JP4753036B2 - Positive photosensitive resin composition and cured film obtained therefrom - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition and a method for producing the same, a pattern forming method using the resin composition, and a cured film obtained from the resin composition. More specifically, the present invention relates to a positive photosensitive resin composition suitable for use in display materials and a method for producing the same, a pattern forming method using the resin composition, a cured film obtained from the resin composition, and The present invention relates to various materials using the cured film.

  In general, in a display element such as a thin film transistor (TFT) type liquid crystal display element or an organic EL (electroluminescent) element, a patterned electrode protective film, a planarizing film, an insulating film, and the like are provided. As a material for forming these films, among the photosensitive resin compositions, there are photosensitive resin compositions having a feature that the number of steps for obtaining a required pattern shape is small and sufficient flatness is provided. It is widely used than before.

  These films described above have excellent process resistance such as heat resistance, solvent resistance, and long-term baking resistance, good adhesion to the substrate, and various processes that are suitable for the purpose of use. Various characteristics such as having a wide process margin capable of forming a pattern under conditions, high sensitivity and high transparency, and less film unevenness after development are required. Therefore, from the viewpoint of such required characteristics, conventionally, resins containing a naphthoquinonediazide compound have been widely used as the photosensitive resin composition.

  By the way, sensitivity is mentioned as one of the 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.

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 patent applications have been filed 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). However, this proposed material has a problem in storage stability due to the high symmetry of the photosensitive agent.

  Further, a positive-type radiation-sensitive resin composition containing an alkali-soluble phenol resin and a radiation-sensitive compound (see, for example, Patent Document 2), and a positive-type photosensitive resin composition containing a specific alkali-soluble resin and a quinonediazide compound The thing (for example, refer patent document 3) is proposed. However, since these use a novolak resin as a binder polymer, there is a problem in transparency and stability during firing for a long time.

As described above, it is very difficult to develop a photosensitive resin composition that satisfies other characteristics and has a desired level of high sensitivity. It was difficult to obtain a functional resin composition.

  In general, in the conventional photosensitive resin material containing a naphthoquinonediazide compound, photobleaching is performed to prevent coloring of the cured film and deterioration of transparency by the naphthoquinonediazide compound after exposure and development. Even if this photobleaching process is performed, the obtained film is colored by decreasing the light transmittance when baked at a high temperature of about 250 ° C., and baked at a lower temperature, for example, 230 ° C. for a long time. However, the light transmittance is reduced (colored), and the chemical treatment such as amine solution of the resist stripping solution causes the problem that the light transmittance is lowered and the transparency is deteriorated. Conventional photosensitive resin materials containing a compound have a problem in terms of such heat resistance and chemical resistance (see, for example, Patent Document 4).

On the other hand, a chemically amplified resist has been developed as a photosensitive material with high sensitivity and high resolution. Conventional chemically amplified resists that have been developed as resists for semiconductors can be applied to light sources (KrF, ArF) having wavelengths shorter than those of i-line, and can form finer patterns. In the presence of a resist stripping solution and at a high temperature as used in the present invention, the bonding part of the protective group and the thermal crosslinking part of the ether bond are easily decomposed, and the heat resistance and chemical resistance are extremely low. It was almost impossible to use as (see, for example, Patent Document 5). In addition, in order to enable thermosetting, even if an epoxy or aminoplast cross-linking system is introduced into a chemically amplified resist, the effect of the acid generated from the photoacid generator (PAG) in the resist by exposure Further, since problems such as disappearance of the dissolution contrast with the unexposed portion occur due to the progress of the crosslinking of the exposed portion, it is difficult to introduce such a crosslinked system into the chemically amplified resist.
JP-A-4-21255 Japanese Patent Laid-Open No. 9-006000 JP-A-8-044053 JP-A-4-352101 US Pat. No. 5,075,199

  The present invention has been made in view of the above circumstances, and the problem to be solved is sufficiently high sensitivity, and there is virtually no film loss at an unexposed portion is not measured during development. In addition, high transmittance is maintained even when baked at a high temperature after film formation, and even when exposed to a resist stripping solution (amine-based solution) treatment, the film thickness decreases and the transmittance decreases. It is an object of the present invention to provide a positive photosensitive resin composition and to provide a pattern forming method using the positive photosensitive resin composition, particularly a pattern forming method excellent in resolution. Moreover, this invention makes it a subject to provide the manufacturing method by which the said positive photosensitive resin composition which has such a characteristic is obtained.

  Furthermore, the present invention is a cured film obtained using such a positive photosensitive resin composition, and the reduction in transmittance is remarkably small even by high-temperature baking or resist stripping solution (amine-based solution) treatment. It is an object of the present invention to provide a cured film excellent in heat resistance and chemical resistance that maintains high transparency, and various elements and materials made using such a cured film.

