TWI411883B - Positive type photosensitive resin composition and cured coating prepared therefrom - Google Patents

Abstract

[PROBLEMS] To provide: a positive photosensitive resin composition which has excellent storage stability and high sensitivity and is reduced in film thickness loss in unexposed areas and which, even when subjected after film formation to burning at a high temperature or a treatment with a resist stripper liquid, retains a high transmittance and suffers no decrease in film thickness; and a cured film which is obtained from the positive photosensitive resin composition and is suitable for use as a film material for various displays, e.g., an array planarization film for TFT liquid-crystal elements. [MEANS FOR SOLVING PROBLEMS] The positive photosensitive resin composition comprises: ingredient (A) which is a thermally crosslinked polymer formed from a base polymer having a functional group capable of undergoing heat curing reaction by bonding the base polymer to itself through a chemical structure comprising two or more heat-crosslinkable groups represented by the formula (1); [Chemical formula 1] formula (1) ingredient (B) which is a compound having two or more blocked isocyanate groups per molecule; ingredient (C) which is a photo-acid generator; and a solvent (D).

Description

The present invention relates to a positive photosensitive resin composition and a cured film obtained therefrom. More specifically, it relates to a positive photosensitive resin composition suitable for display use and a cured film thereof, and various materials using the cured film.

A display element such as a thin film transistor (TFT) type liquid crystal display element or an organic electroluminescence (EL) element is provided with an electrode protective film, a planarization film, an insulating film, and the like which form a pattern. As a material for forming these films, a photosensitive resin composition having a small number of steps for obtaining a desired pattern shape and having sufficient flatness in the photosensitive resin composition is more widely used than before.

Therefore, these films are required to have excellent process resistance such as heat resistance, solvent resistance, and resistance to long-time firing, and have good adhesion to the substrate, and have a process limit for forming a pattern under various process conditions suitable for the purpose of use. The range is large, and it has high sensitivity and high transparency, and various characteristics such as film unevenness after development. Therefore, from the point of such demand characteristics, a resin containing a naphthoquinonediazide compound has been used as a photosensitive resin composition.

However, among the characteristics required for such a photosensitive resin composition, one of important characteristics is, for example, sensitivity. In the industrial production of display elements and the like, in the industrial production of display elements and the like, the sensitivity becomes one of the most important characteristics of such photosensitive resin materials in the current state in which the amount of display required is significantly increased.

However, the above-mentioned conventional photosensitive resin material containing a naphthoquinonediazide compound cannot be completely satisfied in sensitivity. The polymer in the material may improve the sensitivity by increasing the solubility in the alkali developing solution, but the method has a limit, and the dissolution of the unexposed portion causes a decrease in the residual film rate. With the substrate, it is a disadvantage of the cause of film unevenness.

Therefore, many patent applications for the purpose of high sensitivity of photosensitive resin materials have been achieved so far. For example, a radiation-sensitive resin composition containing at least one of an alkali-soluble resin and a specific polyhydroxy compound and a derivative thereof has been proposed (for example, see Patent Document 1). However, the material of this proposal has a problem of preservation stability due to high symmetry of photosensitivity.

Further, a positive-type radiation-sensitive resin composition containing an alkali-soluble phenol resin and a sensitizing radioactive compound (for example, refer to Patent Document 2) and a positive photosensitive resin composition containing a specific alkali-soluble resin and a quinonediazide compound have been proposed. (For example, refer to Patent Document 3). However, these have problems in terms of transparency and long-term firing stability due to the use of a phenol resin in the binder polymer.

As described above, development of a photosensitive resin composition which satisfies other characteristics and has a high level of sensitivity at a desired level is extremely difficult, and it is difficult to obtain a satisfactory photosensitive resin composition by combining conventional techniques.

Further, a conventional photosensitive resin material generally containing a naphthoquinonediazide compound is subjected to photobleaching even after the coloring of the cured film due to the naphthoquinonediazide compound after exposure and development, and the transparency is lowered. In the photobleaching step, when the obtained film is fired at a high temperature of about 250 ° C, the light transmittance is lowered and colored, or is baked at a temperature lower than the temperature, for example, at 230 ° C for a long time, and the visible light transmittance is lowered (coloring). In addition, even if it is treated with a drug such as an amine-based solution of a photoresist stripping solution, the light transmittance is lowered, and the problem of deterioration of transparency is caused, and a conventional photosensitive resin material containing a naphthoquinone diazide compound has such a The problem of heat resistance and drug resistance (for example, refer to Patent Document 4).

