TWI431425B - Method for producing transparent cured coating by using positive photosensitive resin layer for half exposure - Google Patents

Description

Method for producing transparent cured film using positive photosensitive resin layer for half exposure

The present invention relates to a method for producing a transparent cured film obtained by using a positive photosensitive resin layer.

More specifically, a method of producing a transparent cured film by exposing two layers of positive photosensitive resin layers having different exposure sensitivities formed on a substrate and finally performing a post-baking step.

In the case where the photosensitive resin layer having the above-described structure is subjected to half exposure, a method of producing a reflective layer of any shape, a flat transmission layer, and a contact hole with high precision can be applied, and in particular, Manufacturer of transmissive liquid crystal display elements.

In general, a thin film transistor (TFT) type liquid crystal display device has a reflection type, a semi-transmissive type, a transmission type structure, and the like, and can be appropriately selected by a device to be used. Among them, a semi-transmissive type that can be displayed in a high-definition manner, both indoors and outdoors, can be used. In such a transflective liquid crystal display device, a flattening film is used for the purpose of flattening the TFT and widening the aperture ratio. Thus, the light scattering property of the reflecting portion can be maintained on the flattening film, and irregularities in the surface can be produced by improving the reflection efficiency. On the unevenness, an aluminum or molybdenum-like metal can be used as a reflector and a pixel electrode to form a film. On the other hand, in the transmissive portion, an ITO-like transparent electrode is used as a pixel electrode. In order to make the pixel electrodes and the common electrode conductive, a contact hole is formed in the planarization film.

In the method of producing the unevenness and the contact hole, a thick film protrusion is formed on the substrate by using a photosensitive material, and a photosensitive material is applied thereon to planarize the protrusion to a certain extent to form a reflection unevenness. The method of contacting the holes is often used.

However, in this method, since it is necessary to form the pattern of the photosensitive material twice, the production efficiency (through-put) of the component manufacturing cannot be improved, and therefore, the improvement in production efficiency is required.

Therefore, in recent years, it has been proposed to apply a photosensitive material and then expose it by a halftone mask (half exposure), whereby the contact hole and the unevenness for reflection can be simultaneously produced.

When the photosensitive material used here is excellent in handling resistance such as heat resistance and solvent resistance, and the adhesion to the underlayer is good, the pattern can be formed with high precision under various processing conditions suitable for the purpose of use. In addition, a wide range of processes are required, and those having high sensitivity and high transparency, and those having less film unevenness after development are required.

Therefore, from the viewpoint of such a desired property, a photosensitive resin composition containing a naphthoquinonediazide compound is widely used in the above-mentioned photosensitive material.

However, among the required characteristics of such a photosensitive resin material, sensitivity and process margin can be exemplified as important characteristics. In the industrial production such as display components, it is feasible to shorten the production time, so the sensitivity is required for such photosensitive resin materials in the current situation where the demand for liquid crystal displays is significantly increased. One of the most important features. Further, it is very important that the process range is such that a high-precision reflective layer is formed. In recent years, as the substrate is enlarged to an exposure limit, the wide development limit is necessary to improve the productivity yield.

However, the conventional photosensitive resin material containing the above naphthoquinonediazide compound is not sufficiently satisfactory in the surface of sensitivity. In the material, the solubility of the polymer to the alkali developing solution is improved, and although the effect of improving the sensitivity is improved, the method has a limit, and the dissolution of the unexposed portion is also caused to cause a decrease in the residual film rate, which is used for a large display. The substrate has the disadvantage of causing film unevenness.

Therefore, until now, there have been some proposals for the purpose of high sensitivity of photosensitive resin materials.

For example, there is a proposal for a radiation-sensitive linear resin composition containing at least one of an alkali-soluble resin and a specific polyhydroxy compound and a derivative thereof (see, for example, Patent Document 1), and a naphthoquinonediazide-based compound It is understood that the photosensitive resin material exhibits higher sensitivity when exposed to a halftone mask, and the exposure limit of the half-exposure region tends to decrease, so that it is impossible to coexist high sensitivity and exposure limit.

On the other hand, there is a proposal for developing a chemically enhanced photoresist as a photosensitive material having high sensitivity and high resolution, and a conventional chemically enhanced photoresist developed as a photoresist for semiconductors is more complicated than the i-line. A light source (KrF, ArF) which is short-wavelength can also be adapted, and a finer pattern can be formed (see, for example, Patent Document 2).

However, in the above chemically enhanced photoresist, in the presence of a photoresist stripping liquid at a high temperature for film hardening, the thermal crosslinking portion of the bonding group or the ether bond of the protective group is easily decomposed. The heat resistance and chemical resistance are remarkably lowered, and it is almost impossible to use it as a permanent film.

Further, in order to make heat hardening possible, it is intended to introduce an epoxy group or an amine-based plastic into a chemically-enhanced photoresist, and a photo-acid generator (hereinafter referred to as PAG) in the photoresist due to exposure. The influence of the acid generated and the crosslinking of the exposed portion cause a new problem such as the disappearance of the dissolution of the unexposed portion, so that the introduction of the chemically enhanced photoresist is difficult. .

In such a case, in the manufacture of a transflective liquid crystal display element, particularly in the production of a planarizing film, the aperture or the interval of the opening portion of the reticle pattern for half exposure can be exposed to form a contact hole. Or the concave and convex pattern for reflection. However, there is a limit to the amount of adjustment of the mask, and it is considered that it is necessary to lower the exposure sensitivity of the planarizing film in order to form an uneven pattern having high precision. Therefore, in the formation of the contact hole, it is necessary to increase the exposure amount, and as a result, it is difficult to improve the manufacturing efficiency of the device manufacturing.

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. 4-211255. Patent Document 2: U.S. Patent No. 5,075,199

Invention

The present invention has been made to overcome the above-mentioned problems, and an object thereof is to provide a method for producing a transparent cured film which can maintain a high sensitivity and has a wide exposure limit as it is. Among them, in the transflective liquid crystal display device, it can be applied to the production of a TFT flattening film, and in particular, the object thereof is to provide a transparent cured film which can simultaneously form a contact hole and a reflective unevenness by half exposure. method.

In other words, the first aspect of the present invention provides a method for producing a transparent cured film comprising: two layers of a positive photosensitive resin layer having different exposure sensitivities on a substrate, laminated to a low sensitivity The step of exposing the positive photosensitive resin layer to the position between the substrate and the high-sensitivity positive photosensitive resin layer, exposing the laminated two-layer positive photosensitive resin layer to the two-layer positive photosensitive The step of heating the two layers of the positive photosensitive resin layer by the step of heating the two layers of the positive photosensitive resin layer, and the step of baking the two positive photosensitive resin layers, in the method for producing the transparent cured film, The low-sensitivity positive photosensitive resin layer contains the following (A) component, (B) component, (C) component, and (D) component of the positive photosensitive resin layer,

(A) component: alkali-soluble resin (B) component: Compound (C) which has two or more vinyl ether groups in one molecule: Compound (D) component which cross-reacts and (A) component by post-baking. : Photoacid generator.

The second viewpoint is that the exposure is a method of producing a transparent cured film of the first aspect of the half exposure.

The third aspect is a method for producing a transparent cured film according to the first aspect or the second aspect in which 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.

According to a fourth aspect, the high-sensitivity positive photosensitive resin layer each contains the following (A) component, (B) component, (C) component, and (D) component of the positive photosensitive resin layer, A method of producing a transparent cured film according to any one of the first aspect to the third aspect.

(A) component: alkali-soluble resin (B) component: Compound (C) which has two or more vinyl ether groups in one molecule: Compound (D) component which cross-reacts and (A) component by post-baking: Photoacid generator.

According to a fifth aspect, the low-sensitivity positive photosensitive resin layer contains the component (B) in an amount of 1 to 80 parts by mass based on 100 parts by mass of the component (A), and is 1 to 70 parts by mass ( And a method of producing a transparent cured film according to any one of the first aspect to the fourth aspect, wherein the component (C) is 0.5 to 50 parts by mass of the component (D).

The sixth aspect is a method for producing a transparent cured film according to any one of the first aspect to the fifth aspect, wherein the substrate is a substrate for forming a TFT element.

The seventh aspect is the TFT array planarizing film obtained by the transparent cured film obtained by the manufacturing method of any one of the first aspect to the fifth aspect.

The eighth aspect is the display element of the transparent cured film obtained by the manufacturing method of any one of the first aspect to the fifth aspect.

The ninth aspect is a liquid crystal display element having a transparent cured film obtained by the production method of any one of the first aspect to the fifth aspect.