As a result of intensive studies to solve the above problems, the present inventors have found the present invention.
That is, as a first aspect, a positive photosensitive resin composition containing the following component (A), component (B), component (C), component (D), and solvent (E).
Component (A): Functional group for allowing thermal crosslinking reaction with compound of component (B), and functional for film curing capable of thermal curing reaction with compound of component (C) Alkali-soluble resin (B) component having a group and a number average molecular weight of 2,000 to 30,000: Compound (C) component having two or more vinyl ether groups in one molecule: Two in one molecule Compound (D) component having the above blocked isocyanate group: Photoacid generator (E) solvent As a second aspect, the functional group for the thermal crosslinking reaction is at least one selected from the group of a carboxyl group and a phenolic hydroxy group In addition, the functional group for film curing is at least one selected from the group of amino groups having hydroxy groups other than phenolic hydroxy groups and active hydrogen, according to the first aspect. Positive photosensitive resin composition.
As a third aspect, based on 100 parts by mass of component (A), 1 to 80 parts by mass of component (B), 1 to 80 parts by mass of component (C), and 0.5 to 80 parts by mass of component. The positive photosensitive resin composition according to the first aspect or the second aspect, containing the component (D).
As a fourth aspect, the positive photosensitive resin composition according to any one of the first to third aspects, which further contains an alkali-soluble resin other than the component (A) as the component (F). .
As a fifth aspect, as the component (G), the amine compound is further contained in an amount of 0.001 to 5 parts by mass based on 100 parts by mass of the component (A), according to any one of the first to fourth aspects. A positive photosensitive resin composition.
As a sixth aspect, the positive component according to any one of the first to fifth aspects, wherein the surfactant is further contained in an amount of 0.2% by mass or less as the component (H) in the positive photosensitive resin composition. Type photosensitive resin composition.
A step of applying the positive photosensitive resin composition according to any one of the first to sixth aspects to a semiconductor substrate as a seventh aspect, a step of irradiating the application surface with ultraviolet rays through a pattern mask, The pattern formation method including the process of developing the said coating surface and forming a pattern on a semiconductor substrate, and performing the post-baking for film | membrane hardening with respect to the said pattern formation surface.
As a eighth aspect, the pattern forming method according to the seventh aspect, wherein the ultraviolet ray is light having at least one wavelength among i-line, g-line, and h-line.
As a ninth aspect, the pattern forming method according to the seventh aspect, wherein the ultraviolet light is ArF, KrF, or F ₂ laser light.
As a tenth aspect, the following (A) component, (B) component, (C) component, (D) component and (E) solvent are mixed, and the mixed solution is maintained at a temperature higher than room temperature for a required period. As a result, the following thermal crosslinking reaction proceeds somewhat, and in addition to the components (A) to (D), a positive photosensitive resin composition containing a crosslinked product of the components (A) and (B) is produced. A method for producing a positive photosensitive resin composition, comprising:
Component (A): Functional group for allowing thermal crosslinking reaction with compound of component (B), and functional for film curing capable of thermal curing reaction with compound of component (C) Alkali-soluble resin (B) component having a group and a number average molecular weight of 2,000 to 30,000: Compound (C) component having two or more vinyl ether groups in one molecule: Two in one molecule Compound (D) component having the above blocked isocyanate group: Photoacid generator (E) solvent As an eleventh aspect, the mixed solution is maintained at a temperature of 30 ° C. to 70 ° C. for 2 hours to 5 days, The manufacturing method of the positive photosensitive resin composition as described in a 10th viewpoint.
As a twelfth aspect, the functional group for the thermal crosslinking reaction in the component (A) is at least one selected from the group of a carboxyl group and a phenolic hydroxyl group, and the functional group for film curing is a phenolic hydroxyl group The manufacturing method of the positive photosensitive resin composition of the 10th viewpoint or the 11th viewpoint which is at least 1 type chosen from the group of the amino group which has a hydroxyl group and active hydrogen other than.
As a thirteenth aspect, based on 100 parts by mass of the component (A), 1 to 80 parts by mass of the component (B), 1 to 80 parts by mass of the component (C), and 0.5 to 80 parts by mass of The manufacturing method of the positive photosensitive resin composition as described in any one of 10th viewpoint thru | or 12th viewpoint containing the said (D) component.
As a fourteenth aspect, the positive photosensitive resin composition according to any one of the tenth aspect to the thirteenth aspect, which further contains an alkali-soluble resin other than the component (A) as the component (F). Manufacturing method.
As a fifteenth aspect, as the component (G), the amine compound is further contained in an amount of 0.001 to 5 parts by mass based on 100 parts by mass of the component (A), according to any one of the tenth aspect to the fourteenth aspect. Of producing a positive photosensitive resin composition.
As a sixteenth aspect, 0.2 parts by mass of the surfactant as the component (H) is further added in the positive photosensitive resin composition produced by the production method according to any one of the tenth to fifteenth aspects. % Manufacturing method of the positive photosensitive resin composition as described in any one of 10th viewpoint thru | or 15th viewpoint contained.
As a seventeenth aspect, the positive photosensitive resin composition according to any one of the first to sixth aspects or the positive produced by the method according to any one of the tenth to sixteenth aspects. Type cured resin composition obtained by using a photosensitive resin composition.
A liquid crystal display device having the cured film according to the seventeenth aspect as an eighteenth aspect.
An array planarizing film for a liquid crystal display comprising the cured film according to the seventeenth aspect as a nineteenth aspect.
An interlayer insulating film comprising the cured film according to the seventeenth aspect as a twentieth aspect.
A microlens comprising the cured film according to the seventeenth aspect as a twenty-first aspect.

According to the present invention, a positive photosensitive resin composition having a composition capable of being thermally crosslinked with a compound having a vinyl ether group and capable of thermally curing a film with a compound having a blocked isocyanate group. Therefore, it is sufficiently high in sensitivity and practically insignificant so that the film loss in the unexposed area is not measured during development. Moreover, after film formation, baking is performed at a high temperature such as 250 ° C. (or 230, for example). Even if it is baked for a long time at 0 ° C., it maintains the high transmittance, and even when exposed to the resist stripping solution (amine-based solution) treatment, the film thickness can be reduced and the transmittance can be reduced.
According to the present invention, when a pattern is formed using the positive photosensitive resin composition, an excellent resolution pattern (fine pattern size) can be obtained.

  Further, according to the present invention, by obtaining a cured film using such a positive photosensitive resin composition, the transmittance is remarkably lowered even by high-temperature (250 ° C.) baking or resist stripping solution (amine-based solution) treatment. It is a cured film with excellent heat resistance and chemical resistance that maintains small and high transparency. Therefore, liquid crystals such as array flattening films of TFT type liquid crystal elements where chemical amplification resist has not been applied so far. Or the effect that it is suitable also for the use of various film | membrane materials in an organic EL display, and uses, such as a micro lens, is acquired.

Furthermore, according to the production method of the present invention, the composition can be thermally crosslinked with a compound having a vinyl ether group and can be thermally cured with a compound having a blocked isocyanate group, and A positive photosensitive resin composition containing some cross-linked product of an alkali-soluble resin and a compound having a vinyl ether group can be obtained, which is of course compared with the conventional method using a naphthoquinonediazide compound or the like. In addition, it achieves an improvement in sensitivity as compared with the positive photosensitive resin composition not containing the cross-linked product, and there is virtually no film loss at the unexposed area at the time of development. Even after baking at a high temperature such as 250 ° C. after film formation (or even baking for a long time at 230 ° C., for example), high transmittance is maintained, and a resist stripping solution (amine-based solution) Reduction and decrease of the transmittance of the film thickness even when exposed to reason is quite small.

  By the manufacturing method of the present invention, the use of various film materials in liquid crystal or organic EL displays such as an array flattening film of a TFT type liquid crystal element to which a chemically amplified resist has not been applied so far, and microlenses, etc. Production of a positive photosensitive resin composition that can provide a cured film that is also suitable for applications is very advantageously possible.

[Positive photosensitive resin composition]
The positive photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a compound having a vinyl ether group, (C) a compound having a blocked isocyanate group, and (D) a light component. A composition containing an acid generator and (E) a solvent, and optionally containing another alkali-soluble resin of component (F), an amine compound of component (G) or a surfactant of component (H) It is.
In addition, the positive photosensitive resin composition produced by the method of the present invention includes the above-mentioned (A) component to (E) solvent, as well as a crosslinked product of the (A) component and the (B) component described later, and a desired one. (F) component thru | or (H) component are included by.
In addition, the blending ratio of the component (A) and the component (B) is determined based on the blending amount in the blending stage, and after the blending, the thermal crosslinking reaction proceeds somewhat by keeping it at an elevated temperature. When the crosslinked product of the component (A) and the component (B) is formed, the sum of the component (A) forming the crosslinked product and the component (A) not involved in crosslinking is Similarly, the sum of the component (B) that forms the crosslinked body and the component (B) that is not involved in crosslinking is the amount of the component (B).
Hereinafter, details of each component will be described.

<A component>
The component (A) is a compound having a functional group for allowing a thermal crosslinking reaction with the compound having a vinyl ether group of the component (B) in the structure of the resin, and a block isocyanate group of the component (C). Having a functional group for film curing capable of undergoing a thermosetting reaction between and a polystyrene-reduced number average molecular weight (hereinafter referred to as a number average molecular weight) of 2,000 to 30,000 Resin.

  The functional group for the thermal crosslinking reaction reacts with the vinyl ether group in the component (B) compound at an elevated temperature to form a resist film by thermal crosslinking with the component (B) compound. The representative 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). A group capable of causing a crosslinking reaction via an isocyanate group in which a block portion is dissociated with the compound of component (C) at a given temperature, and curing the film. It is at least one selected from the group of an amino group having a hydroxy group other than a group and an active hydrogen. Here, the amino group having active hydrogen means a primary or secondary amino group capable of releasing hydrogen by reaction. Therefore, the amide group does not correspond to an amino group having active hydrogen because it does not have active hydrogen.