On the other hand, a chemical gain type photoresist has been conventionally developed as a photosensitive material having high sensitivity and high resolution. Developed as a conventional chemical gain type photoresist for semiconductor photoresists, it can be applied to light sources (KrF, ArF) that are shorter than i-line, and can form finer patterns, at high temperatures used for film hardening, or light. In the presence of the anti-stripping liquid, the bond portion of the protective group and the thermal cross-linking portion of the ether bond are easily decomposed, and heat resistance and chemical resistance are remarkably lowered, and it is almost impossible to use it as a permanent film (see, for example, Patent Document 5). Further, in order to allow thermal hardening, the crosslinking of the epoxy-based and the amine-based plastics is introduced into the chemical gain type photoresist, and the influence of the acid generated by the photoacid generator (PAG) in the exposure and the photoresist is also performed. The cross-linking of the exposed portion causes a new problem such as dissolution of the unexposed portion and disappearance of the contrast, and it is difficult to introduce such a cross-linking to the chemical gain type resist.

[Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Kaiping No. 4-352101, Patent Document 5: US Patent No. 5,075,199

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a positive photosensitive resin composition which has sufficient high sensitivity and which does not observe a film thinning of an unexposed portion during development, and actually has no film change. In addition, even if the film is fired at a high temperature after the film formation, the high transmittance and the exposure to the photoresist stripping solution (amine-based solution) are small, and the film thickness is reduced and the transmittance is lowered to a small extent.

Further, the present invention provides a cured film obtained by using such a positive photosensitive resin composition, and even if it is treated by high-temperature baking or photoresist peeling liquid (amine-based solution), the transmittance is particularly reduced, and high transparency is maintained. , a heat-resistant and chemically resistant cured film, and various components made using such a cured film. Materials are the subject.

The inventors of the present invention have found the present invention in order to solve the above problems and have conducted intensive studies.

In other words, the first aspect is a positive photosensitive resin composition containing the following components (A), (B), (C), and (D) a solvent.

(A) component: a matrix polymer having a functional group for film hardening which is capable of undergoing a thermosetting reaction with a compound of the component (B), and two or more formulas (1) derived from a polyfunctional vinyl ether compound ) The thermally crosslinked body formed by bonding the chemical structures of the thermal crosslinking groups to each other, and having a weight average molecular weight of 10,000 to 250,000, and (B) component: having two or more in one molecule a segment isocyanate group-containing compound; (C) component: photoacid generator; (D) solvent.

In a positive-type photosensitive resin composition according to the first aspect, the film-curing functional group is at least one member selected from the group consisting of a hydroxyl group other than a phenolic hydroxyl group and an active hydrogen group. base.

A positive photosensitive resin composition according to the first aspect or the second aspect, wherein the thermally crosslinked body of the component (A) further contains a functional group capable of thermal crosslinking reaction and a vinyl ether. base.

According to a fourth aspect, the positive photosensitive resin composition according to the third aspect, wherein the functional group for the thermal crosslinking reaction is at least one functional group selected from the group consisting of a carboxyl group and a phenolic hydroxyl group.

The positive photosensitive resin composition according to any one of the first aspect to the fourth aspect, wherein the component (A) is a functional group having a heat crosslinkable reaction and has a number average molecular weight of 2,000. A thermally crosslinked body obtained by thermally crosslinking a compound of up to 30,000 of an alkali-soluble resin and a compound having two or more vinyl ether groups in one molecule.

In a positive-type photosensitive resin composition according to the fifth aspect, the component (A) is obtained by using 1 to 80 parts by mass of the vinyl ether group-containing compound based on 100 parts by mass of the alkali-soluble resin. Thermal crosslinks formed by thermal crosslinking reactions.

The positive photosensitive resin composition according to any one of the first aspect to the sixth aspect, wherein the thermally crosslinked body based on the component (A) is contained in an amount of from 0.5 to 80 parts by mass per 100 parts by mass. (B) component, and 0.2 to 80 parts by mass of component (C).

The positive photosensitive resin composition according to any one of the first aspect to the seventh aspect, further comprising an alkali-soluble resin as the component (E).