The transparent cured film obtained by the present invention has an effect of high sensitivity at the time of half exposure and a wide exposure limit, and in particular, it is possible to form a half of the unevenness of the TFT flattening film and the contact hole with high sensitivity and at the same time with high precision. The manufacture of a transmissive liquid crystal display element can be suitably used.

Best form for implementing the invention

The present invention comprises: a two-layer positive photosensitive resin layer having different exposure sensitivities on a substrate, and a layer formed into a low-sensitivity positive photosensitive resin layer which can be located on the substrate and a high-sensitivity positive photosensitive resin A method of manufacturing a transparent cured film characterized by exposing the two layers of the positive photosensitive resin layer to a position, and performing post exposure heating (Post Exposure Bake: PEB), development, and post-baking .

Specifically, the method comprises: forming a low-sensitivity positive photosensitive resin layer on a substrate, and further laminating the high-sensitivity positive photosensitive resin layer on the substrate on the low-sensitivity layer to make the exposure sensitivity different. a step of laminating two layers of the positive photosensitive resin layer, exposing the two layers of the positive photosensitive resin layer to be exposed, and subjecting the two positive photosensitive resin layers to a post-exposure heating step The step of developing the two positive photosensitive resin layers and subjecting the two positive photosensitive resin layers to a post-baking step, wherein the low-sensitivity positive photosensitive resin is used in the method for producing a transparent cured film The layer contains the following (A) component, (B) component, (C) component, and the positive photosensitive resin layer of (D) component, and the manufacturing method of a transparent cured film.

(A) component: alkali-soluble resin (B) component: Compound (C) which has two or more vinyl ether groups in one molecule: Compound (D) component which cross-reacts and (A) component by post-baking: Photoacid generator.

According to the production method of the present invention, a two-layer positive photosensitive resin layer having different exposure sensitivities is laminated on a substrate, and a high-sensitivity positive photosensitive resin layer is exposed while being exposed through a halftone mask. (hereinafter, referred to as a high-sensitivity layer) and a low-sensitivity positive photosensitive resin layer (hereinafter referred to as a low-sensitivity layer) can form a different pattern shape. That is, according to the manufacturing method of the present invention, the half-tone mask can be passed through the high-sensitivity layer and the low-sensitivity layer to form a different screen shape in one exposure.

In the present invention, since the layer is synthesized such that the low-sensitivity layer is located between the substrate and the high-sensitivity layer, the high-sensitivity layer and the low-sensitivity layer remain as unexposed portions during development, and the high-sensitivity layer of the half-exposure portion is The low-sensitivity layer remains after removal, and the positive photosensitive resin layer (high-sensitivity layer and low-sensitivity layer) of the fully exposed portion is completely removed to expose the substrate.

The so-called half exposure portion can be developed with a smaller exposure amount than the full exposure portion, and is a portion that can form a desired image.

In order to obtain a desired picture, intermixing of the low sensitivity layer and the high sensitivity layer of the laminate can be suppressed. In the case where the suppression of the mutual mixing is insufficient in the two layers, the interface between the low-sensitivity layer and the high-sensitivity layer is unclear, and it is difficult to obtain a desired picture at the time of half exposure.

In the present invention, when a solution of a positive photosensitive resin composition forming the layer is applied and then subjected to preliminary drying (heat treatment), the components contained in the resin composition can be mutually formed. Cross-linking is carried out whereby a film which is insoluble in an organic solvent can be formed on the substrate. Therefore, when a high-sensitivity layer is formed on the low-sensitivity layer, even if a solution of the positive-type photosensitive resin composition forming the layer is applied, no intermixing of the low-sensitivity layer and the high-sensitivity layer occurs. .

Next, in the case where the high-sensitivity layer and the low-sensitivity layer are irradiated with light having a smaller amount of exposure than necessary for the start of development, film thinning is suppressed during development, and light having a necessary exposure amount at the start of irradiation and development is suppressed. After that, rapid development (high precision and high sensitivity) is desirable.

Here, in the half-exposure portion, at the time of development, the dissolution of the low-sensitivity layer is the completed exposure amount, and the difference between the exposure amount of the high-sensitivity layer and the start of the exposure becomes a half-exposure limit. In this system, the sensitivity difference between the high-sensitivity layer and the low-sensitivity layer is closely related, and the half-exposure limit is larger as the sensitivity difference between the two layers is larger. That is, if the sensitivity of the high-sensitivity layer is higher, the lower the sensitivity of the low-sensitivity layer, the wider the exposure limit can be. In order to obtain a high-precision picture, the half exposure limit is preferably 10 mJ or more.

On the other hand, in order to improve the manufacturing efficiency of component manufacturing, it is important that the low-sensitivity layer has a certain degree of high sensitivity. In this case, the purpose is to increase the half exposure limit, and if the amount of exposure necessary for the development of the low-sensitivity layer is too large, the sensitivity of the low-sensitivity layer is lowered, and the manufacturing efficiency is lowered.

Therefore, in terms of the low-sensitivity layer, for example, a chemically-sensitive photosensitive layer having high sensitivity is preferred.

Therefore, a high-sensitivity layer is required to be compared with a high-sensitivity low-sensitivity layer, and a high-sensitivity photosensitive layer is preferable, and a more sensitive chemically-enhanced photosensitive layer is preferable.

As described above, the positive-type photosensitive resin layer of the present invention can be obtained by subjecting a desired image to a post-baking to obtain a transparent cured film.

Hereinafter, a more preferable positive photosensitive resin layer will be described.

<Low-sensitivity positive photosensitive resin layer (low sensitivity layer)>

The low-sensitivity layer used in the present invention is an alkali-soluble resin of the component (A), a compound having two or more vinyl ether groups in one molecule of the component (B), and (C) component by post-baking and ( A) A compound obtained by crosslinking a component, and a positive photosensitive resin composition containing a photoacid generator of the component (D).

Usually, in the low sensitivity layer, the positive photosensitive resin composition is dissolved in (E) a solvent to form a solution, and the solution is applied to a substrate and formed under drying. The components are described below.

[(A) ingredient]

The component (A) is an alkali-soluble resin, and has a functional group for thermal crosslinking reaction with a compound having a vinyl ether group of the component (B) in a resin structure; and An alkali-soluble resin having a number average molecular weight of 2,000 to 50,000, which is a functional group for curing a film which is subjected to a thermosetting reaction between a compound which is cross-linked by the component (C) and a component which is cross-linked by the component (A).

In other words, the component (A) is an alkali-soluble resin, and in terms of a suitable material, in the resin structure, has a thermal crosslinking reaction with a compound having a vinyl ether group in the component (B) by prebaking. The functional group to be used, and the functional group for curing the film which can be thermally hardened by a crosslinking reaction with the component (C), and an alkali-soluble resin having a number average molecular weight of 2,000 to 50,000.

a functional group for the thermal crosslinking reaction, which reacts with a vinyl ether group in the compound of the component (B) at an elevated temperature (prebaking temperature), and a thermal crosslinking group between the compound of the component (B) The representative functional group is at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group.

Further, the functional group for film hardening is in the thermal crosslinked body of the component (A) and the component (B) (in the case of the exposed portion, the thermal crosslinked body is further dissociated from the decrosslinked body), Under the high temperature (the temperature after the baking), a crosslinking reaction is carried out between the compound of the component (C) to make the film harden.

As described below, in the case where the component (C) has two or more blocked isocyanate groups, the functional group for film hardening of the component (A) is cleaved through the block portion between the compound of the component (C) and the compound of the component (C). The isocyanate group undergoes a crosslinking reaction to harden the film.

A typical functional group as a functional group for film hardening is at least one selected from the group consisting of a hydroxyl group and an active hydrogen group other than a phenolic hydroxyl group.

Here, the amine group having an active hydrogen means that the proton can be released from the amine group of the first or second stage by the reaction. Therefore, the guanamine group, since it does not have an active hydrogen, should not be used as an amine group having an active hydrogen.

The alkali-soluble resin having the above-described structure is preferably an alkali-soluble resin having such a structure, and the skeleton of the polymer main chain constituting the resin and the type of the side chain are not particularly limited.

However, the resin of the component (A) has a number average molecular weight of 2,000 to 50,000. When the number average molecular weight exceeds 50,000 and is excessive, the development residue is liable to occur, and the sensitivity is largely lowered. On the other hand, when the number average molecular weight is less than 2,000 and is too small, the film of the exposed portion is reduced in a considerable amount at the time of development, and there is a case where the curing is insufficient.

The alkali-soluble resin of the component (A) may, for example, be an acrylic resin, a polyhydroxystyrene resin, a polybenzamine precursor or a polyimine.