  The resin of 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 30,000. If the number average molecular weight exceeds 30,000, a development residue is likely to be generated, and the sensitivity is remarkably reduced. On the other hand, if the number average molecular weight is less than 2,000, the development is insufficient. At this time, a considerable amount of film loss occurs in the unexposed area, which may result in insufficient curing.

  Examples of the alkali-soluble resin (A) include acrylic resins and polyhydroxystyrene resins. In particular, acrylic resins are more preferable because of their high transparency.

  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 having a functional group for thermal crosslinking reaction, 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 film A monomer having a functional group for curing, 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, an essential constituent unit The number average molecular weight is 2,000 to 30,000.

  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 is obtained by carrying out a polymerization reaction at a temperature of ˜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 such as a solvent (E) described later and used as a solution.

<B component>
Component (B) is a compound having two or more vinyl ether groups in one molecule. This may be a compound having at least two vinyl ether groups in one molecule that can be thermally crosslinked with the alkali-soluble resin (A) at a conventional pre-bake temperature. It is not limited.

  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 the advantage that the shape of the formed film 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 a positive number of 2 to 10, k is a positive number 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 formula (1) and formula (2) include bis (4- (vinyloxymethyl) cyclohexylmethyl) glutarate, tri (ethylene glycol) divinyl ether, adipic acid divinyl ester, diethylene glycol divinyl ether. , Tris (4-vinyloxy) butyl trimellrate, bis (4- (vinyloxy) butyl) terephthalate, bis (4- (vinyloxy) butylisophthalate, and cyclohexanedimethanol divinyl ether.

  The compound of component (B) is used in a proportion of 1 to 80 parts by weight, preferably 5 to 40 parts by weight, per 100 parts by weight of the alkali-soluble resin of component (A). When the amount of the component (B) compound used is an excessively small amount less than the lower limit of the above range, the film reduction in the unexposed area becomes remarkable and the pattern-like relief shape becomes poor. On the other hand, when the amount of the component (B) compound used exceeds the upper limit of the above range, the sensitivity of the film is remarkably lowered, and a residue between patterns is generated after development.

<C component>
Component (C) is a compound having two or more blocked isocyanate groups in one molecule. This is because, for example, a conventional post-bake temperature is applied to a film made of the alkali-soluble resin of the component (A) that has been thermally crosslinked with the compound of the component (B) or further decrosslinked with the compound. As long as it is a compound having two or more blocked isocyanate groups in one molecule that can be thermally cured, the type and structure 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 thermal dissociation of the block portion occurs at a higher temperature such as the post-baking temperature and the crosslinking reaction proceeds via the isocyanate group. In order to prevent crosslinking by isocyanate groups from proceeding at a lower temperature, the temperature of the thermal dissociation of the block portion is considerably higher than the pre-bake temperature, for example, 120 ° C to 230 ° C (C) Particularly preferred as component compounds.

  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.

Moreover, the compound of (C) component is used in the ratio of 1 to 80 parts by mass, preferably 5 to 40 parts by mass with respect to 100 parts by mass of the alkali-soluble resin of (A) component. 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>
(D) A component is a photo-acid generator (PAG). This is because acids (sulfonic acids, carboxylic acids, etc.) are used directly or indirectly by irradiation with light used for exposure (ultraviolet rays such as g, h, i rays, ArF, KrF, F ₂ laser light, electron beams, etc.). As long as it has such properties, its type and structure are not particularly limited.

  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) iodonium tetra Fluoroborate, 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) Phosphonium hexafluorophosphonate, tri (p- ethoxyphenyl) phosphonium tetrafluoroborate,

  In the present invention, one kind of photoacid generator selected from the above compound group can be used alone, or two or more kinds of photoacid generators selected from the above compound group can be used in combination. .

  The photoacid generator of component (D) is used in a proportion of 0.5 to 80 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 less than the lower limit of the above range, from the alkali-soluble resin as the component (A), the compound of the component (B) that has been thermally crosslinked upon exposure. If the amount of the photoacid generator used as the component (D) exceeds the upper limit of the above range, it is difficult to obtain a desired pattern-like relief. The storage stability of the photosensitive resin composition becomes inferior.

<E solvent>
The solvent (E) used in the present invention dissolves the components (A) to (D) and dissolves the components (F) to (H), which will be described later, if desired. The solvent is not particularly limited in its type and structure as long as it has a good solubility.

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 alone 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 an alkali-soluble resin other than component (A). In the positive photosensitive resin composition of the present invention, an alkali-soluble resin other than the component (A) can be further contained as long as the effects of the present invention are not impaired.
Preferably, the component (F) is contained in an amount of 1 to 90 parts by mass with respect to 100 parts by mass of the component (A).

  Examples of such component (F) include acrylic resins and hydroxystyrene resins other than the component (A), phenol novolac resins, polyamide resins, polyimide precursors, polyimide resins, and the like.

<G component>
The component (G) is an amine compound. The positive photosensitive resin composition of the present invention may further contain an amine compound for the purpose of enhancing its storage stability, as long as the effects of the present invention are not impaired.

  The amine compound of component (G) is not particularly limited, and examples thereof include triethanolamine, tributanolamine, trimethylamine, triethylamine, trinormalpropylamine, triisopropylamine, trinormalbutylamine, tri-tert-butylamine, and diaza. Examples include tertiary amines such as bicyclooctane, aromatic amines such as pyridine and 4-dimethylaminopyridine, and primary amines such as benzylamine and normal butylamine, and secondary amines such as diethylamine and dinormalbutylamine. Also included are amines.

  (G) The amine compound of a component can be used individually by 1 type or in combination of 2 or more types.

When an amine compound is used, the content thereof is, for example, 0.001 to 5 parts by mass with respect to 100 parts by mass of the alkali-soluble resin of the component (A), and optionally 0.005 to 1 part by mass. Yes, and preferably 0.01 to 0.5 parts by mass. When the amount of the amine compound used as the component (G) is too small below the lower limit of the above range, the storage stability of the positive photosensitive resin composition cannot be sufficiently increased. When the amount of the amine compound used exceeds the upper limit of the above range, the sensitivity of the positive photosensitive resin composition may be lowered.

<H component>
The component (H) is a surfactant. The positive photosensitive resin composition of the present invention can further contain a surfactant for the purpose of improving the coating properties as long as the effects of the present invention are not impaired.

  The surfactant of the component (H) is not particularly limited, and examples thereof include a fluorine-based surfactant, a silicon-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 (manufactured by Dainippon Ink and Chemicals), Florard FC430, FC431 (Sumitomo 3M) Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), and the like.

  Component (H) may be used alone 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. Even if the amount of the surfactant used as the component (H) 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, the positive type photosensitive resin composition of the present invention is provided with an adhesive aid such as a rheology modifier and a silane coupling agent, a pigment, a dye, and a storage stabilizer, as necessary, as long as the effects of the present invention are not impaired. , Antifoaming agents, or dissolution accelerators such as polyphenols and polycarboxylic acids.

<Positive photosensitive resin composition>
The positive photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a compound having a vinyl ether group, (C) a compound having a blocked isocyanate group, and (D) a light component. An acid generator and (E) a solvent, and, if desired, other alkali-soluble resins of component (F), amine compounds of component (G), surfactants of component (H), and other additives It is a composition which can further contain one or more of them.