According to a ninth aspect, the positive-type photosensitive resin composition according to the eighth aspect, wherein the alkali-soluble resin of the component (E) is a base other than the alkali-soluble resin of the thermally crosslinked body of the component (A). Soluble resin.

The positive photosensitive resin composition according to any one of the first aspect to the ninth aspect, wherein the thermally crosslinked product based on the component (A) is 100 parts by mass, and further contains 0.0005 to 5 parts by mass. The amine compound is used as the component (F).

The positive photosensitive resin composition according to any one of the first aspect to the tenth aspect, wherein the positive photosensitive resin composition further contains 0.2% by mass or less of a surfactant ( G) ingredients.

The cured film of the positive photosensitive resin composition as described in any one of the first aspect to the eleventh aspect is used.

A liquid crystal display element having the cured film described in the twelfth aspect is the thirteenth aspect.

According to a fourteenth aspect, an array flattening film for a liquid crystal display comprising the cured film described in the twelfth aspect is used.

The fifteenth aspect is an interlayer insulating film formed of the cured film described in the twelfth aspect.

According to a sixteenth aspect, the microlens formed of the cured film described in the twelfth aspect is used.

According to the present invention, a positive photosensitive resin composition containing a composition capable of undergoing thermal curing of a film and a thermal crosslinking group represented by the above formula (1) is contained in a compound having a blocked isocyanate group. High sensitivity, and the degree of film thinning of the unexposed portion is not observed during development, and practically no film is thinned. Further, even after the film is formed, it is fired even at a high temperature of, for example, 250 ° C (or for example, at 230 ° C. In the case of maintaining the high transmittance and being exposed to the resist stripping solution (amine-based solution), the effect of reducing the film thickness and reducing the transmittance is small.

Further, as a component of the positive photosensitive resin composition, storage stability can be obtained by using a thermally crosslinked body comprising the above-mentioned heat-curable group and the thermal crosslinking group represented by the above formula (1). Excellent composition effect.

Further, by using the cured film obtained from the positive photosensitive resin composition of the present invention, even when the film is fired at a high temperature (250 ° C) or treated with a photoresist (amine solution), the decrease in transmittance is particularly small and maintained. Highly transparent, it is a cured film which is excellent in heat resistance and chemical resistance. Therefore, it is possible to obtain materials for various films such as liquid crystal or organic EL display which are suitable for array planarizing films of TFT liquid crystal elements which are not suitable for chemical gain type photoresists. The use, and the effect of the use of microlenses and the like.

The positive photosensitive resin composition of the present invention contains a thermally crosslinked product of the component (A), a compound having a blocked isocyanate group as the component (B), a photoacid generator of the component (C), and (D) a solvent. Further, the composition of the alkali-soluble resin of the component (E), the amine compound of the component (F) or the surfactant of the component (G) is contained as desired. The details of each component are explained below.

<Component A>

The component (A) is a matrix polymer having a functional group for film hardening which is capable of undergoing a thermosetting reaction with the compound of the component (B), and two or more formulas (1) derived from the polyfunctional vinyl ether compound are contained. ) The thermal crosslinks of the thermally crosslinked groups are thermally bonded to each other and have a weight average molecular weight of 10,000 to 250,000.

The functional group for film hardening is a thermal crosslinked body of the above component (A) (decrosslinked body in which the exposed portion is thermally crosslinked and dissociated), and is interposed at a higher temperature with the compound (B). The isocyanate group in which the block portion is dissociated, and the crosslinking reaction is carried out to form a group which hardens the film, and the functional group represented by the block is at least one selected from the group consisting of a hydroxyl group other than a phenolic hydroxyl group and an active hydrogen group. Here, the amine group having an active hydrogen means a primary or secondary amine group which can release hydrogen from the reaction. Therefore, the guanamine group, because it does not have active hydrogen, does not belong to an amine group having an active hydrogen.

The thermal crosslinked body of the component (A) is not particularly limited as long as it is a thermal crosslinked body having such a structure, and other skeletons and types of the matrix polymer constituting the thermally crosslinked body.

However, the heat-crosslinked body of the component (A) has a weight average molecular weight of from 10,000 to 250,000. When the weight average molecular weight exceeds 250,000 and is too large, a subsequent preparation process for hindering the positive photosensitive resin composition is caused. On the other hand, if the weight average molecular weight is less than 10,000 and is too small, positive photosensitiveness cannot be sufficiently obtained. The effect of preservation stability of the resin composition.