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

That is, the specific copolymer described above is an alkali-soluble monomer, that is, at least one monomer selected from the group consisting of a monomer having at least one of a carboxyl group and a phenolic hydroxyl group, and a functional group having a film hardening property. a monomer of a group, that is, a monomer which is at least one selected from the group consisting of a monomer having at least one of a hydroxyl group and an amine group other than a phenolic hydroxyl group, as a constituent unit formed copolymer The number average molecular weight (in terms of polystyrene) is 2,000 to 50,000.

Further, the number average molecular weight and the weight average molecular weight of the above specific copolymer are, for example, a GPC apparatus (Shodex (registered trademark) column KF803L and KF804L) manufactured by JASCO Corporation, and the dissolved solvent tetrahydrofuran is placed in a column at a flow rate of 1 ml/min (column temperature). The conditions under which the flow was eluted at 40 ° C were measured.

The above-mentioned "monomer having at least one of a carboxyl group and a phenolic hydroxyl group" includes a monomer having a carboxyl group, a monomer having a phenolic hydroxyl group, and a monomer having both a carboxyl group and a phenolic hydroxyl group. The monomers are not limited to those having one carboxyl group or phenolic hydroxyl group, and may have plural numbers.

Further, the monomer having at least one of a hydroxyl group having a hydroxyl group and an active hydrogen other than a phenolic hydroxyl group is a monomer having a hydroxyl group other than a phenolic hydroxyl group, and a monomer having an active hydrogen group. And a monomer other than a phenolic hydroxyl group having both a hydroxyl group and an amine group of an active hydrogen. The monomers are not limited to one having a hydroxyl group or an active hydrogen group other than the phenolic hydroxyl group, and may have plural numbers.

Hereinafter, specific examples of the above monomers will be given by way of example, but are not limited thereto.

The monomer having a carboxyl group may, for example, be acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acrylenyloxy)ethyl) phthalate, mono-(2-(methacryl) Mercaptooxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)propene oxime Amines, etc.

The monomer having a phenolic hydroxyl group may, for example, be hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)pyrene. Ene diimine and the like.

The monomer having a hydroxyl group other than the phenolic hydroxyl group may, for example, be 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-propylene fluorenyloxy-6-hydroxyl group. Norbornene-2-carboxy(carboxylic)-6-lactone, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 5-methylpropenyloxy-6-hydroxyl drop Alkenyl-2-carboxy-6-lactone and the like.

Further, the monomer having an amine group having an active hydrogen may, for example, be 2-aminoethyl acrylate or 2-aminomethyl methacrylate.

In addition, the specific copolymer can be formed by using a monomer other than the monomer having a functional group for thermal crosslinking reaction and a monomer having a functional group for film hardening (hereinafter referred to as another monomer) as a constituent unit. Copolymer.

The other monomer, specifically, a monomer having at least one of a carboxyl group and a phenolic hydroxyl group, and a monomer having at least one of a hydroxyl group having a hydroxyl group and an active hydrogen other than a phenolic hydroxyl group is copolymerized. It is preferably as far as possible, and does not limit the characteristics of the component (A), especially without limitation.

Specific examples of the other monomer include an acrylate compound, a methacrylate compound, a maleimide compound, acrylonitrile, maleic anhydride, a styrene compound, and a vinyl compound.

As the acrylate compound, for example, methacrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, mercapto acrylate, mercapto methacrylate, phenyl acrylic acid can be exemplified. Ester, 2,2,2-trifluoroethyl acrylate, tertiary butyl acrylate, cyclohexyl acrylate, different Acrylate, 2-methoxyethyl acrylate, methoxy triethylene 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 8-ethyl-8- Tricyclodecyl acrylate and the like.

As the methacrylate compound, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, fluorenyl group can be exemplified. Acrylate, mercaptomethyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, different Methyl methacrylate, 2-methoxyethyl methacrylate, methoxy triethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate , 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclic Mercapto methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, and the like.

The vinyl compound may, for example, be methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, or propyl vinyl ether.

The styrene compound may, for example, be styrene, methyl styrene, chlorostyrene or bromostyrene.

The maleimide compound may, for example, be maleic imide, N-methylbutylimide, N-phenyl maleimide, and N-ring. Hexyl maleimide and the like.

The method for obtaining the specific copolymer used in the present invention is not particularly limited, and for example, at least one monomer which is appropriately selected from a group of monomers having at least one of a carboxyl group and a phenolic hydroxyl group, and a phenolic hydroxyl group At least one monomer selected from the group consisting of a hydroxyl group and an active hydrogen group having at least one of the monomers, and a monomer other than the above-mentioned monomer, and a polymerization initiator as desired In the solvent, the polymerization is carried out at a temperature of 50 to 110 °C. In this case, the solvent to be used is not particularly limited as long as it is a monomer constituting the specific copolymer and a specific copolymer is dissolved. Specific examples thereof include the solvents described in (E) the solvent described below.

Thus, the specific copolymer obtained is usually in a solution state in which the specific copolymer is dissolved in a solvent.

Further, a solution of the specific copolymer obtained as described above is put into a reprecipitation under stirring with diethyl ether or water, and the resulting precipitate is filtered. After washing, it can be a powder of a specific copolymer under normal pressure or reduced pressure at room temperature or under heat drying. By such an operation, the polymerization initiator or the unreacted monomer which coexists with the specific copolymer can be removed, and as a result, the powder of the purified specific copolymer can be obtained. In the case where the primary operation cannot be sufficiently purified, the obtained powder is redissolved in a solvent, and it is preferred to repeat the above operation.

In the present invention, the powder of the specific copolymer may be used as it is, or the powder may be used, for example, by re-dissolving the solvent (E) described later as a solution.

Further, in the case of the alkali-soluble resin of the component (A), polyglycine, polyglycolate, and a part of the polyamidamine precursor of the ruthenium imidized polyamine can also be used. A polyimine such as an acid-based polyimine, and the like, if it is alkali-soluble, can be used without limitation.

From the viewpoint of the solubility of the polyimine precursor or the polyimine with respect to the developability or the solvent used, the number average molecular weight (polyoxyethylene and polyethylene glycol equivalent) is 2,000 to 50,000. Within the scope.

Further, the number average molecular weight and the weight average molecular weight of the above polyimine precursor or polyimine, for example, a GPC apparatus (Shodex (registered trademark) column KD802, KD803 and KD804) manufactured by JASCO Corporation, is used to dissolve the solvent. A 0.1 mol% lithium bromide N,N-dimethylguanamine carbinamide solution was measured at a flow rate of 1 ml/min in a column (column temperature: 40 ° C) to elute.

The polyamic acid which is a polyimine precursor is generally obtained by polycondensing (a) a tetracarboxylic dianhydride compound and (b) a diamine compound.

(a) The tetracarboxylic dianhydride compound is not particularly limited, and specific examples thereof include pyromellitic dianhydride and 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3, 3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyl An aromatic tetracarboxylic acid such as tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane Alkanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid Dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride Tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride like 1,2,3,4-butane tetracarboxylic dianhydride.

These may be used alone or in combination of two or more compounds.