Among these, preferred examples of the positive photosensitive resin composition of the present invention are as follows.
[1]: Based on 100 parts by mass of component (A), 1 to 80 parts by mass of component (B), 1 to 80 parts by mass of component (C), and 0.5 to 80 parts by mass of (D) A positive photosensitive resin composition containing components, wherein these components are dissolved in (E) a solvent.
[2]: The positive photosensitive resin composition according to [1], further comprising 1 part by mass to 90 parts by mass of the component (F) with respect to 100 parts by mass of the component (A).
[3]: A positive photosensitive resin composition further comprising 0.001 to 5 parts by mass of the component (G) in the composition of the above [1] or [2] based on 100 parts by mass of the component (A).
[4]: A positive photosensitive resin composition further containing 0.2% by mass or less of component (H) in the positive photosensitive resin composition of [1], [2] or [3].

  The ratio of the solid content in the positive photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1 to 80% by mass. It is 5-60 mass%, or 10-50 mass%. Here, solid content means what remove | excluded the (E) solvent from all the components of the positive photosensitive resin composition.

[Method for producing positive photosensitive resin composition]
Although the preparation method of the positive photosensitive resin composition of this invention is not specifically limited, As the preparation method, (A) component (alkali-soluble resin) is melt | dissolved in (E) solvent, for example, B) component (compound having two or more vinyl ether groups in one molecule), (C) component (compound having two or more blocked isocyanate groups in one molecule), (D) component (photoacid generator) And (H) component (surfactant) are mixed at a predetermined ratio to make a uniform solution, or at an appropriate stage of this preparation method, (G) component (amine compound), ( F) Component (other alkali-soluble resin) and / or other additives may be further added and mixed.

  In preparing the positive photosensitive resin composition of the present invention, the solution of the specific copolymer obtained by the polymerization reaction in the solvent (E) can be used as it is, and in this case, the solution of the component (A) In the same manner as described above, when the components (B) and (C) are added to obtain a uniform solution, a solvent (E) may be further added for the purpose of adjusting the concentration. At this time, the (E) solvent used in the process of forming the specific copolymer and the (E) solvent used for concentration adjustment at the time of preparing the positive photosensitive resin composition may be the same, May be 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.

Preferably, in the preparation method, the mixed solution containing the components (A) to (E) and optionally the components (F) to (H) is kept at a temperature higher than room temperature for a required period of time, The following thermal crosslinking reaction proceeds somewhat, and in addition to the components (A) to (E) and, optionally, the components (F) to (H), a crosslinked product of the components (A) and (B) It is desirable to obtain a positive photosensitive resin composition that contains the same.
More preferably, by keeping the mixed solution at a temperature of 30 ° C. to 70 ° C. for 2 hours to 5 days, the mixture solution is added to the components (A) to (E) and optionally to the components (F) to (H). Thus, a positive photosensitive resin composition containing a crosslinked product of the component (A) and the component (B) is obtained.

By preparing under the above temperature and time conditions, the homogeneity of the resulting resin composition is increased, whereby the photoacid generator is efficiently dispersed in the film when it is subjected to a subsequent film forming step. This leads to a dramatic improvement in the sensitivity of the resulting film.
When the stirring temperature is higher than 70 ° C., the crosslinking reaction and curing reaction proceed and the composition becomes non-uniform, and the sensitivity of the resulting film is significantly reduced. When the stirring temperature is lower than 30 ° C., the uniformity of the composition is obtained. It does not lead to improvement of sensitivity.

[Method for producing coating film, pattern formation and cured film]
The positive photosensitive resin composition of the present invention is applied to a semiconductor substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, or an ITO substrate. Etc.) by spin coating, flow coating, roll coating, slit coating, spin coating following slit, ink jet coating, etc., and then pre-dried in a hot plate or oven to form a coating film can do. Then, a positive photosensitive resin film is formed by heat-treating this coating film.

As conditions for this heat treatment, 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 to 60 minutes are employed. The heating temperature and heating time are preferably 80 to 140 ° C. and 0.5 to 10 minutes.
The film thickness of the positive photosensitive resin film formed from the positive photosensitive resin composition is, for example, 0.1 to 50 μm, for example, 0.3 to 30 μm, and further, for example, 0.5 to 10 μm. It is.

  The formed positive photosensitive resin film is hardly soluble in an alkaline developer by crosslinking the compound having the vinyl ether group (B) with the resin (A) by heat treatment during formation. Become a film. In this case, when the temperature of the heat treatment is lower than the lower limit of the above temperature range, the thermal crosslinking is insufficient, and the film may be reduced in the unexposed area. In addition, when the temperature of the heat treatment exceeds the upper limit of the above temperature range and is too high, the once formed thermal bridge portion may be cut again to cause film reduction in the unexposed portion.

When the positive photosensitive resin film formed from the positive photosensitive resin composition of the present invention is exposed by irradiation with ultraviolet rays, ArF, KrF, F ₂ laser light or the like using a mask having a predetermined pattern, Due to the action of the acid generated from the photoacid generator (PAG) of component (D) contained in the positive photosensitive resin film, the exposed portion of the film becomes soluble in an alkaline developer.
The exposure is preferably performed with 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 (PEB) is performed on the positive photosensitive resin film. 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 150 ° C. and a time of 0.3 to 60 minutes are employed.

  Thereafter, development is performed using an alkaline developer. As a result, the exposed portion of the positive photosensitive resin film is removed, and 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 to 180 seconds.

  After the development, the positive photosensitive resin film 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, and A patterned film is obtained.

  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.

  The post-bake is generally processed at a heating temperature selected from the range of 140 ° C. to 250 ° C. for 5 to 30 minutes when on a hot plate and 30 to 90 minutes when in an oven. The method is taken.

  Thus, such a post-bake can provide a target cured film having a good pattern shape.

  As described above, with the positive photosensitive resin composition of the present invention, a coating film having a fine pattern that is sufficiently high in sensitivity and practically not so much that the film loss in the unexposed area is not measured during development. Can be formed.

  Moreover, the cured film obtained from this coating film is excellent in heat resistance, solvent resistance, and transparency.

  In addition, when this type of cured film is used as, for example, an array flattening film for liquid crystal display, it is exposed to heating at a higher temperature (for example, 250 ° C.) during metal deposition in the subsequent process. Baking is performed for a long time at a high temperature (for example, 230 ° C.), and when the resist is stripped after etching, the resist is placed in contact with a resist stripping solution that is an amine-based solution such as monoethanolamine (MEA). Accordingly, such a cured film is required to have high resistance against high-temperature baking (or baking for a long time) and resist stripping solution (amine-based solution) treatment.

  The cured film obtained by the present invention maintains high transparency without decreasing the transmittance even when subjected to high-temperature baking (or baking for a long time) or treatment with a resist stripping solution (amine-based solution). Accordingly, the cured film is excellent in heat resistance and chemical resistance. Therefore, not only the array flattening film of the TFT type liquid crystal element but also various films in the liquid crystal or organic EL display, such as an interlayer insulating film and a protective film. In addition, it is suitable for applications such as an insulating film and a concavo-convex film below the reflective film, and can be suitably used as a microlens by selecting the shape of the cured film.

