is more preferably an integer of 2 to 4. And m in the formula (2) also represents the number of vinyl ether groups in one molecule, and m is preferably an integer of 2 to 4.

  Specific examples of the compounds represented by the formula (1) and the formula (2) include bis (4- (vinyloxymethyl) cyclohexylmethyl) glutarate, tri (ethylene glycol) divinyl ether, adipic acid divinyl ester, diethylene glycol. Cyclohexanedi, such as divinyl ether, tris (4- (vinyloxy) butyl) trimellitate, bis (4- (vinyloxy) butyl) terephthalate, bis (4- (vinyloxy) butyl isophthalate, and 1,4-cyclohexanedimethanol divinyl ether And methanol divinyl ether.

  Moreover, the compound of (B) component is used in the ratio of 1-80 mass parts with respect to 100 mass parts of (A) component, Preferably it is 5-40 mass parts. When the amount of the component (B) compound used is an excessive amount less than the lower limit of the above range, the film reduction in the unexposed area becomes remarkable and the relief pattern of the formed pattern becomes poor. On the other hand, if the amount of the component (B) compound used exceeds the upper limit of the above range, the sensitivity of the film is greatly reduced, and residues between patterns are generated after development.

[Component (C)]
The component (C) is a compound that undergoes a crosslinking reaction with the component (A) by post-baking, and a compound having two or more blocked isocyanate groups in one molecule is preferably used. This is because, for example, a film made of an alkali-soluble resin of component (A) that has been thermally crosslinked with or further decrosslinked with the compound of component (B) can be heated at a conventional post-bake temperature, for example. Any compound having at least two blocked isocyanate groups that can be cured per molecule may be used, and the type and structure thereof are not particularly limited.

  The compound of component (C) has two or more blocked isocyanate groups in which one or more isocyanate groups (—NCO) are blocked by an appropriate protecting group, and when exposed to a high temperature during thermal curing, The protective group (block portion) is removed by thermal dissociation, and the functional group for thermal curing in the alkali-soluble resin of the component (A) (for example, hydroxy group other than phenolic hydroxy group and active hydrogen) through the generated isocyanate group A crosslinking reaction proceeds between each other, for example, the formula (3)

(In the formula, R ² represents an organic group in the block part) A compound having two or more groups in one molecule (this group may be the same or different) may be mentioned. It is done.

  The compound of component (C) having two or more blocked isocyanate groups in one molecule can be obtained, for example, by allowing a suitable blocking agent to act on a compound having two or more isocyanate groups in one molecule. .

  Examples of the compound having two or more isocyanate groups in one molecule include isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, etc., or their dimers, three And a reaction product of these with diols, triols, diamines, and triamines.

  Examples of the blocking agent include methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, cyclohexanol, and other alcohols, phenol, o-nitrophenol. , P-chlorophenol, phenols such as o-, m- or p-cresol, lactams such as ε-caprolactam, oximes such as acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime And pyrazoles such as pyrazole, 3,5-dimethylpyrazole and 3-methylpyrazole, and thiols such as dodecanethiol and benzenethiol.

  The compound of component (C) is one in which the block portion undergoes thermal dissociation at a higher temperature such as the post-baking temperature and the crosslinking reaction proceeds via the isocyanate group, but at a lower temperature such as the pre-baking temperature, the isocyanate In order to prevent the cross-linking by the group from proceeding, it is particularly preferable as the component (C) that the thermal dissociation temperature of the block portion is considerably higher than the pre-baking temperature, for example, 120 ° C. to 230 ° C.

  Examples of the compound (C) include the following specific examples.

In the formula, the compound of component (C) in which the isocyanate compound is derived from isophorone diisocyanate is more preferable from the viewpoint of heat resistance and coating properties, and examples of such compounds include the following.
R in the following formula represents an organic group.

  In the present invention, the compound of component (C) may be used alone or in combination of two or more.

  Further, the compound of component (C) is used in a proportion of 3 to 70 parts by mass, preferably 5 to 40 parts by mass with respect to 100 parts by mass of component (A). When the amount of the component (C) compound used is too small below the lower limit of the above range, the thermosetting is insufficient and a satisfactory cured film cannot be obtained, while the amount of the component (C) compound used. If the amount exceeds the upper limit of the above range, the development is insufficient and a development residue is generated.