Further, the (b) diamine compound is not particularly limited, and examples thereof include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, and 4,6-diamine. -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)anthracene, bis(4-amino-3,5-dicarboxyphenyl)anthracene, 4,4'-di Amino-3,3'-dicarboxybiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethylbiphenyl, 4,4'-diamine 3-,3'-dicarboxy-5,5'-dimethoxybiphenyl, 1,4-bis(4-amino-3-carboxyphenoxy)benzene, 1,3-double (4 -amino-3-carboxyphenoxy)benzene, bis[4-(4-amino-3-carboxyphenoxy)phenyl]anthracene, bis[4-(4-amino-3-carboxyphenoxy) Phenyl]propane, 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]hexafluoropropane, 2,4-diaminophenol, 3,5-diamine Phenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis(3-amino-4-hydroxyphenyl)ether, double (4-amino-3-hydroxyl) Phenyl)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)indole, bis(4-amino-3-hydroxyphenyl)indole , bis(4-amino-3,5-dihydroxyphenyl)anthracene, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino group 3-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3,5-dihydroxyphenyl)hexafluoropropane, 4,4'-diamino-3,3'-di Hydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy -5,5'-dimethoxybiphenyl, 1,4-bis(3-amino-4-hydroxyphenoxy)benzene, 1,3-bis(3-amino-4-hydroxyphenoxyl) Benzene, 1,4-bis(4-amino-3-hydroxyphenoxy)benzene, 1,3-bis(4-amino-3-hydroxyphenoxy)benzene, bis[4-(3 -amino-4-hydroxyphenoxy)phenyl]indole, bis[4-(3-amino-4-hydroxyphenoxy)phenyl]propane, 2,2-bis[4-(3-amine a diamine compound having a phenolic hydroxyl group such as -4-hydroxyphenoxy)phenyl]hexafluoropropane, 1,3-diamino-4-hydrothiobenzene, 1,3-diamino-5- Hydrogenthiobenzene, 1,4-diamino-2-hydrothiobenzene, bis(4-amino-3-hydrothiophenyl) ether, 2,2-bis(3-amino-4- a diamine compound having a thiophenol group such as thiophenyl hexafluoropropane, 1,3-diaminobenzene-4-nonanoic acid, 1,3-diaminobenzene-5-nonanoic acid, 1, 4-diaminobenzene-2-decanoic acid, bis(4-aminophenyl-3-indoleic acid) ether, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4, A diamine compound having a decanoic acid group such as 4'-diamino-3,3'-dimethylbiphenyl-6,6'-dicarboxylic acid. Further, p-phenylenediamine, phenyldiamine, 4,4'-methylene-bis(2,6-ethylaniline), 4,4'-methylene-bis(2-iso) Propyl-6-methylaniline), 4,4'-methylene-bis(2,6-diisopropylaniline), 2,4,6-trimethyl-1,3-phenylene Amine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, toildine, m-toluidine, 3,3',5,5'-tetramethyl Benzidine, bis[4-(3-aminophenoxy)phenyl]anthracene, 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-tolylmethyl)hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 1,3-double (4-Aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane , 2,2-bis[4-(4-amino) Oxy) phenyl] hexafluoropropane the diamine compound.

These may be used in combination of one or two or more compounds.

In the case where the polylysine used in the present invention is produced from (a) a tetracarboxylic dianhydride compound and (b) a diamine compound, the compounding ratio of the two compounds, that is, <(b) the total amount of the diamine compound The number of ears/(a) The total number of moles of the tetracarboxylic dianhydride compound is preferably from 0.7 to 1.2. As with the usual polycondensation reaction, the closer the molar ratio is to 1, the greater the degree of polymerization of the polylysine produced increases the molecular weight.

Further, when the diamine compound is used in excess and is polymerized, the terminal amine group can be protected by reacting the carboxylic acid anhydride with respect to the terminal amine group of the remaining polyamine.

Examples of such a carboxylic anhydride include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, and methyl-5-nor. Alkenne-2,3-dicarboxylic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, and the like.

In the production of polyamic acid, the reaction temperature of the reaction of the diamine compound with the tetracarboxylic dianhydride compound is -20 to 150 ° C, preferably at any temperature of -5 to 100 ° C. In the case of obtaining a high molecular weight polylysine, the reaction temperature is 5 ° C to 40 ° C, and the reaction time is suitably selected from the range of 1 hour to 48 hours. In order to obtain a partially ruthenium imidized polyamine acid having a low molecular weight and high storage stability, the reaction temperature is preferably from 40 ° C to 90 ° C, and the reaction time is more than 10 hours.

Further, the reaction temperature in the case where the terminal amine group is protected by an acid anhydride is -20 to 150 ° C, preferably at any temperature of -5 to 100 ° C.

The reaction of the diamine compound with the tetracarboxylic dianhydride compound can be carried out in a solvent. Solvents which can be used herein include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methyl Caprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl hydrazine, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate, ethyl lactate , methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate ,2-ethoxypropionic acid ethyl ester, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol 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 glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate, cyclohexanone, A Ketoethyl ketone, methyl isobutyl ketone, 2-heptanone, and the like. These may be used singly or in combination. Further, in the solvent in which the polylysine is not dissolved, the polylysine produced by the polymerization reaction can be used in the above solvent without being precipitated.

Thus, the polyglycine-containing solution obtained as described above can be used as it is for the solution of the positive photosensitive resin composition. Further, the polyglycolic acid may be precipitated and isolated in a weak solvent such as water, methanol or ethanol to be recovered and used.

The polylysine obtained in this manner is esterified with a carboxyl group and can also be used as a polyphthalate.

The polylysine obtained in this manner can be used alone or in combination with the above alkali-soluble resin.

Further, in the present invention, any polyimine can be used. The polyimine used in the present invention means that the polyimine precursor such as polylysine is chemically or thermally subjected to 50% or more quinone imidization. These polyimines may contain a copolymer of polyamidoximine, polyether quinone or the like.

The polyimine in the positive photosensitive resin composition used in the present invention may have a carboxyl group or a phenolic hydroxyl group in order to impart alkali solubility, or may have a carboxylic acid or a phenolic hydroxyl group by the action of heat or acid. The base is better.

For introducing a carboxyl group or a phenolic hydroxyl group of a polyimine, a method of blocking an amine terminal with an acid anhydride having a carboxyl group or a phenolic hydroxyl group, or a method of using a monomer having a carboxyl group or a phenolic hydroxyl group, or A method in which the ruthenium imidization ratio is 99% or less when the polyimide is imidized.

Further, a method of introducing a group in which a carboxylic acid or a phenolic hydroxyl group is formed by a heat or an acid of a polyimine, a method of forming a monomer having a carboxyl group or a phenolic hydroxyl group by heat or an acid may be used. A method in which a carboxyl group or a phenolic hydroxyl group which has been previously introduced or a carboxylic acid residue which is imidized by hydrazine is reacted by a group which is dissociated by the action of heat or acid.

Such a polyimine is obtained by synthesizing the above polyimine and then performing chemical hydrazine imidization or thermal hydrazylation.

The method of chemical imidization is generally carried out by adding an excess of acetic anhydride and pyridine to a polyimine precursor solution to react from room temperature to 100 ° C. Further, in the method of hot hydrazine imidization, a method in which a polyiminoimine precursor solution is heated while being dehydrated at a temperature of 180 ° C to 250 ° C is generally used.

The polyimine obtained in this manner may be used singly or in combination with other alkali-soluble resins (for example, a specific copolymer or the like) described above.

[(B) ingredients]

The component (B) is a compound having two or more vinyl ether groups in one molecule. In this case, the vinyl ether group which is thermally crosslinked with the alkali-soluble resin of the component (A) is preferably a compound having two or more compounds in one molecule, and the type and structure thereof are not particularly limited.

The compound of the component (B), after being thermally crosslinked with the alkali-soluble resin of the component (A), is acid-soluble by exposure in the presence of a photoacid generator, and is soluble in the alkali of the component (A). The resin is separated (decrosslinked), and then removed by development with an alkali developing solution together with the alkali-soluble resin of the component (A). Therefore, in view of such a compound, a vinyl ether compound or the like which is used for a component of a vinyl ether type chemically amplified photoresist can be generally used. In the use of such compounds, the amount of the compound is varied to adjust the thermal crosslink density to provide the benefit of controlling the resulting image.

Next, in the compound of the component (B), among the above-mentioned vinyl ether-based compounds, in particular, the compounds represented by the formulae (1) and (2) can be developed without any residual film or residue in the exposed portion. The point is better.

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

(where m is an integer from 2 to 10).

The n of the formula (1) shows the number of vinyl ether groups in one molecule, and in the n aspect, it is more preferably an integer of 2 to 4. Next, m of the formula (2) also shows the number of vinyl ether groups in one molecule, and m is more preferably an integer of 2 to 4.

Specific examples of the compound represented by the formula (1) and the formula (2) may, for example, be bis(4-(vinyloxymethyl)cyclohexylmethyl)glutarate or tris(ethylene glycol) diethylene. Ether, divinyl adipate, diethylene glycol divinyl ether, tris(4-(vinyloxy)butyl) trimellitate, bis(4-(vinyloxy)butyl)terephthalic acid An ester, bis(4-(ethyleneoxy)butyl isophthalate, and cyclohexanedimethanol divinyl ether such as 1,4-cyclohexanedimethanol divinyl ether.

Further, the compound of the component (B) may be used in an amount of from 1 to 80 parts by mass, preferably from 5 to 40 parts by mass, per 100 parts by mass of the component (A). When the amount of the compound of the component (B) is less than the lower limit of the range, the shape of the relief pattern in which the film is thinned in the unexposed portion to be conspicuous is defective. On the other hand, when the amount of the compound of the component (B) exceeds the upper limit of the range and the amount is excessive, the sensitivity of the film is largely lowered, and the residue between the patterns is caused after development.