  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 NHPMA: N-hydroxyphenyl methacrylamide PEMA: mono- (2- (methacryloyloxy) ethyl) phthalate AIBN: azobisisobutyro Nitrile PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether PAG1: CGI 1397 (trade name) manufactured by Ciba Specialty Chemicals
PAG2: Midori Chemical Co., Ltd. TPS105 (trade name)
PVE1: Tris (4- (vinyloxy) butyl) trimellitate PVE2: Triethylene glycol divinyl ether PVE3: 1,4-cyclohexanedimethanol divinyl ether NCO1: VESTAGON (registered trademark) B 1065 (trade name) manufactured by Degussa AG
NCO2: Degussa AG VESTAGON (registered trademark) BF 1540 (trade name)
R30: Mega Japan R-30 (trade name) manufactured by Dainippon Ink & Chemicals, Inc.
MEA: Monoethanolamine GT4: Daicel Chemical Industries, Ltd. GT-401 (trade name)
MPTS: γ-methacryloxypropyltrimethoxysilane P200: P-200 (trade name) 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] manufactured by Toyo Gosei Co., Ltd. ] Photosensitizer synthesized by condensation reaction of 1 mol of phenyl] ethylidene] bisphenol and 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride

[Measurement of number average molecular weight and weight average molecular weight]
The number-average molecular weight and weight-average molecular weight of the alkali-soluble resin (specific copolymer) obtained according to the following synthesis examples are obtained using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation. Tetrahydrofuran was flowed through the column at a flow rate of 1 ml / min (column temperature: 40 ° C.) for elution. 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 of specific copolymer]
<Synthesis Example 1>
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 as component (A), and AIBN 5 g is used as a radical polymerization initiator. These are polymerized at a temperature of 60 ° C. to 100 ° C. in 200 g of the solvent PGMEA, whereby a solution of the component (A) (specific copolymer) of Mn 4,100 and Mw 7,600 (specific copolymer concentration: 27). 0.5% by mass). (P1)

<Synthesis Examples 2 to 5>
Instead of the monomer components and solvents used in Synthesis Example 1, the monomer components and solvents described in the respective columns of Synthesis Examples 2 to 5 in Table 1 below were used, and the same procedures and conditions as in Synthesis Example 1 were used. According to the polymerization reaction, each solution (P2 to P6) of the component (A) (specific copolymer) was obtained, and Mn and Mw of each obtained specific copolymer were measured.
Table 1 shows the measurement results of the monomer components and molecular weights used in Synthesis Examples 1 to 6.

[Production and performance test of positive photosensitive resin composition: 1]
<Examples 1 to 10 and Comparative Examples 1 to 4>
In accordance with the composition shown in Table 2 below, the component (A) solution contains (B) component, (C) component, (D) component and (E) solvent, and further (G) component to (H) component. By mixing at a ratio and stirring at room temperature for 3 hours to obtain a uniform solution, positive type photosensitive resin compositions of Examples and Comparative Examples were prepared.

<Comparative Example 5>
5.5 g of the specific copolymer (P1) solution obtained in Synthesis Example 1 as an alkali-soluble resin solution, 1.1 g of P200 as a 1,2-quinonediazide compound, 1.1 g of GT4 as an epoxy-based crosslinkable compound, By adding 0.0039 g of R30 as a surfactant, 0.25 g of MPTS as an adhesion assistant, and 25.6 g of PGMEA as a solvent, and stirring the mixture at room temperature for 8 hours to obtain a uniform solution, A positive photosensitive resin composition of Comparative Example 5 was prepared.

  For each of the obtained positive photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 5, sensitivity, film reduction (in the unexposed area), light transmittance after high temperature baking (transparency), Each item of the light transmittance after MEA processing, MEA tolerance, and dimensional accuracy was evaluated according to the following procedures.

  When obtaining a cured film from the positive photosensitive resin composition, Comparative Example 5 was subjected to photobleaching at a stage after development and before post-baking, while Examples 1 to 10 and Comparative Example 1 were used. For No. 4 to No. 4, since the post-exposure heating (PEB) is performed after the exposure and before the development without the photobleaching, the evaluation procedures of both are different as follows. It has become.

[Evaluation of sensitivity]
<Examples 1 to 10 and Comparative Examples 1 to 4>
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 120 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. The film thickness was measured using F20 manufactured by FILMETRICS. The light intensity at 365 nm was applied to this coating film by a UV irradiation device PLA-600FA made by Canon.
Irradiation with ultraviolet rays of mW / cm ² was performed for a certain period of time, followed by post-exposure heating (PEB) on a hot plate at a temperature of 110 ° C. for 120 seconds. Thereafter, development was performed by immersing in a 0.4% by mass tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution for 60 seconds, followed by washing with running ultrapure 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.

<Comparative Example 5>
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 120 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5.5 mW / cm ² for a certain period of time by means of an ultraviolet irradiation device PLA-600FA manufactured by Canon. Then, add 60% TMAH aqueous solution to 0.4% by mass.
After developing by dipping for 2 seconds, running water was washed with ultrapure 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.

[Evaluation of film reduction]
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 120 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. This membrane was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds and then washed with running ultrapure water for 20 seconds. Next, by measuring the thickness of this film, the degree of film reduction in the unexposed area due to development was evaluated. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.

[Evaluation of light transmittance (transparency) after high-temperature firing]
<Examples 1 to 10 and Comparative Examples 1 to 4>
The 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 120 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. This coating film was immersed in a 0.4% by mass 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 1.9 micrometers. The cured film was measured for transmittance at a wavelength of 400 nm using an ultraviolet-visible spectrophotometer (SIMADSU UV-2550 model number, manufactured by Shimadzu Corporation). Furthermore, after heating this coating film at 250 degreeC for 30 minute (s), the transmittance | permeability with a wavelength of 400 nm was measured. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.

<Comparative Example 5>
The positive photosensitive resin composition was applied onto 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 2.4 μm. This coating film was immersed in a 0.4% by mass TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. By irradiating this coating film with UV light having a light intensity at 365 nm of 5.5 mW / cm ² at 800 mJ / cm ² (photo bleaching) using a Canon UV irradiation device PLA-600FA, and then heating at 230 ° C. for 30 minutes. Post-baking was performed to form a cured film having a thickness of 1.9 μm. The cured film was measured for transmittance at a wavelength of 400 nm using an ultraviolet-visible spectrophotometer (SIMADSU UV-2550 model number, manufactured by Shimadzu Corporation). Furthermore, after heating this coating film at 250 degreeC for 30 minute (s), the transmittance | permeability with a wavelength of 400 nm was measured. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.

[Evaluation of light transmittance and MEA resistance after MEA treatment]
<Examples 1 to 10 and Comparative Examples 1 to 4>
The 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 120 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. This coating film was immersed in a 0.4% by mass 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 1.9 micrometers. This coating film was immersed in monoethanolamine heated to 60 ° C. for 20 minutes, and then washed with pure water for 20 seconds. Next, after drying on a hot plate for 10 minutes at a temperature of 180 ° C., the film thickness was measured and the transmittance at a wavelength of 400 nm was measured using an ultraviolet-visible spectrophotometer (SIMADSU UV-2550 model number, manufactured by Shimadzu Corporation). . The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS. The film thickness after the post-baking and the MEA treatment, those having no change in the film thickness after drying were marked with MEA resistance ◯, and those with decreased were marked with x.