[(D) component]
The component (D) is a photoacid generator (also referred to as PAG). This is a substance that generates an acid (sulfonic acid, carboxylic acid, etc.) directly or indirectly by irradiation of light used for exposure. If it has such properties, its type and structure are There is no particular limitation.

  Examples of the photoacid generator of component (D) include diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzoin tosylate compounds, iron arene complexes, and halogen-containing triazines. Compounds, acetophenone derivative compounds, cyano group-containing oxime sulfonate compounds, and the like. Any conventionally known or conventionally used photoacid generator can be applied in the present invention without any particular limitation. In addition, in this invention, the photo-acid generator of (D) component may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specific examples of such a photoacid generator include the following. However, these compounds are just a few of the very many applicable photoacid generators and are of course not limited thereto.

  Diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis (p-tert- Butylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium mesylate, bis (p-tert-butylphenyl) iodonium tosylate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis ( p-tert-butylphenyl) iodoniumtetraf Oroborate, bis (p-tert-butylphenyl) iodonium chloride, bis (p-chlorophenyl) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium trifluoromethanesulfonate , Tri (p-methoxyphenyl) sulfonium tetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphonate, tri (p-ethoxyphenyl) sulfonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, tri (p -Methoxyphenyl) phosphonium tetrafluoroborate, tri (p-methoxyphenyl) phospho Phosphonium hexafluorophosphonate, tri (p- ethoxyphenyl) phosphonium tetrafluoroborate,

  The photoacid generator of component (D) is used in a proportion of 0.5 to 50 parts by mass, preferably 1 to 30 parts by mass with respect to 100 parts by mass of the alkali-soluble resin of component (A). When the amount of the photoacid generator used as the component (D) is an excessive amount less than the lower limit of the above range, the compound (A) of the component (B) which has been thermally crosslinked at the time of exposure is exposed from the alkali-soluble resin. Dissociation does not proceed, and it becomes difficult to obtain a relief having a desired pattern. On the other hand, if the amount of the photoacid generator (D) used exceeds the upper limit of the above range, a positive photosensitive resin composition It becomes inferior in the storage stability of things.

[(E) Solvent]
The positive photosensitive resin composition used in the present invention contains the above components (A) to (D) and is usually applied with a solution obtained by dissolving these components in the solvent (E). Form a layer.

This (E) solvent dissolves the (A) component to the (D) component and dissolves the (F) component, which will be described later if desired, and is a solvent having such a dissolving ability. For example, the type and structure are not particularly limited.
Examples of such a solvent (E) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol. Monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethoxyacetic acid Ethyl, hydroxyethyl acetate, 2-hydroxy-3-methyl Methyl tannate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, lactic acid Examples include butyl, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.
These solvents can be used singly or in combination of two or more.

  Among these solvents (E), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, etc. have good coating properties and safety. Is preferable from the viewpoint of high. These solvents are generally used as solvents for photoresist materials.

[(F) component]
Component (F) is a surfactant. In preparing the positive photosensitive resin composition solution, a surfactant may be further added for the purpose of improving the coating property as long as the effects of the present invention are not impaired.

The surfactant as the component (F) is not particularly limited, and examples thereof include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. As this type of surfactant, for example, commercially available products such as those manufactured by Sumitomo 3M Co., Ltd., Dainippon Ink Chemical Co., Ltd., or Asahi Glass Co., Ltd. can be used. These commercial products are convenient because they can be easily obtained. Specific examples include F-top EF301, EF303, EF352 (manufactured by Gemco), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink & Chemicals, Inc.), Florard FC430, FC431 (Sumitomo) 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) and the like.
These surfactants can be used singly or in combination of two or more.

  When the surfactant is used, the content thereof is usually 0.2% by mass or less, preferably 0.1% by mass or less, in 100% by mass of the positive photosensitive resin composition solution. Even if the amount of the surfactant used as the component (F) is set to an amount exceeding 0.2% by mass, the effect of improving the coating property becomes dull and not economical.