Further, the thermal crosslinked body of the component (A) may further contain a functional group capable of a thermal crosslinking reaction and a vinyl ether group.

The functional group for the thermal crosslinking reaction reacts with the vinyl ether group at an elevated temperature to form a thermal crosslinkable body, and forms a group of the photoresist film, and the functional group represented by the group is selected from a carboxyl group and a phenolic hydroxyl group. At least one functional group in a group.

Further, the thermal crosslinked body of the component (A) is a thermally crosslinked functional group containing a thermal crosslinking reaction with a vinyl ether group and a blocked isocyanate compound of the component (B) in a resin structure. The heat-crosslinking body formed by the thermal crosslinking reaction of the functional group of the reaction film hardening and the alkali-soluble resin having a number average molecular weight of 2,000 to 30,000 and the compound having two or more vinyl ether groups in one molecule is preferable. .

The skeleton of the main chain of the above-mentioned alkali-soluble resin of the thermal crosslinked product of the component (A) and the type of the side chain, and the type and structure of the compound having the vinyl ether group are not particularly limited.

Further, the above-mentioned alkali-soluble resin forming the thermal crosslinked body of the component (A) has a number average molecular weight of 2,000 to 30,000. If the number average molecular weight is more than 30,000, the development residue is liable to be generated, and the sensitivity is remarkably lowered. On the other hand, if the number average molecular weight is less than 2,000, the film of the unexposed portion is thinned during development. There is a situation of insufficient hardening.

Hereinafter, an alkali-soluble resin forming a thermal crosslinked body of the component (A) and a compound having a vinyl ether group will be described.

The alkali-soluble resin which forms the thermal crosslinked body of the component (A) is, for example, an acrylate-based resin or a polyhydroxystyrene-based resin. In particular, the acrylate resin is more preferable because of its high transparency.

Further, in the present invention, an alkali-soluble resin obtained by polymerizing a plurality of monomers (hereinafter referred to as a specific copolymer) obtained by polymerizing a plurality of monomers can be used as a component of the thermally crosslinked body forming the component (A). In this case, the alkali-soluble resin forming the thermal crosslinked body of the component (A) may be a mixture of a plurality of specific copolymers.

That is, the specific copolymer described above is a monomer having a functional group for thermal crosslinking reaction, that is, at least one monomer suitably selected from the group consisting of a monomer having at least one of a carboxyl group and a phenolic hydroxyl group. a monomer having a functional group for film hardening, that is, at least one monomer appropriately selected from the group consisting of a monomer having at least one of a hydroxyl group other than a phenolic hydroxyl group and an active hydrogen-containing amine group, The copolymer formed as a necessary constituent unit has a number average molecular weight of 2,000 to 30,000.

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

Further, the above-mentioned "a monomer having at least one of a hydroxyl group other than a phenolic hydroxyl group and an active hydrogen-containing amine group" includes a monomer having a hydroxyl group other than a phenolic hydroxyl group, a monomer having an active hydrogen-containing amine group, and A monomer having both a hydroxyl group other than a phenolic hydroxyl group and an active hydrogen-containing amine group. These monomers are not limited to a hydroxyl group other than one phenolic hydroxyl group or an active hydrogen-containing amine group, and may be plural.

Specific examples of the above monomers are listed below, but are not limited thereto. As a monomer having a carboxyl group, for example, acrylic acid, methacrylic acid, 2-butenoic acid, mono(2-propenyloxy)ethyl phthalate, mono(2-methylpropenyloxy) phthalate Ethyl ester, N-(carboxyphenyl) maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)propenamide, and the like.

As a monomer having a phenolic hydroxyl group, for example, hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)butylene Imine and the like.

As a monomer having a hydroxyl group other than a phenolic hydroxyl group, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-propenyloxy-6-hydroxy norbornene-2-carboxy-6-lactone, A 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 5-methylpropenyloxy-6-hydroxy norbornene-2-carboxy-6-lactone, and the like.

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

Further, the specific copolymer may be a copolymer formed of a monomer having a functional group for thermal crosslinking reaction and a monomer other than a monomer having a functional group for film hardening (hereinafter referred to as another monomer) as a constituent unit. .