<Comparative Example 5>
The positive photosensitive resin composition was applied onto 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 2.4 μm. This coating film was immersed in a 0.4% by mass TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. This coating film is irradiated with UV light having a light intensity at 365 nm of 5.5 mW / cm ² at 800 mJ / cm ² (photo bleaching) by a Canon UV irradiation device PLA-600FA, and then heated at 230 ° C. for 30 minutes. Was post-baked to form a cured film having a thickness of 1.9 μm. This coating film was immersed in monoethanolamine heated to 60 ° C. for 20 minutes, and then washed with pure water for 20 seconds. Next, after drying on a hot plate at a temperature of 180 ° C. for 10 minutes, a film thickness measurement and a transmittance at a wavelength of 400 nm are measured using an ultraviolet-visible spectrophotometer (SIMADSU UV-2550 model number, manufactured by Shimadzu Corporation). did. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS. The film thickness after the post-baking and the MEA treatment, those having no change in the film thickness after drying were marked with MEA resistance ◯, and those with decreased were marked with x.

[Dimensional accuracy]
<Examples 1 to 10 and Comparative Examples 1 to 4>
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 120 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. The film thickness was measured using F20 manufactured by FILMETRICS. On this coating film, UV light having a light intensity at 365 nm of 5.5 mW / cm ² was applied by a Canon UV irradiation device PLA-600FA through a mask of 8 μm line and space pattern to 40 m.
After irradiation with J / cm ² , post-exposure heating (PEB) was performed on a hot plate at a temperature of 110 ° C. for 120 seconds. Thereafter, development was performed by immersing in a 0.4 mass% TMAH aqueous solution for 60 seconds, followed by washing with running ultrapure water for 20 seconds. Thereafter, post-baking was performed on a hot plate at 230 ° C. for 30 minutes. The cross section of the formed pattern was observed using a scanning electron microscope (hereinafter referred to as SEM), and the line width was measured. The case where the pattern width was maintained at 8 μm was marked as ◯, and the case where the pattern width was widened or reduced and was not maintained at 8 μm was marked as x.

<Comparative Example 5>
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 120 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. The film thickness was measured using F20 manufactured by FILMETRICS. To this coating film, UV light having a light intensity at 365 nm of 5.5 mW / cm ² was passed through a mask with an 8 μm line and space pattern by a Canon UV irradiation apparatus PLA-600FA.
Irradiated mJ / cm ² . Thereafter, development was performed by immersing in a 0.4% by mass TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. Thereafter, post-baking was performed on a hot plate at 230 ° C. for 30 minutes. The cross section of the formed pattern was observed using SEM, and the line width was measured. The case where the pattern width was maintained at 8 μm was marked as ◯, and the case where the pattern width was widened or reduced and was not maintained at 8 μm was marked as x.

[Result of evaluation]
The results of the above evaluation are shown in Table 3 below.

  As can be seen from the results shown in Table 3, each of Examples 1 to 10 is highly sensitive, and the film loss in the unexposed area is virtually not observed in the measurement results, and is 250 ° C. (or 230 ° C.). Even after 30 minutes of high-temperature baking, the light transmittance is small and high transparency is maintained. Further, even after the MEA treatment, the transmittance is small and has excellent MEA resistance and dimensional accuracy. It was.

  On the contrary, in Comparative Examples 1 to 3, the pattern forming film was reflowed by post-baking at 230 ° C. for 30 minutes, and a pattern having a desired shape and size could not be obtained. Moreover, the film | membrane without pattern formation also produced the film loss when the MEA process was carried out after the post-baking for 30 minutes at 230 degreeC. The film thickness after the MEA treatment was reduced by about 25% from the film thickness before the MEA treatment. In Table 3, “Transmittance after MEA treatment” is a value for a film in which film reduction after MEA treatment occurs.

In Comparative Example 4, the film was dissolved and disappeared by development.
Furthermore, for Comparative Example 5, the amount of film reduction in the unexposed area during development was 0.2 μm. After the post-baking at 230 ° C. for 30 minutes, the permeability of the film was 91%, but when the film was further baked at 250 ° C. for 30 minutes, the permeability of the film was reduced to 85%. Further, when the MEA treatment was performed after post-baking at 230 ° C. for 30 minutes, the membrane permeability decreased from 91% to 86%.

[Production and performance test of positive photosensitive resin composition: 2]
<Examples 11 to 13 and Comparative Examples 6 to 9>
According to the composition shown in the following Table 4, the solution of the specific copolymer (P1, P4 and P6) obtained in the same manner as in the synthesis example described above as the solution of the component (A) is added to the component (B), (C) Components, (D) and (E) solvent, and further (H) component are mixed in a predetermined ratio, and stirred at room temperature for 3 hours to obtain a uniform solution. A photosensitive resin composition was prepared.

  For each of the positive photosensitive resin compositions of Examples 11 to 13 and Comparative Examples 6 to 9 obtained, the followings were obtained for each item of film reduction (in the unexposed area), resolution, and film thickness change after MEA treatment. Evaluation was performed according to the procedure.

[Evaluation of film reduction]
The positive photosensitive resin composition was applied onto 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 0.5 μm. This membrane was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds and then washed with running ultrapure water for 20 seconds. Next, by measuring the thickness of this film, the degree of film reduction in the unexposed area due to development was evaluated. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.

〔resolution〕
An antireflective film solution for KrF (DUV-30J (trade name) manufactured by Nissan Chemical Industries, Ltd.) was applied on a silicon wafer using a spin coater, and then baked on a hot plate at a temperature of 205 ° C. for 60 seconds. An antireflection film having a thickness of 140 nm was formed. A positive photosensitive resin composition was applied onto the antireflection film using a spin coater, and then baked on a hot plate at a temperature of 110 ° C. for 90 seconds to form a coating film having a thickness of 0.5 μm. This coating film was irradiated by a KrF excimer laser reduced projection exposure apparatus (NSR-201A, Nikon Corporation) through a line and space pattern mask at 10 mJ / cm ² , and then at a temperature of 11
Post-exposure heating (PEB) was performed on a hot plate at 0 ° C. for 90 seconds. Thereafter, development was performed by immersing a 0.4 mass% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. Thereafter, post-baking was performed on a hot plate at 230 ° C. for 30 minutes. The cross section of the formed pattern was observed with a scanning electron microscope (hereinafter referred to as SEM), and the line width was measured. The minimum pattern size resolved according to the mask size without any residue between patterns was taken as the resolution.

[Evaluation of MEA resistance]
The positive photosensitive resin composition was applied onto a quartz substrate using a spin coater and then pre-baked on a hot plate at a temperature of 110 ° C. for 90 seconds to form a coating film having a thickness of 0.5 μm. This coating film was immersed in a 0.4% by mass 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 0.4-micrometer-thick cured film. This coating film was immersed in monoethanolamine heated to 60 ° C. for 20 minutes, and then washed with pure water for 20 seconds. Next, the film thickness was measured after drying on a hot plate at a temperature of 180 ° C. for 10 minutes. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS. The film thickness after the post-baking and the MEA treatment, those having no change in the film thickness after drying were marked with MEA resistance ◯, and those with reduced thickness were marked with x.

[Result of evaluation]
The results of the above evaluation are shown in Table 5 below.

  As can be seen from the results shown in Table 5, all of Examples 11 to 13 have high resolution, film loss in the unexposed areas is virtually not observed in the measurement results, and has excellent MEA resistance. there were.

  On the contrary, in Comparative Examples 6 and 7, the pattern forming film was reflowed by post-baking at 230 ° C. for 30 minutes, and a pattern having a mask size could not be obtained. Moreover, the film | membrane without pattern formation also produced the film loss when the MEA process was carried out after the post-baking for 30 minutes at 230 degreeC. The film thickness after the MEA treatment was reduced by about 25% from the film thickness before the MEA treatment.