[Other additives]
Furthermore, as long as the positive photosensitive resin composition used in the present invention does not impair the effects of the present invention, as necessary, adhesion assistants such as rheology modifiers and silane coupling agents, pigments, dyes, storage stability Agents, antifoaming agents, or dissolution accelerators such as polyphenols and polycarboxylic acids.
For example, the silane coupling agent can be used for the purpose of improving the adhesion with the substrate.
Specific examples thereof are shown below, for example, γ-methacryloxypropyltrimethoxysilane, γ-aminopropylsilane, 2- (3,4 epoxycyclohexyl) ethyltriethoxysilane, N-aminoethyl-γ-aminopropyltri Methoxysilane, 3-ureidopropyltriethoxysilane, γ-isocyanatopropyltriethoxysilane, n-octyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ -Glycidoxypropyltrimethoxysilane, γ-mercapto-propyltrimethoxysilane, 3-octanoylthio-1-propyltriethoxysilane and the like.

[Positive photosensitive resin composition and solution thereof]
The positive photosensitive resin composition used in the present invention comprises (A) an alkali-soluble resin, (B) a compound having two or more vinyl ether groups in one molecule, and (C) component post-baking (A And a photoacid generator of the component (D). Usually, these components (A) to (D) are dissolved in a solvent (E) and used for forming a positive photosensitive resin layer in the form of a solution. Furthermore, one or more of surfactant (F) and other additives can be contained as desired.

Especially, the preferable example of this positive type photosensitive resin composition and the solution of this composition is as follows.
[1]: Based on 100 parts by mass of component (A), 1 to 80 parts by mass of component (B), 3 to 70 parts by mass of component (C), and 0.5 to 50 parts by mass of (D). A positive photosensitive resin composition containing components.
[2]: A solution of a positive photosensitive resin composition obtained by dissolving the composition of [1] in (E) a solvent.
[3]: A solution of a positive photosensitive resin composition further containing 0.2% by mass or less of component (F) in the solution of the composition of [2] above.

  The ratio of the solid content in the solution of the positive photosensitive resin composition is not particularly limited as long as each component is uniformly dissolved in the solvent, and is, for example, 1 to 80% by mass. 5 to 60% by mass, or 8 to 50% by mass. Here, solid content means what remove | excluded the (E) solvent from all the components of the solution of the positive photosensitive resin composition.

  The method for preparing the positive photosensitive resin composition solution is not particularly limited. For example, (A) component (alkali-soluble resin) is dissolved in (E) solvent and (B) ) Component (compound having two or more vinyl ether groups in one molecule), (C) component (compound that crosslinks with (A) component by post-baking), (D) component (photoacid generator) and (F) A method of mixing the components (surfactant) in a predetermined ratio to make a uniform solution, or a method of further adding other additives as necessary at an appropriate stage of this preparation method and mixing. .

  In preparing the positive photosensitive resin composition solution, a solution of a specific copolymer obtained by a polymerization reaction in a solvent can be used as it is. In this case, the solution of the component (A) Similarly, when a (B) component, (C) component, (D) component, and the like are added to obtain a uniform solution, a solvent may be further added for the purpose of adjusting the concentration. At this time, the solvent used in the process of forming the specific copolymer and the solvent used for adjusting the concentration when preparing the solution of the positive photosensitive resin composition may be the same or different. .

  Thus, the prepared positive photosensitive resin composition solution is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

<High sensitivity positive photosensitive resin layer (high sensitivity layer)>
The high-sensitivity layer used in the present invention is not particularly limited as long as it is a positive photosensitive resin layer having sufficiently high sensitivity as compared with the sensitivity of the low-sensitivity layer described above. As such a high-sensitivity layer, a positive photosensitive resin composition is used.

The high sensitivity layer used in the present invention may be the same type as the positive photosensitive resin composition used in the low sensitivity layer. This is preferable in terms of high sensitivity and improved throughput, ease of pattern shape control, and suppression of film loss in unexposed areas during development.
In this case, in order to increase the sensitivity difference between the low-sensitivity layer and the high-sensitivity layer, the contents of the component (B) and the component (C) in the positive photosensitive resin composition of the high-sensitivity layer are set to those of the low-sensitivity layer. It is preferable that the content (mass) is less than the above. Specifically, the component (B) and the component (C) in the positive photosensitive resin composition of the high sensitivity layer are contained in the component (B) contained in the positive photosensitive resin composition of the low sensitivity layer. The content is preferably 10 to 80% of the amount (mass) and 30 to 70% of the content (mass) of the component (C). More preferably, the component (B) and the component (C) in the positive photosensitive resin composition of the high sensitivity layer are the contents of the component (B) contained in the positive photosensitive resin composition of the low sensitivity layer. The content is preferably 10 to 50% of (mass) and 40 to 60% of the content (mass) of component (C).