[(C) ingredient]

The component (C) is a compound which is crosslinked with the component (A) by post-baking, and a compound having two or more blocked isocyanate groups in one molecule can be suitably used. This is formed by thermally crosslinking the compound with the component (B) or further forming an alkali-soluble resin of the component (A) which is decrosslinked therewith, and is, for example, baked after the usual use. It is preferable that the temperature has two or more compounds in one molecule of the thermoistable block isocyanate group, and the type and structure thereof are not particularly limited. In the compound of the component (C), the isocyanate group (-NCO) has two or more blocked isocyanate groups in one molecule by a suitable protecting group, and then, when exposed to heat at a high temperature, The protective group (block portion) is removed by thermal dissociation, and the functional group which is thermally hardened in the alkali-soluble resin of the component (A) by the generated isocyanate group (for example, a hydroxyl group and an active hydrogen other than the phenolic hydroxyl group) Amines which crosslink with each other, for example, formula (3) The compound represented by the formula (wherein R ² is an organic group of the block moiety) has two or more groups in one molecule (the group may be the same or may be a different one).

A compound having a component (C) having two or more blocked isocyanate groups in one molecule can be obtained, for example, by a function of a suitable blocker with respect to a compound having two or more isocyanate groups in one molecule.

The compound having two or more isocyanate groups in one molecule may, for example, be isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylene bis(4-cyclohexyl isocyanate), trimethyl group. Hexamethylene diisocyanate or the like, or a dimer, a trimer, or the like, and a reaction with a glycol, a triol, a diamine, or a triamine.

As the block agent, there are, for example, methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N,N-dimethylaminoethanol, 2-ethoxyethanol, cyclohexanol Alcohols such as phenol, o-nitrophenol, p-chlorophenol, phenols such as o-, m- or p-cresol, decylamine such as ε-caprolactam, acetone oxime, methyl ethyl ketoxime, Methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone quinone, diphenyl ketone oxime and the like, pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, etc. Mercaptans such as pyrazoles, dodecanethiols, and benzenethiols.

The compound of the component (C), at a higher temperature after the baking temperature, causes thermal dissociation of the block portion, and the crosslinking reaction is carried out through the isocyanate group, and the temperature is lower at the prebaking temperature, in order not to proceed. Crosslinking by the isocyanate group causes the thermal dissociation temperature of the block portion to be considerably higher than the prebaking temperature, and for example, a compound having a component (C) of 120 ° C to 230 ° C is particularly preferable.

The compound of the component (C) may, for example, be a specific example.

In the formula, the isocyanate compound is a compound of the component (C) derived from isophorone diisocyanate, and the heat resistance and the film coating property are more preferable. Examples of such a compound include the following.

R in the following formula shows an organic group.

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

Further, the compound of the component (C) may be used in an amount of from 3 to 70 parts by mass, preferably from 5 to 40 parts by mass, per 100 parts by mass of the component (A). When the amount of the compound of the component (C) is too small to reach the lower limit of the range, the thermal curing is insufficient to obtain a satisfactory cured film, and on the other hand, the amount of the compound of the component (C) exceeds the upper limit of the range. On the other hand, when it is excessive, development is not sufficient, and development residue is generated.

[(D) ingredient]

The component (D) is a photoacid generator (also referred to as PAG). This is a substance which directly or indirectly causes an acid (such as a decanoic acid, a carboxylic acid, etc.) to be used for irradiation with exposure light, and the type, structure, and the like are not particularly limited as long as they have such properties.

The photoacid generator of the component (D) may, for example, be a diazomethane compound, an onium salt compound, a quinone compound, a diterpenoid compound, a decanoic acid derivative compound, a nitrobenzyl compound or a benzoin toluene. Acid salt compound, iron aromatic hydrocarbon complex, halogen containing three A compound, an acetophenone derivative compound, and a cyano group-containing sulfonate compound. The photoacid generator which is known or known in the art is not particularly limited and can be suitably used in the present invention. Further, in the present invention, the photoacid generator of the component (D) may be used singly or in combination of two or more.

Specific examples of such a photoacid generator include the following. In particular, these compounds are a few of the most suitable photoacid generators, and of course there is no limitation to them.

Diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyl Iodine iodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate (arsenate), bis(p-terphenyl)iodonium hexafluorophosphate , bis(p-terphenyl)phenyl iodonium sulfonate, bis(p-tert-butylphenyl)iodonium tosylate, bis(p-terphenyl)iodonium trifluoromethane Sulfonate, bis(p-terphenyl)iodonium tetrafluoroborate, bis(p-terphenyl)iodonium chloride, bis(p-chlorophenyl)iodonium chloride, double (p-chlorophenyl) iodonium tetrafluoroborate, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium trifluoromethanesulfonate, tris(p-methoxyphenyl)phosphonium Fluoroborate, tris(p-methoxyphenyl)phosphonium hexafluorophosphonate, tris(p-ethoxyphenyl)phosphonium tetrafluoroborate, triphenylsulfonium chloride, triphenylphosphonium bromide , tris(p-methoxyphenyl)phosphonium tetrafluoroborate, tris(p-methoxyphenyl)phosphonium hexafluorophosphonate, tris(p-ethoxyphenyl)phosphonium tetrafluoro Esters,

In addition, the photoacid generator of the component (D) is used in an amount of from 0.5 to 50 parts by mass, preferably from 1 to 30 parts by mass, per 100 parts by mass of the alkali-soluble resin of the component (A). When the amount of the photoacid generator of the component (D) is less than the lower limit of the range and is too small, the alkali-soluble resin of the component (A) of the compound of the component (B) which is thermally crosslinked upon exposure is thermally exposed. The dissociation cannot be performed, and the undulating pattern of the desired pattern is difficult to obtain. On the other hand, when the amount of the photoacid generator of the component (D) exceeds the upper limit of the range and is excessive, the positive photosensitive resin composition is The storage stability becomes degraded.

[(E) Solvent]

The positive photosensitive resin composition of the present invention contains the above components (A) to (D), and usually these components are dissolved in (E) a solvent to apply a solution to form a positive photosensitive resin layer. .

In the solvent (E), the component (A) to the component (D) is dissolved, and the component (F) to be added is dissolved as desired, and the solvent is used as the solvent having the solubility. The structure and the like are not particularly limited.

The solvent (E) may, for example, be 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-methylpropanoate, ethyl ethoxyacetate, glycolic acid Ester, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxy Methyl propionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethyl Acetamide, and N-methylpyrrolidone.

These solvents may be used alone or in combination of two or more.

Among the (E) solvents, 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. It is more preferable from the viewpoint of good film coating property and high safety. These solvents are generally used as a solvent for a photoresist material.

[(F) ingredient]

The component (F) is a surfactant. In the preparation of the solution of the positive photosensitive resin composition, it is possible to add a surfactant in order to improve the coatability without impairing the effects of the present invention.

The surfactant of the component (F) is not particularly limited, and examples thereof include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant. For the surfactant, for example, a commercially available product manufactured by Dainippon Ink Co., Ltd., or manufactured by Dainippon Ink Co., Ltd., or Asahi Glass Co., Ltd. can be used. These commercial products are suitable because they are easily available. Specific examples thereof include f-top EF301, EF303, EF352 (manufactured by Jemco Co., Ltd.), magafuck F171, F173, R-30 (manufactured by Dainippon Ink and Chemicals, Inc.), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.) A fluorine-based surfactant such as Asahi guard AG710, Safron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.).

These surfactants may be used alone or in combination of two or more.

In the case of using a surfactant, the content thereof is usually 0.2% by mass or less, preferably 0.1% by mass or less, based on 100% by mass of the solution of the positive photosensitive resin composition. When the amount of the surfactant used in the component (F) is set to be more than 0.2% by mass, the effect of improving the coating property is inactivated, and there is no economic effect.

[Other additives]

Further, the positive-type photosensitive resin composition used in the present invention may contain a binder, a pigment, a dye, etc., including a rheology modifier, a decane coupling agent, etc., as long as the effect of the present invention is not impaired. A stabilizer, an antifoaming agent, or a dissolution promoter such as a polyvalent phenol or a polyvalent carboxylic acid is stored. For example, a decane coupling agent can be used for the purpose of improving adhesion to a substrate.

Specific examples thereof include, for example, γ-methacryloxypropyltrimethoxydecane, γ-aminopropyl decane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxylate. Decane, N-aminoethyl-γ-aminopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, γ-isocyanatepropyltriethoxydecane, n-octyltriethoxy Decane, ethylene tris(2-methoxyethoxy)decane, β-(3,4 epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidylpropyltrimethoxydecane, γ- Hydrogenthio-propyltrimethoxydecane, 3-octylthiol-1-propyltriethoxydecane, and the like.