In Comparative Example 8, the film was dissolved and disappeared by development.
Further, in Comparative Example 9, the amount of film reduction in the unexposed area during development was 0.2 μm, and the exposed area was not completely dissolved and a pattern could not be formed.

[Production and performance test of positive photosensitive resin composition: 3]
<Examples 14 to 18>
According to the composition shown in Table 6 below, the solution (P1) of the specific copolymer obtained in the same manner as in Synthesis Example 1 as the solution of the component (A) is added to the component (B), the component (C), and (D). The positive photosensitive resin composition of each Example was prepared by mixing the component, the solvent (E), and the component (H) at a predetermined ratio and stirring the mixture at 35 ° C. for 3 days to obtain a uniform solution. .
<Example 19>
According to the same composition as Example 16 shown in the following Table 6, the solution (P1) of the specific copolymer obtained in the same manner as in Synthesis Example 1 as the solution of the component (A) was added to the component (B), (C) The positive photosensitive resin composition is prepared by mixing the component, the component (D), the solvent (E), and the component (H) at a predetermined ratio and stirring at 60 ° C. for 3 hours to obtain a uniform solution. did.
<Example 20>
According to the same composition as Example 16 shown in the following Table 6, the solution (P1) of the specific copolymer obtained in the same manner as in Synthesis Example 1 as the solution of the component (A) was added to the component (B), (C) The positive photosensitive resin composition is prepared by mixing the component, the component (D), the solvent (E), and the component (H) at a predetermined ratio and stirring at 50 ° C. for 3 hours to obtain a uniform solution. did.
<Example 21>
According to the same composition as Example 16 shown in the following Table 6, the solution (P1) of the specific copolymer obtained in the same manner as in Synthesis Example 1 as the solution of the component (A) was added to the component (B), (C) The positive photosensitive resin composition is prepared by mixing the component, the component (D) and the solvent (E) and the component (H) at a predetermined ratio and stirring the mixture at 50 ° C. for 9 hours to obtain a uniform solution. did.

<Comparative Examples 10 to 13>
According to the composition shown in the following Table 6, the solution of the specific copolymer (P1, P5 and P6) obtained in the same manner as in the synthesis example described above as the solution of the component (A) was added to the component (B), (C) The positive photosensitive resin composition of each comparative example is prepared by mixing the components, the component (D) and the solvent (E), and further the component (H) at a predetermined ratio and stirring at room temperature for 3 hours to obtain a uniform solution. A product was prepared.

<Comparative example 14>
As a substitute for the component (A) solution, 20 g of the specific copolymer solution (P1) obtained in Synthesis Example 1 was used, and 1.1 g of P200 as the 1,2-quinonediazide compound of component (C), (B) In place of the component, 1.1 g of GT4 as an epoxy-based crosslinkable compound, 0.0039 g of R30 as a surfactant of the component (G), 0.25 g of MPTS as an adhesion assistant, and 10.6 g of PGMEA as a solvent are mixed, This mixture was stirred at room temperature for 8 hours to obtain a uniform solution, whereby a positive photosensitive resin composition of Comparative Example 14 was prepared.

  For each of the obtained positive photosensitive resin compositions of Examples 14 to 21 and Comparative Examples 10 to 14, sensitivity, film reduction (in the unexposed area), light transmittance (transparency) after high-temperature baking, Each item of the light transmittance after MEA processing, MEA tolerance, and dimensional accuracy was evaluated according to the following procedures.

  When obtaining a cured film from the positive photosensitive resin composition, Comparative Example 14 was subjected to photobleaching at the stage after development and before post-baking, while Examples 14 to 21 and Comparative Example 10 were used. As for No. 13 to No. 13, since the post-exposure heating (PEB) is performed at the stage after exposure and before development without performing the photobleaching, the evaluation procedures of both are different as follows. It has become.

[Evaluation of sensitivity]
<Examples 14 to 21 and Comparative Examples 10 to 13>
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 2.5 μm. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was irradiated with ultraviolet light having a light intensity at 365 nm of 5.5 mW / cm ² for a certain period of time by a Canon ultraviolet irradiation apparatus PLA-600FA, and then subjected to post-exposure heating (PEB) on a hot plate at a temperature of 110 ° C. for 120 seconds. went. Thereafter, development was performed by immersing in a 0.4% by mass TMAH aqueous solution for 60 seconds, and then washed with running ultrapure 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.

<Comparative example 14>
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 2.5 μm. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5.5 mW / cm ² for a certain period of time by means of an ultraviolet irradiation device PLA-600FA manufactured by Canon. Then, add 60% TMAH aqueous solution to 0.4% by mass.
After developing by dipping for 2 seconds, running water was washed with ultrapure 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.

[Evaluation of film reduction]
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 2.5 μm. This membrane was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds and then washed with running ultrapure water for 20 seconds. Next, by measuring the thickness of this film, the degree of film reduction in the unexposed area due to development was evaluated. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.

[Evaluation of light transmittance (transparency) after high-temperature firing]
<Examples 14 to 21 and Comparative Examples 10 to 13>
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 110 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. This coating film was immersed in a 0.4% by mass 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 1.9 micrometers. The cured film was measured for transmittance at a wavelength of 400 nm using an ultraviolet-visible spectrophotometer (SIMADSU UV-2550 model number, manufactured by Shimadzu Corporation). Furthermore, after heating this coating film at 250 degreeC for 30 minute (s), the transmittance | permeability with a wavelength of 400 nm was measured. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.

<Comparative example 14>
The positive photosensitive resin composition was applied onto a quartz substrate 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 2.4 μm. This coating film was immersed in a 0.4% by mass TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. By irradiating this coating film with UV light having a light intensity at 365 nm of 5.5 mW / cm ² at 800 mJ / cm ² (photo bleaching) using a Canon UV irradiation device PLA-600FA, and then heating at 230 ° C. for 30 minutes. Post-baking was performed to form a cured film having a thickness of 1.9 μm. The cured film was measured for transmittance at a wavelength of 400 nm using an ultraviolet-visible spectrophotometer (SIMADSU UV-2550 model number, manufactured by Shimadzu Corporation). Furthermore, after heating this coating film at 250 degreeC for 30 minute (s), the transmittance | permeability with a wavelength of 400 nm was measured. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.

[Evaluation of light transmittance and MEA resistance after MEA treatment]
<Examples 14 to 21 and Comparative Examples 10 to 13>
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 110 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. This coating film was immersed in a 0.4% by mass 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 1.9 micrometers. This coating film was immersed in monoethanolamine heated to 60 ° C. for 20 minutes, and then washed with pure water for 20 seconds. Next, after drying on a hot plate for 10 minutes at a temperature of 180 ° C., the film thickness was measured and the transmittance at a wavelength of 400 nm was measured using an ultraviolet-visible spectrophotometer (SIMADSU UV-2550 model number, manufactured by Shimadzu Corporation). . The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS. The film thickness after the post-baking and the MEA treatment, those having no change in the film thickness after drying were marked with MEA resistance ◯, and those with decreased were marked with x.