  Further, in the case of using the same type of positive photosensitive resin composition as that of the low sensitivity layer in the high sensitivity layer used in the present invention, the positive photosensitive resin composition used in the high sensitivity layer is <low sensitivity positive type It can be obtained in the same manner as the preparation method of [Positive photosensitive resin composition and solution thereof] of photosensitive resin layer (low sensitivity layer)>.

At this time, preferably, the following thermal crosslinking reaction is carried out by maintaining the mixed solution containing the components (A) to (E) and, optionally, the component (F) at a temperature higher than room temperature for a required period. Progressing somewhat, solution of positive photosensitive resin composition containing (A) component to (E) solvent, and optionally (F) component, plus cross-linked product of (A) component and (B) component Get.
More preferably, by maintaining the mixed solution at a temperature of 30 ° C. to 70 ° C. for 2 hours to 5 days, in addition to the components (A) to (E) and, optionally, the component (F), (A) A solution of a positive photosensitive resin composition containing a component and a crosslinked product of component (B) is obtained.

By adjusting under the above temperature and time conditions, the homogeneity of the resulting resin composition solution is increased, whereby the photoacid generator is efficiently contained in the film when it is subjected to a subsequent film forming step. Dispersion leads to dramatic improvement in sensitivity of the resulting film.
If the stirring temperature is higher than 70 ° C., the crosslinking reaction and curing reaction proceed and the composition solution becomes non-uniform, and the sensitivity of the resulting film is greatly reduced. If the stirring temperature is lower than 30 ° C., the composition solution Uniformity is not high and sensitivity is not improved.

<Positive photosensitive resin layer (photosensitive layer) and pattern formation>
In the present invention, two positive photosensitive resin layers having different exposure sensitivities are disposed on the substrate, and the low-sensitivity positive photosensitive resin layer is positioned between the substrate and the high-sensitivity positive photosensitive resin layer. However, the method for forming these layers is not particularly limited.

  For example, a positive photosensitive resin composition solution for a low-sensitivity layer is coated with a substrate (for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, or a metal such as aluminum, molybdenum, or chromium). Spin coating, flow coating, roll coating, slit coating, slit coating followed by spin coating, inkjet, etc. on a substrate, glass substrate, quartz substrate, ITO substrate, etc. and a substrate on which an element such as a transistor is formed) The low-sensitivity layer can be formed by coating by coating or the like and then pre-drying with a hot plate or oven. Subsequently, the high-sensitivity layer is formed by applying a positive photosensitive resin composition solution for the high-sensitivity layer in the same manner as the low-sensitivity layer and pre-drying it with a hot plate or oven.

As the preliminary drying conditions, for example, a heating temperature and a heating time appropriately selected from the range of a temperature of 70 ° C. to 160 ° C. and a time of 0.3 minutes to 60 minutes are employed. The heating temperature and the heating time are preferably 80 to 140 ° C. and 0.5 to 10 minutes.
In this preliminary drying, the solvent is removed, and the compound having the vinyl ether group as the component (B) is crosslinked with the resin as the component (A), thereby forming a film that is hardly soluble in an alkaline developer. In this case, if the temperature of the preliminary drying is lower than the lower limit of the above temperature range, the solvent remains in the film so that the desired pattern is not formed, or when the high sensitivity layer is applied, In some cases, intermixing may occur, and thermal crosslinking may be insufficient, resulting in film loss in unexposed areas. In addition, when the temperature exceeds the upper limit of the temperature range and is too high, when the unexposed portion is cross-linked and development failure occurs, the once formed thermal cross-linked portion is cut again, and the film is reduced in the unexposed portion. May be caused.

The film thickness of the positive photosensitive resin layer (the layer combining the low sensitivity layer and the high sensitivity layer) is, for example, 0.1 to 30 μm, for example, 0.2 to 10 μm, and further, for example, 0.2 To 5 μm.
At that time, the film thicknesses of the low-sensitivity layer and the high-sensitivity layer can be arbitrarily selected as long as the effects of the present invention are not impaired.