Other monomers, specifically, may be copolymerized with a monomer having at least one of a carboxyl group and a phenolic hydroxyl group, and a monomer having at least one of a hydroxyl group other than a phenolic hydroxyl group and an active hydrogen-containing amine group. The properties of the alkali-soluble resin of the thermal crosslinked body of the component (A) are not impaired, and are not particularly limited.

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

As the acrylate compound, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, decyl acrylate, decyl methacrylate, phenyl acrylate, 2,2,2-trifluoroacrylate Ethyl ester, 3 butyl acrylate, cyclohexyl acrylate, isodecyl acrylate, 2-methoxyethyl acrylate, methoxy triethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydro acrylate Oxime ester, 3-methoxybutyl acrylate, 2-methyl-2-adamantylacrylate, 2-propyl-2-adamantyl acrylate, 8-methyl Alkyl-8-tricyclodecane acrylate and 8-ethyl-8-tricyclodecane acrylate.

As a methacrylate compound, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, decyl methacrylate, ruthenium methacrylate Methyl ester, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 3 butyl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, methacrylate 2- Methoxyethyl ester, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2- 2-methyl-2-adamantylmethacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecylylene A acrylate 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.

As the styrene compound, for example, styrene, methyl styrene, chlorostyrene, bromostyrene, and the like.

As a maleimide compound such as maleimide, N-methyl maleimide, N-phenyl maleimide, and N-cyclohexyl-n-butene Diimine and the like.

The method of obtaining the specific copolymer used in the present invention is not particularly limited, and for example, at least one monomer selected from a group having at least one of a carboxyl group and a phenolic hydroxyl group is appropriately selected. At least one monomer grouped from a monomer having at least one of a hydroxyl group other than a phenolic hydroxyl group and an active hydrogen-containing amine group, a monomer other than the desired monomer, a desired polymerization initiator, etc. It is obtained by polymerization in a solvent at a temperature of 50 to 110 °C. In this case, the solvent to be used is not particularly limited as long as it can dissolve the monomer constituting the specific copolymer and the specific copolymer. As a specific example, the solvent described in (D) solvent mentioned later is mentioned, for example.

The specific copolymer thus obtained is usually in a state in which the specific copolymer is dissolved in a solvent.

Further, the specific copolymer obtained above is added to diethyl ether or water under stirring to cause reprecipitation, and the resulting precipitate is filtered, washed, and then dried at normal temperature or under reduced pressure or under reduced pressure. Drying can be a powder of a specific copolymer. By such an operation, the polymerization initiator and the unreacted monomer which coexist with the specific copolymer can be removed, and as a result, the purified specific copolymer powder can be obtained. In the case where the single operation cannot be sufficiently purified, 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 its powder may be redissolved in a solvent such as the solvent (D) described later, and used as a solution.

The heat-crosslinked body in which the component (A) is formed and the compound having two or more vinyl ether groups in one molecule means the heat of the alkali-soluble resin which can form the same component (A) at the conventional pre-baking temperature. The cross-linking reaction is a vinyl ether group thermally crosslinked with a functional group, and has two or more compounds in the molecule, and the kind and structure thereof are not particularly limited.

The thermal crosslinking reaction of the above compound with the alkali-soluble resin portion forming the component (A) is thermally crosslinked with a functional group, and then the acid generated by the exposure is exposed to the acid-soluble agent from the alkali-soluble resin portion. The separation (decrosslinking) is followed by removal with the alkali-soluble resin portion by development using an alkali developing solution. Therefore, as such a compound, a vinyl ether compound or the like which is generally used for a component of a vinyl ether type chemical gain type resist is used. In the case of using such a compound, changing the compounding amount of the compound, by adjusting the thermal crosslinking density, has an advantage of controlling the shape of the formed film.

Therefore, as the above-mentioned compound, the compound represented by the formula (2) and the formula (3) in the above-mentioned vinyl ether-based compound is preferably developed because the exposed portion has no residual film and no residue.

(wherein, n is a positive number from 2 to 10, k is a positive number from 1 to 10, and R ¹ represents an n-valent organic group.)

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

n of the formula (2) represents the number of vinyl ether groups in one molecule, and n is more preferably an integer of 2 to 4. Therefore, m of the formula (3) also represents the number of vinyl ether groups in one molecule, and m is more preferably an integer of 2 to 4.