<Comparative example 14>
The positive photosensitive resin composition was applied onto a quartz substrate 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 2.4 μm. This coating film was immersed in a 0.4% by mass TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. This coating film is irradiated with UV light having a light intensity at 365 nm of 5.5 mW / cm ² at 800 mJ / cm ² (photo bleaching) by a Canon UV irradiation device PLA-600FA, and then heated at 230 ° C. for 30 minutes. Was post-baked to form a cured film having a thickness of 1.9 μm. This coating film was immersed in monoethanolamine heated to 60 ° C. for 20 minutes, and then washed with pure water for 20 seconds. Next, after drying on a hot plate at a temperature of 180 ° C. for 10 minutes, a film thickness measurement and a transmittance at a wavelength of 400 nm are measured using an ultraviolet-visible spectrophotometer (SIMADSU UV-2550 model number, manufactured by Shimadzu Corporation). did. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS. The film thickness after the post-baking and the MEA treatment, those having no change in the film thickness after drying were marked with MEA resistance ◯, and those with reduced thickness were marked with x.

[Dimensional accuracy]
<Examples 14 to 21 and Comparative Examples 10 to 13>
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 2.5 μm. The film thickness was measured using F20 manufactured by FILMETRICS. On this coating film, UV light having a light intensity at 365 nm of 5.5 mW / cm ² was applied by a Canon UV irradiation device PLA-600FA through a mask of 8 μm line and space pattern to 40 m.
After irradiation with J / cm ² , post-exposure heating (PEB) was performed on a hot plate at a temperature of 110 ° C. for 120 seconds. Thereafter, development was performed by immersing in a 0.4 mass% TMAH aqueous solution for 60 seconds, followed by washing with running ultrapure water for 20 seconds. Thereafter, post-baking was performed on a hot plate at 230 ° C. for 30 minutes. The cross section of the formed pattern was observed using a scanning electron microscope (hereinafter referred to as SEM), and the line width was measured. The case where the pattern width was maintained at 8 μm was marked as ◯, and the case where the pattern width was widened or reduced and was not maintained at 8 μm was marked as x.

<Comparative example 14>
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 2.5 μm. The film thickness was measured using F20 manufactured by FILMETRICS. To this coating film, UV light having a light intensity at 365 nm of 5.5 mW / cm ² was passed through a mask with an 8 μm line and space pattern by a Canon UV irradiation apparatus PLA-600FA.
Irradiated mJ / cm ² . Thereafter, development was performed by immersing in a 0.4% by mass TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. Thereafter, post-baking was performed on a hot plate at 230 ° C. for 30 minutes. The cross section of the formed pattern was observed using SEM, and the line width was measured. The case where the pattern width was maintained at 8 μm was marked as ◯, and the case where the pattern width was widened or reduced and was not maintained at 8 μm was marked as x.

[Result of evaluation]
The results of the above evaluation are shown in Table 7 below.
FIG. 1 is a diagram showing the film thickness (μm, film thickness of the undissolved portion in the exposed portion) with respect to the irradiation dose (mJ / cm ² ) in Example 15, Example 16, and Comparative Example 14 (DNQ system). Show.

As can be seen from the results shown in Table 7, all of Examples 14 to 21 are highly sensitive, and the film loss in the unexposed area is virtually not observed in the measurement results, and is 250 ° C. (or 230 ° C.). Even after 30 minutes of high-temperature baking, the light transmittance is small and high transparency is maintained. Further, even after the MEA treatment, the transmittance is small and has excellent MEA resistance and dimensional accuracy. It was.
Moreover, the result shown in FIG. 1 has shown that the sensitivity in Example 15 and Example 16 improved dramatically rather than the conventional naphthoquinone diazide (DNQ) type | system | group (comparative example 14).

  On the contrary, in Comparative Examples 10 to 12, the pattern forming film was reflowed by post baking at 230 ° C. for 30 minutes, and a pattern having a desired shape and size could not be obtained. Moreover, the film | membrane without pattern formation also produced the film loss when the MEA process was carried out after the post-baking for 30 minutes at 230 degreeC. The film thickness after the MEA treatment was reduced by about 25% from the film thickness before the MEA treatment. The “transmittance after MEA treatment” in Table 7 is a value for a film in which film reduction after MEA treatment occurs.

In Comparative Example 13, the film was dissolved and disappeared by development.
Furthermore, for Comparative Example 14, the amount of film reduction in the unexposed area during development was 0.2 μm. After the post-baking at 230 ° C. for 30 minutes, the transmittance of the film was 92%, but when the film was further baked at 250 ° C. for 30 minutes, the transmittance of the film was reduced to 85%. Further, when the MEA treatment was performed after post-baking at 230 ° C. for 30 minutes, the membrane permeability decreased from 92% to 86%.

The positive photosensitive resin composition according to the present invention is suitable as a material for forming a cured film such as a protective film, a planarizing film, and an insulating film in various displays such as a thin film transistor (TFT) type liquid crystal display element and an organic EL element. In particular, it is also suitable as a material for forming an interlayer insulating film of a TFT type liquid crystal element, a protective film for a color filter, an array flattening film, a concavo-convex film below a reflective film of a reflective display, an insulating film of an organic EL element, etc. Furthermore, it is also suitable as various electronic materials such as a microlens material.

FIG. 1 is a diagram showing a film thickness (μm, a film thickness of an undissolved portion in an exposed portion) with respect to an irradiation dose (mJ / cm ² ).

Claims (14)

A positive photosensitive resin composition comprising the following component (A), component (B), component (C), component (D) and solvent (E).
Component (A): Functional group for allowing thermal crosslinking reaction with compound of component (B), and functional for film curing capable of thermal curing reaction with compound of component (C) Alkali-soluble resin (B) component having a group and a number average molecular weight of 2,000 to 30,000: Compound (C) component having two or more vinyl ether groups in one molecule: Two in one molecule Compound (D) component having the above blocked isocyanate group: Photoacid generator (E) solvent The functional group for the thermal crosslinking reaction is at least one selected from the group of carboxyl group and phenolic hydroxy group, and the functional group for film curing is a hydroxy group other than the phenolic hydroxy group and active hydrogen The positive photosensitive resin composition of Claim 1 which is at least 1 type chosen from the group of the amino group which has these. Based on 100 parts by mass of component (A), 1 to 80 parts by mass of component (B), 1 to 80 parts by mass of component (C), and 0.5 to 80 parts by mass of (D). The positive photosensitive resin composition of Claim 1 or Claim 2 containing a component. The positive photosensitive resin composition according to any one of claims 1 to 3, further comprising an alkali-soluble resin other than the component (A) as the component (F). The positive photosensitive composition according to any one of claims 1 to 4, further comprising 0.001 to 5 parts by mass of an amine compound as component (G) based on 100 parts by mass of component (A). Resin composition. The positive photosensitive resin according to any one of claims 1 to 5, further comprising 0.2% by mass or less of a surfactant as a component (H) in the positive photosensitive resin composition. Composition. A step of applying the positive photosensitive resin composition according to any one of claims 1 to 6 to a semiconductor substrate, a step of irradiating the application surface with ultraviolet rays through a pattern mask, and the application surface. A pattern forming method including a step of developing and forming a pattern on a semiconductor substrate, and a step of performing post-baking for film hardening on the pattern forming surface. The pattern formation method according to claim 7, wherein the ultraviolet light is light having at least one wavelength among i-line, g-line, and h-line. The ultraviolet ArF, a KrF or _{F 2} laser beam, a pattern forming method according to claim 7 wherein. Cured film obtained using the positive photosensitive resin composition as claimed in any one of claims 1 to 6. The liquid crystal display element which has a cured film of Claim 10 . The array flattening film for liquid crystal displays which consists of a cured film of Claim 10 . An interlayer insulating film comprising the cured film according to claim 10 . A microlens comprising the cured film according to claim 10 .

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