When the positive photosensitive resin layer obtained by the above method is exposed to light such as ultraviolet rays, ArF, KrF, and F ₂ laser light using a halftone mask having a predetermined pattern, the positive photosensitive resin layer is obtained. Due to the action of the acid generated from the photoacid generator of component (D) contained in the resin layer, the exposed portion of the film becomes soluble in an alkaline developer.
The exposure is preferably performed by light having at least one wavelength of i-line, g-line, and h-line, or ArF, KrF, or F ₂ laser light.

  Next, post-exposure heating is performed on the positive photosensitive resin layer. As heating conditions in this case, a heating temperature and a heating time appropriately selected from the range of a temperature of 80 ° C. to 140 ° C. and a time of 0.3 minutes to 60 minutes are employed.

  Thereafter, development is performed using an alkaline developer. As a result, in the positive photosensitive resin layer, only the high-sensitivity layer is removed in the half-exposed portion, and the low-sensitivity layer is removed together with the high-sensitivity layer in the completely exposed portion, so that a pattern-like relief is formed.

Examples of the alkaline developer that can be used include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline. Alkaline aqueous solutions such as amine aqueous solutions such as ethanolamine, propylamine, and ethylenediamine. Further, a surfactant or the like can be added to these developers.
Among the above, a tetraethylammonium hydroxide 0.1 to 2.38 mass% aqueous solution is generally used as a photoresist developer, and the alkaline developer is also used in the photosensitive resin composition of the present invention. It can be developed satisfactorily without causing problems such as swelling.

  Further, as a developing method, any of a liquid piling method, a dipping method, a rocking dipping method and the like can be used. The development time at that time is usually 15 seconds to 180 seconds.

  After development, the positive photosensitive resin layer is washed with running water, for example, for 20 to 90 seconds, and then air-dried with compressed air or compressed nitrogen or by spinning to remove moisture on the substrate, A patterned film is then obtained.

<Formation of transparent cured film>
Subsequently, the pattern forming film is subjected to post-baking for thermosetting, specifically by heating using a hot plate, an oven, etc., thereby providing heat resistance, transparency, and flatness. In addition, a film having a good relief pattern with excellent water absorption and chemical resistance can be obtained.

  Post bake is generally performed at a heating temperature selected from the range of 150 ° C. to 270 ° C. for 5 minutes to 30 minutes when on a hot plate, and 30 minutes to 90 minutes when in an oven. The method of processing is taken.

  Thus, by such post-baking, a target transparent cured film having a good pattern shape can be obtained.

  In the present invention, it is possible to produce a TFT array planarizing film of a transflective liquid crystal display element by imparting high transparency to the low sensitivity layer and high reflowability to the high sensitivity layer.

  As described above, according to the manufacturing method of the present invention, it is possible to form a coating film having a fine pattern with a sufficiently high sensitivity, a very small film loss at an unexposed portion during development, and a wide half exposure margin. it can.

  Therefore, for example, high throughput can be realized in a manufacturing process of various types of films in an array flattening film of a TFT type liquid crystal element, a liquid crystal or an organic EL display, such as an interlayer insulating film, a protective film, an insulating film, and a color filter. .

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these Examples.

[Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
MAA: methacrylic acid MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate CHMI: N-cyclohexylmaleimide AIBN: azobisisobutyronitrile PGMEA: propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether PAG1: Ciba Specialty Chemicals ( CGI1397 (trade name) / compound name: 2-methyl-α- [5-[[(propylsulfonyl) oxy] imino]-(5H) -thienylidene] benzeneacetonitrile (compound of formula (7))
PVE1: tris (4- (vinyloxy) butyl) trimellitate PVE2: 1,4-cyclohexanedimethanol divinyl ether NCO1: manufactured by Degussa AG VESTAGON (registered trademark) B 1065 (trade name) / compound name: ε-caprolactam block polyisocyanate (Compound of formula (S-4))
R30: Mega Japan R-30 (trade name) (fluorine surfactant) manufactured by Dainippon Ink and Chemicals, Inc.
MPTS: γ-methacryloxypropyltrimethoxysilane P200: P-200 (trade name) 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] manufactured by Toyo Gosei Co., Ltd. ] Sensitive agent synthesized by condensation reaction of 1 mol of phenyl] ethylidene] bisphenol and 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride (1,2-quinonediazide compound)
GT4: Epoxidized butanetetracarboxylic acid tetrakis- (3-cyclohexenylmethyl) modified ε-caprolactone