[Positive Photosensitive Resin Composition and Solution]

The positive photosensitive resin composition used in the present invention contains an alkali-soluble resin of the component (A), and a compound having two or more vinyl ether groups in one molecule of the component (B), and is post-baked by the component (C). Further, a compound which crosslinks with the component (A) and a photoacid generator of the component (D). Usually, the component (A) to the component (D) are dissolved in the solvent (E), and a positive photosensitive resin layer is formed in the form of a solution. Further, each of the surfactants of the component (F) and other additives may be contained as desired.

Here, a suitable example of the positive photosensitive resin composition and the solution of the composition is as follows.

[1]: based on 100 parts by mass of the component (A), containing 1 to 80 parts by mass of the component (B), 3 to 70 parts by mass of the component (C), and 0.5 to 50 parts by mass of the positive component of the component (D) A photosensitive resin composition.

[2]: A solution in which the composition of the above [1] is dissolved in a positive photosensitive resin composition of the solvent (E).

[3] A solution containing a positive photosensitive resin composition of 0.2% by mass or less of the component (F) in the composition solution of the above [2].

The ratio of the solid content in the solution of the positive photosensitive resin composition is not particularly limited as long as the components can be uniformly dissolved in the solvent, and is, for example, 1 to 80% by mass, for example, 5 to 60% by mass. %, or 8 to 50% by mass. Here, the solid-forming component means that the (E) solvent is removed from the entire component of the solution of the positive-type photosensitive resin composition.

The preparation method of the solution of the positive photosensitive resin composition is not particularly limited, and examples of the preparation method include, for example, dissolving the component (A) (alkali-soluble resin) in the solvent (E), and the solution is B) component (a compound having two or more vinyl ether groups in one molecule), (C) component (a compound which is crosslinked by (A) component by post-baking), and (D) component (photoacid generation) The method of mixing the agent (F) and the component (F) at a predetermined ratio to form a uniform solution, or a method of mixing other additives as needed in an appropriate stage of the preparation method.

In the case of preparing a solution of the positive photosensitive resin composition, a solution of a specific copolymer obtained by polymerization in a solvent can be used as it is. In this case, the solution of the component (A) is the same as above. When the component (B), the component (C), and the component (D) are added to a uniform solution, the solvent may be added for the purpose of concentration adjustment. In this case, the solvent used in the formation of the specific copolymer may be the same as the solvent used for the concentration adjustment in the preparation of the solution of the positive photosensitive resin composition, and the same may be used.

Therefore, it is preferred that the solution of the positive photosensitive resin composition prepared is filtered using a filter having a pore diameter of about 0.2 μm or the like.

<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 a sufficiently high sensitivity as compared with the sensitivity of the low-sensitivity layer. As the high sensitivity layer, a positive photosensitive resin composition can be used.

The high-sensitivity layer used in the present invention may be the same as the positive-type photosensitive resin composition used for the low-sensitivity layer. In this case, in terms of improving the manufacturing efficiency with high sensitivity, the control of the shape of the pattern is easy, and it is preferable to suppress the thinning of the unexposed film during development.

In this case, in order to increase the sensitivity difference between the low-sensitivity layer and the high-sensitivity layer, the content of the (B) component and the (C) component in the positive photosensitive resin composition of the high-sensitivity layer becomes a lower sensitivity layer. The content (mass) of less content is preferred. Specifically, the component (B) and the component (C) in the positive photosensitive resin composition of the high-sensitivity layer are content of the component (B) which is a positive photosensitive resin composition contained in the low-sensitivity layer ( 10 to 80% of the mass) and 30 to 70% of the content (mass) of the component (C) are preferred. More preferably, the component (B) and the component (C) in the positive photosensitive resin composition of the high-sensitivity layer are (B) component content (mass) of the positive photosensitive resin composition contained in the low-sensitivity layer. 10 to 50%, and the content of (C) component (mass) is preferably 40 to 60%.

Further, in the high-sensitivity layer used in the present invention, when a positive photosensitive resin composition of the same kind as the low-sensitivity layer is used, the positive-type photosensitive resin composition used for the high-sensitivity layer can be compared with the above-mentioned <low sensitivity The preparation method of the [positive photosensitive resin composition and its solution] of the photosensitive resin layer (low sensitivity layer)> is similarly obtained.

In this case, it is preferred that the (A) component to the (E) solvent and the mixed solution containing the component (F) are maintained at a temperature higher than room temperature for a desired period, and some are preferably carried out. The thermal crosslinking reaction, adding the (A) component to the (E) solvent, and adding the component (F) as desired, and obtaining a positive photosensitive resin containing the crosslinked body of the component (A) and the component (B) a solution of the composition.

Further preferably, the mixed solution is maintained at a temperature of 30 ° C to 70 ° C for 2 hours to 5 days, and the (A) component to the (E) solvent is added, and the desired component (F) is added to obtain a content ( A) A solution of a positive photosensitive resin composition of a crosslinked body of the component (B).

By adjusting under the above temperature and time conditions, the uniformity of the obtained resin composition solution can be increased, whereby the photoacid generator can be more efficiently dispersed in the film at the time of the subsequent film formation step. This is associated with a dramatic increase in the sensitivity of the resulting film.

When the stirring temperature is higher than 70 ° C, the crosslinking reaction or the hardening reaction is carried out so that the solution of the composition becomes non-uniform, the sensitivity of the obtained film is largely lowered, and if it is lower than 30 ° C, the composition of the composition is lowered. Uniformity cannot be improved, and it is not related to the improvement of sensitivity.

<Formation of Positive Photosensitive Resin Layer (Photosensitive Layer) and Pattern>

In the present invention, a two-layer positive photosensitive resin layer having different exposure sensitivities on a substrate is layer-formed so that a low-sensitivity positive photosensitive resin layer is interposed between the substrate and the high-sensitivity positive photosensitive resin layer. The position and the method of forming the layers are not particularly limited.

For example, a solution of a positive photosensitive resin composition for a low sensitivity layer, a substrate used for a semiconductor (for example, a ruthenium/yttrium oxide coated substrate, a Si ₃ N ₄ (silicon nitride) substrate, a metal such as aluminum, molybdenum, On a substrate coated with chromium or the like, a glass substrate, a quartz substrate, an ITO substrate, or the like, or a substrate on which a device such as a transistor is formed, by spin coating, flow coating, roll coating, slit coating The slit is then subjected to spin coating, inkjet coating, or the like, and then pre-dried by a hot plate or an oven to form a low-sensitivity layer. Next, a solution of the positive photosensitive resin composition for the high-sensitivity layer is applied in the same manner as the low-sensitivity layer, and is preliminarily dried by a hot plate or an oven to form a high-sensitivity layer.

In terms of the conditions for the preliminary drying, for example, a heating temperature and a heating time which are suitably selected from a temperature of 70 ° C to 160 ° C and a time of 0.3 minutes to 60 minutes may be employed. The heating temperature and the heating time are preferably from 80 ° C to 140 ° C and from 0.5 minutes to 10 minutes.

In the preliminary drying, the solvent is removed, and the compound having a vinyl ether group of the component (B) is crosslinked with the resin of the component (A), whereby the alkali developing solution becomes a film which is insoluble. In this case, the temperature of the preliminary drying is lower than the lower limit of the above temperature range, and the solvent may be mostly left in the film and may not be formed into a pattern for the purpose, or may be applied during the coating of the high sensitivity layer. In the case where the low-sensitivity layer is mixed with each other, thermal crosslinking becomes insufficient, and the film is thinned in the unexposed portion. Further, when the temperature exceeds the upper limit of the temperature range, the crosslinking is not performed, and the development of the unexposed portion may occur, and the formed thermally crosslinked portion may be cut again in the unexposed portion. There is a case where the film is thinned.

Further, the film thickness of the positive photosensitive resin layer (the layer in which the low sensitivity layer and the high sensitivity layer are combined) is, for example, 0.1 to 30 μm, for example, 0.2 to 10 μm, and further, for example, 0.2 to 5 μm.

In this case, the film thickness of each of the low-sensitivity layer and the high-sensitivity layer can be arbitrarily selected without impairing the effects of the present invention.

In the positive photosensitive resin layer obtained by the above method, when the film is exposed to light such as ultraviolet rays, ArF, KrF, F ₂ laser light or the like using a halftone mask having a predetermined pattern, self-positive photosensitive light is used. The action of the acid generated by the photoacid generator of the component (D) contained in the resin layer is such that the exposed portion of the film is soluble in the alkaline developer.

I-line exposure to the above, at least one optical wavelength of the g-line and h-line having, or to ArF, KrF F ₂ laser light, or to the better.