Specific examples of the compound represented by the formula (2) and the formula (3), for example, bis(4-(vinyloxymethyl)cyclohexylmethyl)glutarate, tris(ethylene glycol) divinyl ether , divinyl adipate, diethylene glycol divinyl ether, tris(4-ethyleneoxy)butyl trimellitate, bis(4-(ethyleneoxy)butyl)terephthalate And bis(4-(vinyloxy)butyl) isophthalate and cyclohexane dimethanol divinyl ether.

Further, the vinyl ether group-containing compound is used in an amount of from 1 to 80 parts by mass, more preferably from 5 to 40 parts by mass, per 100 parts by mass of the alkali-soluble resin to form a thermally crosslinked body of the component (A). . When the amount of the compound having a vinyl ether group is less than the lower limit of the above range, the film thickness of the unexposed portion becomes remarkable, and the release form of the pattern becomes poor. On the other hand, when the amount of the compound having a vinyl ether group exceeds the upper limit of the above range, the sensitivity of the film is largely lowered, and a residue between the patterns is generated after development.

The method for obtaining the thermal crosslinked body of the component (A) used in the present invention is not particularly limited, and for example, the above alkali-soluble resin and the above compound having a vinyl ether group are kept at a temperature of 35 to 70 ° C in a solvent. The thermal crosslinking reaction of an alkali-soluble resin is obtained by partially crosslinking a functional group with a vinyl ether group. In this case, the solvent to be used is not particularly limited as long as it can dissolve the alkali-soluble resin and the compound having a vinyl ether group, and a specific example thereof is, for example, a solvent described in the solvent (D) described later.

Further, as the heat-crosslinking body of the component (A), as described above, the specific copolymer (the specific copolymer is in a solution state dissolved in a solvent or in a refined powder state) can be used as the alkali-soluble resin ( Further, a thermal crosslinked body of the component (A) obtained by using a specific copolymer, hereinafter referred to as a specific crosslinked body).

When a specific copolymer is used in a solution state (or when a powder is dissolved in a solvent), when a compound having a vinyl ether group is placed therein to form a uniform solution, in order to adjust the concentration, it may be further added. Put in (D) solvent. At this time, the (D) solvent used in the formation process of the specific copolymer (or when the powder is dissolved) and the (D) solvent used in the adjustment of the concentration of the specific crosslinked body may be the same or different. .

<B ingredient>

The component (B) is a compound having two or more blocked isocyanate groups in one molecule. This is the above-mentioned alkali-soluble resin which forms a crosslinked body of the above-mentioned component having the vinyl ether group of the crosslinked body of the component (A), or a crosslinked body which forms a crosslinked body of the component (A). The partially formed film, for example, a block isocyanate group which is heat-curable at a conventional post-baking temperature, has two or more compounds in one molecule, and the kind and structure thereof are not particularly limited.

The compound of the component (B) is a blocked isocyanate group in which two or more isocyanate groups (-NCO) are blocked by a suitable protecting group in one molecule, and therefore exposed to a high temperature at the time of thermal crosslinking, The protecting group (block portion) is thermally dissociated and detached, and the functional group (for example, a hydroxyl group other than a phenolic hydroxyl group and an active hydrogen-containing amine group) which is thermally hardened in the component (A) is interposed between the isocyanate groups produced. Cross-linking reaction, such as formula (4) (wherein R ² represents an organic group of a block moiety) is a compound represented by two or more (the same may be the same or each different) in one molecule.

A compound having two or more blocked isocyanate groups (B) in one molecule can be obtained, for example, by reacting a compound having two or more isocyanate groups in one molecule with an appropriate block agent.

As a compound having two or more isocyanate groups in one molecule, for example, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylene bis(4-cyclohexyl isocyanate), trimethylhexamethylene a diisocyanate or the like or a dimer, a trimer or a reaction product thereof with a diol, a triol, a diamine or a triamine.

As a block agent, for example, methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N,N-dimethylaminoethanol, 2-ethoxyethanol, cyclohexanol, etc. Alcohols, phenols, o-nitrophenols, p-chlorophenols, phenols such as o-, m- or p-cresol, indoleamines such as ε-caprolactam, acetone oxime, methyl ethyl ketone Pyrenes such as hydrazine, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, diphenyl ketone oxime, pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, etc. Mercaptans such as azoles, dodecyl mercaptan and benzene mercaptans.