[Measurement of number average molecular weight and weight average molecular weight]
The number average molecular weight and the weight average molecular weight of the specific copolymer obtained according to the following synthesis examples were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation, and the elution solvent tetrahydrofuran was flowed at 1 ml / The measurement was performed under the condition that the column was eluted in a column (column temperature: 40 ° C.). The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.

<Synthesis Example 1>
MAA 19.4 g, CHMI 35.3 g, HEMA 25.5 g, MMA 19.8 g were used as monomer components constituting the specific copolymer, and AIBN 5 g was used as a radical polymerization initiator, and these were used as a solvent PGMEA 212. A solution of (A) component (specific copolymer) having a Mn of 4,100 and Mw of 7,600 (specific copolymer concentration: 32) by polymerization reaction at a temperature of 60 ° C. to 100 ° C. in 0.5 g. 0.0 mass%) was obtained. (P1)

<Synthesis Example 2>
MAA 15.5 g, CHMI 35.3 g, HEMA 25.5 g, MMA 23.7 g are used as monomer components constituting the specific copolymer, and AIBN 5 g is used as a radical polymerization initiator, and these are used as solvent PGMEA 212 The solution (specific copolymer concentration) of (A) component (specific copolymer) whose Mn is 4,400 and Mw is 7,000 by carrying out a polymerization reaction at a temperature of 60 ° C. to 100 ° C. in 0.5 g. 0.0 mass%) was obtained. (P2)

<Composition Examples 1 to 5>
According to the composition shown in the following Table 1, the component (A) is mixed with the component (B), the component (C), the component (D), the solvent (E), and the component (F) at a predetermined ratio. The mixture was stirred at a temperature of 23 ° C. for 30 minutes, or stirred at 35 ° C. for 3 days to obtain a uniform solution, thereby preparing a positive photosensitive resin composition solution of each example and each comparative example.

<Composition Example 6>
As an alkali-soluble resin solution, 1.1 g of P200 as a 1,2-quinonediazide compound and 1.1 g of GT4 as an epoxy-based crosslinkable compound were added to 17.2 g of the specific copolymer solution (P1) obtained in Synthesis Example 1. Then, 0.0039 g of R30 as a surfactant, 0.25 g of MPTS as an adhesion assistant, and 5.2 g of PGMEA as a solvent were mixed and stirred at room temperature for 8 hours to prepare a solution of a positive photosensitive resin composition.

<Composition Example 7>
As an alkali-soluble resin solution, 17.2 g of the specific copolymer solution (P2) obtained in Synthesis Example 2, 1.7 g of P200 as a 1,2-quinonediazide compound, and 1.1 g of GT4 as an epoxy-based crosslinkable compound Then, 0.0039 g of R30 as a surfactant, 0.25 g of MPTS as an adhesion assistant, and 6.5 g of PGMEA as a solvent were mixed and stirred at room temperature for 8 hours to prepare a solution of a positive photosensitive resin composition.

<Examples 1 to 4 and Comparative Examples 1 to 3>
For the two-layer films of Examples 1 to 4 shown in Table 2 and the single-layer films of Comparative Examples 1 to 3, the light transmittance (transparency), sensitivity, and unexposed portions after high-temperature baking are respectively shown. The film was reduced and the half exposure margin was measured.
When obtaining a cured film from the positive photosensitive resin composition, in Comparative Examples 2 and 3, photobleaching is performed at a stage after development and before post baking. On the other hand, with respect to Examples 1 to 4 and Comparative Example 1, post-exposure heating (PEB) is performed after exposure and before development without performing photobleaching. The procedure is different as follows.