Next, post-exposure heating is performed with respect to the positive photosensitive resin layer. In the heating condition in this case, a heating temperature and a heating time which are suitably selected from a temperature of 80 ° C to 140 ° C and a time of 0.3 minutes to 60 minutes may be employed.

Thereafter, development was carried out using an alkaline developer. Thereby, in the positive photosensitive resin layer, the half-exposed portion is only the high-sensitivity layer, and the fully exposed portion is the high-sensitivity layer, and the low-sensitivity layer is also removed, and the pattern-like undulation can be formed. Relief pattern.

The alkaline developing solution which can be used may, for example, be an aqueous solution of an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, or a tetrahydric ammonium hydroxide, tetraethylammonium hydroxide or choline hydroxide. An aqueous solution of an aqueous solution of a quaternary ammonium, an aqueous solution of an amine such as ethanolamine, propylamine or ethylenediamine. Further, a surfactant or the like may be added to the developer.

In the above, tetraethylammonium hydroxide 0.1 to 2.38 mass% aqueous solution can be used as a photoresist developing solution. In the photosensitive resin composition of the present invention, the alkaline developing solution can be used without causing expansion or the like. Developed well between the topics.

Further, the development method may be used arbitrarily by a liquid-filling method, a dipping method, a shaking dipping method, or the like. The development time at this time is usually 15 seconds to 180 seconds.

After the development, the positive photosensitive resin layer is washed with running water for, for example, 20 to 90 seconds, and then the air on the substrate can be removed by using compressed air or compressed nitrogen or spinning to perform air drying. A film formed by the pattern can be obtained.

<Formation of Transparent Curing Film>

Next, a film is formed on such a pattern, and after the film is thermally cured, post-baking is performed. Specifically, it can be heated by using a hot plate or an oven to obtain heat resistance, transparency, flatness, and low water absorption. It is excellent in chemical resistance and has a good undulating pattern.

In the case of post-baking, the heating temperature is selected from the range of 150 ° C to 270 ° C, which is 5 minutes to 30 minutes on a hot plate, and 30 minutes to 90 minutes in an oven. The method was adopted.

Therefore, by such a subsequent baking, a transparent cured film having a good pattern shape can be obtained.

In the present invention, a high-refractive property is imparted to the low-sensitivity layer and a high reflow solderability is imparted to the high-sensitivity layer, whereby a TFT array planarizing film of a transflective liquid crystal display element can be produced.

As described above, according to the production method of the present invention, it is possible to form a coating film having a fine pattern having a wide half exposure limit because the film thickness of the unexposed portion is extremely small at the time of sufficient high sensitivity and development.

Therefore, for example, an array flattening film of a TFT type liquid crystal element, a manufacturing step of various films such as an interlayer insulating film, a protective film, an insulating film, a color filter, and the like in a liquid crystal or an organic EL display can achieve high manufacturing efficiency.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples.

[Simplified Symbols Used in the Embodiments] 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-cyclohexyl maleimide imine AIBN: azobisisobutyronitrile PGMEA: propylene glycol monomethyl Ethyl ether acetate PGME: propylene glycol monomethyl ether PAG1: CGI1397 (trade name) / compound name: 2-methyl-α-[5-[[(propylsulfonyl)oxy) ]imino]-(5H)-thienylene]benzeneacetonitrile (compound of formula (7)) PVE1: three (4-(ethyleneoxy)butyl) trimellitate PVE2: 1,4-cyclohexane Alkane dimethanol divinyl ether NCO1: VESTAGON (registered trademark) B 1065 (trade name) / compound name: ε-caprolactam block polyisocyanate (compound of formula (S-4)) R30: Large Japan Magafuck R-30 (trade name) (fluorine-based surfactant) MPTS: γ-methyl propylene methoxy propyl trimethoxy decane P200: P-200 (trade name) manufactured by Toyo Seiki Co., Ltd. 4,4'-[1-[4-[1-(4-Hydroxyphenyl)-1methylethyl]phenyl]ethylidene]bisphenol 1 molar and 1,2-naphthoquinone-2- Condensation reaction of diazido-5-sulfonyl chloride 2 molar Synthesis of sensitizer (1,2-quinonediazide compound) GT4: epoxidized four butane tetracarboxylic acid - (3-methyl cyclohexenyl) ε- caprolactone modified

[Measurement of the number average molecular weight and the weight average molecular weight] The number average molecular weight and the weight average molecular weight of the specific copolymer obtained in the following synthesis examples were determined by using a GPC apparatus (Shodex (registered trademark) column KF803L and KF804L) manufactured by JASCO Corporation. Tetrahydrofuran was measured under the conditions of a flow rate of 1 ml/min through a column (column temperature: 40 ° C). In addition, the following 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> A monomer component constituting a specific copolymer was obtained by using MAA 19.4 g, CHMI 35.3 g, HEMA 25.5 g, MMA 19.8 g, and a radical polymerization initiator using AIBN 5 g in the solvent PGMEA 212.5 g. The polymerization was carried out at a temperature of from 60 ° C to 100 ° C to obtain a solution of a component (specific copolymer) of Mn 4,100, Mw 7,600 (specific copolymer concentration: 32.0% by mass). (P1)

<Synthesis Example 2> A monomer component constituting a specific copolymer was obtained by using MAA 15.5 g, CHMI 35.3 g, HEMA 25.5 g, MMA 23.7 g, and a radical polymerization initiator using AIBN 5 g in the solvent PGMEA 212.5 g. The polymerization was carried out at a temperature of from 60 ° C to 100 ° C to obtain a solution of a component (specific copolymer) having a Mn of 4,400 and a Mw of 7,000 (specific copolymer concentration: 32.0% by mass). (P2)

<Composition Examples 1 to 5> According to the composition shown in Table 1 below, the (B) component, the (C) component, the (D) component, and the (E) solvent were further added to the solution of the component (A). F) The components are mixed at a predetermined ratio, stirred at a temperature of 23 ° C for 30 minutes, or stirred at 35 ° C for 3 days to form a uniform solution, thereby preparing a positive photosensitive resin composition of each of the examples and the comparative examples. Solution.

<Composition Example 6> An alkali-soluble resin solution, 17.2 g of the specific copolymer solution (P1) obtained in Synthesis Example 1, and 1.1 g of P200 of a 1,2-quinonediazide compound, which was crosslinked by an epoxy group. The compound GT4 1.1 g, the surfactant R30 0.0039 g, the adhesion aid MPTS 0.25 g, the solvent PGMEA 5.2 g were mixed, and the solution of the positive photosensitive resin composition was adjusted by stirring at room temperature for 8 hours.

<Constituent Example 7> An alkali-soluble resin solution, 17.2 g of the specific copolymer solution (P2) obtained in Synthesis Example 2, and 1.7 g of P200 of a 1,2-quinonediazide compound, and an epoxy group cross-linking The compound GT4 1.1 g, the surfactant R30 0.0039 g, the adhesion aid MPTS 0.25 g, the solvent PGMEA 6.5 g were mixed, and the solution of the positive photosensitive resin composition was adjusted by stirring at room temperature for 8 hours.

<Examples 1 to 4 and Comparative Examples 1 to 3> The two-layer films of Examples 1 to 4 shown in Table 2 and the single-layer films of Comparative Examples 1 to 3 were each measured after high-temperature firing. The light transmittance (transparency), sensitivity, film thickness of the unexposed portion, and half exposure limit.

Further, in the case of obtaining a cured film from the positive photosensitive resin composition, in Comparative Examples 2 and 3, photo-bleaching was performed at the stage before the post-baking after development. On the other hand, in Examples 1 to 4 and Comparative Example 1, the photobleaching was not carried out, but after exposure, the post-exposure heating (PEB) was performed at the stage before the development, and the evaluation order of the two was If the following are different.