The compound of the component (B) is a cross-linking reaction at a high temperature such as a post-baking temperature, by dissociating the isocyanate group generated by thermal decomposition of the block portion, in order to prevent the isocyanate at a low temperature such as a pre-bake temperature. The cross-linking of the group, the thermal dissociation temperature of the block portion is much higher than the pre-bake temperature, and for example, a compound of the component (B) is particularly preferable as the compound at 120 ° C to 230 ° C.

The compound of the component (B) is, for example, the following specific examples. In the formula, the isocyanate compound is a compound derived from the component (B) derived from isophorone diisocyanate, and is more preferable from the viewpoints of heat resistance and coating properties, and examples of such a compound are as follows.

R of the following formula represents an organic group.

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

Further, the compound of the component (B) is used in an amount of from 0.5 to 80 parts by mass, more preferably from 2 to 40 parts by mass, per 100 parts by mass of the thermally crosslinked product of the component (A). When the amount of the compound of the component (B) is less than the lower limit of the above range, the thermal curing is insufficient, and a satisfactory cured film cannot be obtained. On the other hand, the amount of the compound of the component (B) exceeds the above. When the upper limit of the range is excessive, development becomes insufficient and development residue is generated.

<C component>

The component (C) is a photoacid generator (PAG). This is a substance which directly or indirectly generates an acid (sulfonic acid, carboxylic acid, etc.) by irradiation of light (ultraviolet rays such as g, h, and i lines, ArF, KrF, F ₂ laser light, or electron beam) used for exposure. As long as it has such a property, its kind and configuration are not particularly limited.

The photoacid generator as the component (C), for example, a diazomethane compound, a phosphonium salt compound, a quinone imine compound, a diterpenoid compound, a sulfonic acid derivative compound, a nitrobenzyl compound, a benzoin tosylate compound , iron aromatic hydrocarbon complex, halogen-containing three A compound, an acetophenone-derived compound, a cyano-containing sulfonium sulfonate compound, and the like. Any of conventionally known or conventionally used photoacid generators is not particularly limited and can be suitably used in the present invention. Furthermore, in the present invention, the photoacid generator of the component (C) may be used alone or in combination of two or more.

Specific examples of such a photoacid generator are as follows. In particular, these compounds are a few examples of a very large number of applicable photoacid generators, and are of course not limited thereto.

Diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium methanesulfonate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyltetrafluoroborate Iodine iodine, diphenyl iodonium hexafluoroantimonate, diphenyl iodonium hexafluoroarsenate, bis(p-butyl phenyl) iodonium hexafluorophosphate, bis(p-butyrethane) Butyl phenyl) iodonium, bis(p-butyl phenyl) iodonium toluene sulfonate, bis(p-butyl phenyl) iodonium trifluoromethanesulfonate, bis(tetrafluoroborate) - 3rd butyl phenyl) iodonium, chlorinated double (pair - first 3-butylphenyl)iodonium, bis(p-chlorophenyl)iodonium chloride, bis(p-chlorophenyl)iodonium tetrafluoroborate, triphenyl sulfonium chloride, bromine Triphenylsulfanthene, triphenylsulfonium trifluoromethanesulfonate, tris(p-methoxyphenyl)sulfonium tetrafluoroborate, tris(p-methoxyphenyl)sulfonium hexafluorophosphonate , tris(p-ethoxyphenyl)phosphonium tetrafluoroborate, triphenylsulfonium chloride, triphenylsulfonium bromide, tris(p-methoxyphenyl)phosphonium tetrafluoroborate, hexafluorophosphonic acid Tris(p-methoxyphenyl)anthracene, tris(p-ethoxyphenyl)anthracene tetrafluoroborate.

Further, the photoacid generator of the component (C) is used in an amount of from 0.2 to 80 parts by mass, more preferably from 0.5 to 30 parts by mass, per 100 parts by mass of the thermally crosslinked product of the component (A). When the amount of the photoacid generator of the component (C) is too small as the lower limit of the above range, the portion of the vinyl ether compound of the thermally crosslinked product of the component (A) is thermally crosslinked upon exposure, The dissociation of the alkali-soluble resin portion of the thermal crosslinked body in which the component (A) is formed is not sufficiently performed, and it is difficult to obtain the unevenness of the desired pattern. On the other hand, the use of the photoacid generator of the component (C) is used. When the amount is excessively larger than the upper limit of the above range, the storage stability of the positive photosensitive resin composition is deteriorated.