[Evaluation of light transmittance (transparency) after high-temperature firing]
<Examples 1 to 4>
After applying the solution of the positive photosensitive resin composition for the lower layer onto a quartz substrate using a spin coater, pre-baking was performed on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 2.0 μm. . Subsequently, a solution of the positive photosensitive resin composition for the upper layer was applied onto the coating film using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to apply a film having a thickness of 1.0 μm. A film was formed. This coating film was immersed in a 0.4% aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 60 seconds, and then washed with running ultrapure water for 20 seconds. Subsequently, it post-baked by heating at 230 degreeC for 30 minutes, and formed the cured film with a film thickness of 2.4 micrometers. The initial transmittance of this cured film was measured at a wavelength of 400 nm using an ultraviolet-visible spectrophotometer (SHIMADZU UV-2550 model number, manufactured by Shimadzu Corporation). Further, the coating film was heated at 250 ° C. for 30 minutes, and the transmittance was similarly measured after heating at a wavelength of 400 nm. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.

<Comparative Example 1>
A solution of the positive photosensitive resin composition was applied on a quartz substrate using a spin coater, and then pre-baked on a hot plate at a temperature of 120 ° C. for 120 seconds to form a coating film having a thickness of 3.0 μm. This coating film was immersed in a 0.4% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. Subsequently, it post-baked by heating at 230 degreeC for 30 minutes, and formed the cured film with a film thickness of 2.4 micrometers. The initial transmittance of this cured film was measured at a wavelength of 400 nm using an ultraviolet-visible spectrophotometer (SHIMADZU UV-2550 model number, manufactured by Shimadzu Corporation). Further, the coating film was heated at 250 ° C. for 30 minutes, and the transmittance was similarly measured after heating at a wavelength of 400 nm. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.

<Comparative Examples 2 and 3>
The positive photosensitive resin composition solution was applied onto a quartz substrate using a spin coater, and then prebaked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 3.0 μm. This coating film was immersed in a 0.4% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. This coating film was irradiated with ultraviolet light having a light intensity of 365 m at 5.5 mW / cm ^{2 at} an exposure dose of 800 mJ / cm ² (photo bleaching) by an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc., and then at 230 ° C. for 30 hours. Post-baking was performed by heating for a minute, and a cured film having a thickness of 2.4 μm was formed. The initial transmittance of this cured film was measured at a wavelength of 400 nm using an ultraviolet-visible spectrophotometer (SHIMADZU UV-2550 model number, manufactured by Shimadzu Corporation). Further, the coating film was heated at 250 ° C. for 30 minutes, and the transmittance was similarly measured after heating at a wavelength of 400 nm. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.

[Evaluation of sensitivity and film loss]
<Examples 1 to 4>
After applying the positive photosensitive resin composition for the lower layer onto a silicon wafer using a spin coater, pre-baking was performed on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film (low sensitivity layer) having a thickness of 2.0 μm. Formed. Subsequently, the positive photosensitive resin composition for the upper layer was applied onto the coating film using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 1.0 μm ( High sensitivity layer) was formed. The film thickness was measured using F20 manufactured by FILMETRICS. The coating film by ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. is the light intensity at 365nm was irradiated with ultraviolet rays of 5.5 mW / cm ² at various exposure amounts, followed by exposure on 120 seconds on a hot plate at a temperature 110 ° C. Post heating was performed. Thereafter, development was performed by immersing in a 0.4% TMAH aqueous solution for 60 seconds, followed by washing with running pure water for 20 seconds. The lowest exposure amount (mJ / cm ² ) at which no undissolved portion remained in the exposed area was defined as sensitivity. Further, the amount of decrease in the film thickness of the unexposed part was defined as film reduction.

<Comparative Example 1>
The positive photosensitive resin composition was applied on a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 3.0 μm. The film thickness was measured using F20 manufactured by FILMETRICS. The coating film by ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. is the light intensity at 365nm was irradiated with ultraviolet rays of 5.5 mW / cm ² at various exposure amounts, followed by exposure on 120 seconds on a hot plate at a temperature 110 ° C. Post heating was performed. Thereafter, development was performed by immersing in a 0.4% TMAH aqueous solution for 60 seconds, followed by washing with running pure water for 20 seconds. The lowest exposure amount (mJ / cm ² ) at which no undissolved portion remained in the exposed area was defined as sensitivity. Further, the amount of decrease in the film thickness of the unexposed part was defined as film reduction.