[Evaluation of Light Transmittance (Transparency) After High-Temperature Firing] <Examples 1 to 4> A solution of a positive-type photosensitive resin composition for a lower layer was applied onto a quartz substrate using a spin coater, and then The film was prebaked on a hot plate at a temperature of 110 ° C for 120 seconds to form a coating film having a film thickness of 2.0 μm. Next, the upper layer was coated with a solution of a positive photosensitive resin composition on a spin coater, and then prebaked on a hot plate at a temperature of 110 ° C for 120 seconds to form a film thickness of 1.0 μm. Coating film. This coating film was immersed in an aqueous solution of 0.4% tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 60 seconds, and then washed with ultrapure water for 20 seconds. Subsequently, it was heated at 230 ° C for 30 minutes to carry out post-baking to form a cured film having a film thickness of 2.4 μm. The cured film was measured for its initial transmittance at a wavelength of 400 nm using an ultraviolet visible spectrophotometer (SHIMADZU UV-2550 model manufactured by Shimadzu Corporation). Further, this coating film was heated at 250 ° C for 30 minutes, and the transmittance after heating was measured in the same manner 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 a positive photosensitive resin composition was applied onto a quartz substrate by a spin coater, and then prebaked on a hot plate at a temperature of 120 ° C for 120 seconds to form a film thickness of 3.0. Μm coating film. The coating film was immersed in a 0.4% aqueous solution of TMAH for 60 seconds, and then washed with ultrapure water for 20 seconds. Subsequently, it was subjected to post-baking by heating at 230 ° C for 30 minutes to form a cured film having a film thickness of 2.4 μm. The cured film was measured for its initial transmittance at a wavelength of 400 nm using an ultraviolet visible spectrophotometer (SHIMADZU UV-2550 model manufactured by Shimadzu Corporation). Further, this coating film was heated at 250 ° C for 30 minutes, and the transmittance after heating was measured in the same manner at a wavelength of 400 nm. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.

<Comparative Examples 2 and 3> A solution of a positive photosensitive resin composition 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 film thickness. 3.0 μm coating film. The coating film was immersed in a 0.4% aqueous solution of TMAH for 60 seconds, and then washed with ultrapure water for 20 seconds. The coating film was irradiated with ultraviolet light having a light intensity of 5.5 mW/cm ² at an exposure amount of 800 mJ/cm ² (photobleaching) in 365 nmn by an ultraviolet irradiation apparatus PLA-600FA manufactured by Canon Co., Ltd., followed by heating at 230 ° C for 30 minutes. After the baking, a cured film having a film thickness of 2.4 μm was formed. The cured film was measured for its initial transmittance at a wavelength of 400 nm using an ultraviolet visible spectrophotometer (SHIMADZU UV-2550 model manufactured by Shimadzu Corporation). Further, this coating film was heated at 250 ° C for 30 minutes, and the transmittance after heating was measured in the same manner at a wavelength of 400 nm. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.

[Evaluation of Sensitivity and Film Thinning] <Examples 1 to 4> The positive-type photosensitive resin composition for the lower layer was applied onto a tantalum wafer using a spin coater, and then at a temperature of 110 ° C for 120 seconds. The hot plate was prebaked to form a coating film (low sensitivity layer) having a film thickness of 2.0 μm. Subsequently, the coating film was coated with a positive-type photosensitive resin composition for an upper layer using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C for 120 seconds to form a film thickness of 1.0 μm. Coating film (high sensitivity layer). The film thickness was measured using F20 manufactured by FILMETRICS. The coating film was irradiated with ultraviolet light having a light intensity of 5.5 mW/cm ² at 365 nm at various exposure amounts in an ultraviolet irradiation apparatus PLA-600FA manufactured by Cannon Co., Ltd., followed by exposure and heating on a hot plate at a temperature of 110 ° C for 120 seconds. Thereafter, development was carried out by dipping in a 0.4% aqueous solution of TMAH for 60 seconds, and then washing with ultrapure water for 20 seconds. The minimum exposure amount (mJ/cm ² ) at which the scum disappeared in the exposed portion was taken as the sensitivity. Moreover, the amount of film thickness reduction of the unexposed part is made thin as a film.

<Comparative Example 1> A positive photosensitive resin composition was applied onto a tantalum wafer using a spin coater, and then prebaked on a hot plate at a temperature of 110 ° C for 120 seconds to form a film thickness of 3.0 μm. Coating film. The film thickness was measured using F20 manufactured by FILMETRICS. Here, the coating film was irradiated with ultraviolet light having a light intensity of 5.5 mW/cm ² at 365 nm at various exposure amounts with an ultraviolet irradiation apparatus PLA-600FA manufactured by Canon Co., Ltd., followed by exposure and heating on a hot plate at a temperature of 110 ° C for 120 seconds. Thereafter, the mixture was developed under a dipping of 0.4% of TMAH aqueous solution for 60 seconds, and then washed with ultrapure water for 20 seconds. The minimum exposure amount (mJ/cm ² ) at which the scum disappeared in the exposure portion was taken as the sensitivity. Moreover, the amount of reduction in the film thickness of the unexposed portion is made thinner as a film.

<Comparative Examples 2 and 3> The positive photosensitive resin composition was applied onto a tantalum wafer using a spin coater, and then prebaked on a hot plate at a temperature of 110 ° C for 120 seconds to form a film thickness of 3.0. Μm coating film. The film thickness was measured using F20 manufactured by FILMETRICS. Here, the coating film was irradiated with ultraviolet light having a light intensity of 5.5 mW/cm ² at various exposure amounts at 365 nm using an ultraviolet irradiation apparatus PLA-600FA manufactured by Canon Inc. Thereafter, the mixture was developed under a dipping of 0.4% of TMAH aqueous solution for 60 seconds, and then washed with ultrapure water for 20 seconds. The minimum exposure amount (mJ/cm ² ) at which the scum disappeared in the exposed portion was taken as the sensitivity. Moreover, the amount of reduction in the film thickness of the unexposed portion is thinned as a film.

[Evaluation of the half-exposure limit] In the same manner as the above [Evaluation of sensitivity and film thinning], a high-sensitivity layer was formed on the low-sensitivity layer, and ultraviolet rays were irradiated, and after exposure, heating, development, and washing were performed. In this case, the exposure amount range in which the residual film amount is 2 μm ± 5% in the exposure portion is used as the half exposure limit.

[Evaluation Results] The results of the above evaluations are shown in Table 2 of the following table.

In the first to fourth embodiments, a high-sensitivity layer was used, and in the lower layer, a low-sensitivity layer was used to maintain a high transmittance, and a high-sensitivity film was not thinned and developed, and a wide exposure limit was obtained at the time of half exposure.

On the other hand, in Comparative Example 1, although development with no film thinning was possible in high sensitivity, the half exposure limit was remarkably lowered.

Further, in any of Comparative Examples 2 and 3, compared with Examples 1 to 4, the sensitivity was low and the film was thinned in the unexposed portion, and as a result of both, the sensitivity was higher in the single layer. High is visible to the half exposure limit, and the transmittance is reduced.

Industrial use possibility

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 device, and in particular, can be simultaneously formed as a contact hole by half exposure. The material for forming the transparent cured film with the unevenness for reflection is appropriate.

Claims (8)

A method for producing a transparent cured film comprising: sandwiching two layers of a positive photosensitive resin layer having different exposure sensitivities on a substrate, and laminating the low-sensitivity positive photosensitive resin layer on the substrate and a step of aligning the positions of the positive photosensitive resin layers with high sensitivity, and performing the half exposure process on the two layers of the positive photosensitive resin layers, and heating the two positive photosensitive resin layers after half exposure. a step of developing the two positive photosensitive resin layers, and a step of post bake the two positive photosensitive resin layers, wherein the method for producing a transparent cured film is characterized in that The low-sensitivity positive photosensitive resin layer contains a positive photosensitive resin layer of the following (A) component, (B) component, (C) component, and (D) component, and (A) component: alkali-soluble resin ( B) Component: a compound (C) having two or more vinyl ether groups in one molecule: a crosslinking reaction with the component (A) by post-baking, and having two or more blocked isocyanate groups in one molecule Compound, component (D): photoacid generator. The method for producing a transparent cured film according to claim 1, wherein the post-exposure heating is carried out at a temperature of from 80 ° C to 140 ° C, and the post-baking is carried out at a temperature of from 150 ° C to 270 ° C. The method for producing a transparent cured film according to the first aspect of the invention, wherein the high-sensitivity positive photosensitive resin layer each contains the following (A) component, (B) component, (C) component, and (D) component, positive photosensitive resin layer, (A) component: alkali-soluble resin (B) component: Two or more vinyl ether groups in one molecule Component (C) component: Compound (D) component which is subjected to a crosslinking reaction with (A) component by post-baking: a photoacid generator. The method for producing a transparent cured film according to the first aspect of the invention, wherein the low-sensitivity positive photosensitive resin layer contains 1 to 80 parts by mass based on 100 parts by mass of the component (A). The component is 3 to 70 parts by mass of the component (C), and is 0.5 to 50 parts by mass of the component (D). The method for producing a transparent cured film according to any one of claims 1 to 4, wherein the substrate is a substrate on which a TFT element has been formed. A TFT array planarizing film comprising a transparent cured film obtained by the production method according to any one of claims 1 to 4. A display element characterized by having a transparent cured film obtained by the production method according to any one of claims 1 to 4. A liquid crystal display element characterized by having a transparent cured film obtained by the production method according to any one of claims 1 to 4.