<Comparative Examples 2 and 3>
The positive photosensitive resin composition was applied on a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 3.0 μm. The film thickness was measured using F20 manufactured by FILMETRICS. The coating film was irradiated with ultraviolet rays having a light intensity of 365 mW / cm ² at 365 nm with various exposure amounts by an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. Thereafter, development was performed by immersing in a 0.4% TMAH aqueous solution for 60 seconds, followed by washing with running pure water for 20 seconds. The lowest exposure amount (mJ / cm ² ) at which no undissolved portion remained in the exposed area was defined as sensitivity. Further, the amount of decrease in the film thickness of the unexposed part was defined as film reduction.

[Evaluation of half exposure margin]
A high-sensitivity layer was formed on the low-sensitivity layer in the same manner as in the above [Evaluation of sensitivity and film reduction], irradiated with ultraviolet rays, heated after exposure, developed, and washed. At that time, an exposure amount range in which the remaining film amount in the exposed portion was 2 μm ± 5% was defined as a half exposure margin.

[Evaluation results]
The results of the above evaluation are shown in Table 2 below.

In Examples 1 to 4, a high sensitivity layer is used for the upper layer and a low sensitivity layer is used for the lower layer, so that high transmittance can be maintained, development can be performed with high sensitivity and no film loss, and a wide exposure margin can be obtained during half exposure. I was able to.
On the other hand, in Comparative Example 1, it was possible to develop with high sensitivity without film loss, but the half exposure margin was extremely low.
Further, both Comparative Examples 2 and 3 have lower sensitivity and less film thickness in the unexposed area compared to Examples 1 to 4. From these results, the sensitivity of these single-layer systems increases as the sensitivity increases. A half exposure margin and a decrease in transmittance were observed.

  The transparent cured film obtained by the method for producing a transparent cured film of the present invention is applicable to the production of a TFT flattening film in a transflective liquid crystal display element. In particular, the contact hole and the unevenness for reflection are formed by half exposure. It is suitable as a material for forming a transparent cured film for simultaneous formation.

Claims (9)

Laminating two layers of positive photosensitive resin layers having different exposure sensitivities on a base material so that the low sensitivity positive photosensitive resin layer is positioned between the base material and the high sensitivity positive photosensitive resin layer. A step of exposing the two layers of the positive photosensitive resin layer, a step of heating the two layers of the positive photosensitive resin layer after exposure, and a step of developing the two layers of the positive photosensitive resin layer. , A method for producing a transparent cured film comprising a step of post-baking the two positive photosensitive resin layers,
The low-sensitivity positive photosensitive resin layer is a positive photosensitive resin layer containing the following components (A), (B), (C) and (D): Manufacturing method of heat-resistant cured film.
(A) Component: Alkali-soluble resin (B) Component: Compound having two or more vinyl ether groups in the molecule (C) Component: Compound that crosslinks with (A) component by post-baking (D) Component: Photoacid generation Agent   The method for producing a transparent cured film according to claim 1, wherein the exposure is half exposure.   The method for producing a transparent cured film according to claim 1 or 2, wherein the post-exposure heating is performed at a temperature of 80 ° C to 140 ° C, and the post-baking is performed at a temperature of 150 ° C to 270 ° C. The high-sensitivity positive photosensitive resin layer is a positive photosensitive resin layer containing the following components (A), (B), (C) and (D), respectively. The manufacturing method of the transparent cured film as described in any one of Claims 3.
(A) Component: Alkali-soluble resin (B) Component: Compound having two or more vinyl ether groups in the molecule (C) Component: Compound that crosslinks with (A) component by post-baking (D) Component: Photoacid generation Agent   In the low-sensitivity positive photosensitive resin layer, based on 100 parts by mass of the component (A), 1 to 80 parts by mass of the component (B), 3 to 70 parts by mass of the component (C), and 0. The manufacturing method of the transparent cured film as described in any one of Claims 1 thru | or 4 containing 5 thru | or 50 mass parts said (D) component.   The manufacturing method of the transparent cured film as described in any one of Claims 1 thru | or 5 whose base material is the base material in which the TFT element was formed.   A TFT array flattened film comprising a transparent cured film obtained by the production method according to claim 1.   The display element which has a transparent cured film obtained by the manufacturing method as described in any one of Claims 1 thru | or 5.   The liquid crystal display element which has a transparent cured film obtained by the manufacturing method as described in any one of Claims 1 thru | or 5.