<D solvent>

The solvent (D) used in the present invention is a solvent which dissolves the components (A) to (C) and dissolves the components (E) to (G) described later, as desired, as long as it has such a dissolving power. The solvent, the kind and the structure thereof are not particularly limited.

As such a solvent (D), for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 2-ethoxyethyl 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, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate , methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate Ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

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

Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, etc., have good coating properties. The idea of high security is more ideal. These solvents are generally used as a solvent for a photoresist material.

<E component>

The component (E) is an alkali-soluble resin, and is a resin different from the alkali-soluble resin portion forming the thermal crosslinked body of the component (A). The positive photosensitive resin composition of the present invention may further contain another alkali-soluble resin which is different from the alkali-soluble resin portion which forms the thermal cross-linking component of (A) without impairing the effects of the present invention.

As such a component (E), for example, an acrylate-based resin in which an alkali-soluble resin portion of the thermal cross-linking component of (A) is different, a hydroxystyrene-based resin, a phenol novolac resin, a polyamido resin, and a polyfluorene-based resin are formed. Amine precursor, polyimine resin, and the like.

<F component>

The component (F) is an amine compound, and the positive photosensitive resin composition of the present invention may further contain an amine compound for the purpose of improving the preservation stability without impairing the effects of the present invention.

The amine compound as the component (F) is not particularly limited, and examples thereof include triethanolamine, tributylamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-butylamine, and a tertiary amine such as azide bicyclooctane or the like, an aromatic amine such as pyridine or 4-dimethylaminopyridine, and further a primary amine such as benzylamine or n-butylamine, diethylamine and di-n-amine. A grade 2 amine such as butylamine.

The amine compound of the component (F) may be used alone or in combination of two or more.

In the case of using an amine compound, the content thereof is, for example, 0.0005 to 5 parts by mass, and optionally 0.002 to 1 part by mass, based on 100 parts by mass of the thermally crosslinked body of the component (A), and more preferably 0.005 to 0.5 parts by mass. When the amount of the amine compound of the component (F) is too small as the lower limit of the above range, the storage stability of the positive photosensitive resin composition cannot be sufficiently improved, and the use of the amine compound of the component (F) When the amount is excessively more than the lower limit of the above range, the sensitivity of the positive photosensitive resin composition may be lowered.

<G component>

The component (G) is a surfactant. In order to improve the coatability of the positive photosensitive resin composition of the present invention, a surfactant may be further contained without impairing the effects of the present invention.

The surfactant of the component (G) is not particularly limited, and examples thereof include a fluorine-based surfactant, a ruthenium-based surfactant, and a nonionic surfactant. As such a surfactant, commercially available products such as Sumitomo 3M Co., Ltd., Dainippon Ink Chemical Industry Co., Ltd., or Asahi Glass Co., Ltd. can be used. These commercial products are suitable because they are easily available. Specific examples thereof include EFTOP EF301, EF303, EF352 (made by JEMCO), MEGAFAC F171, F173 (made by Dainippon Ink Chemical Industry Co., Ltd.), FLUORAD FC430, FC431 (Sumitomo 3M (share) system), ASAHIGUARD A fluorine-based surfactant such as AG710, SURFLON S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.).

The surfactant of the component (G) 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, and preferably 0.1% by mass or less, based on 100% by mass of the thermally crosslinked body of the component (A). Even if the amount of use of the surfactant of the component (G) is more than 0.2% by mass, the effect of improving the coating property becomes slow and uneconomical.

<Other additives>

Further, the positive-type photosensitive resin composition of the present invention may contain an adhesion promoter such as a rheology modifier, a decane coupling agent, a pigment, a dye, a storage stabilizer, and a defoaming, as needed, without impairing the effects of the present invention. A dissolution promoter such as a polyvalent phenol or a polyvalent carboxylic acid.

<Positive Photosensitive Resin Composition>

The positive photosensitive resin composition of the present invention contains a thermally crosslinked product of the component (A), a compound having a blocked isocyanate group as the component (B), a photoacid generator of the component (C), and (D) a solvent. Further, one or more of the alkali-soluble resin of the component (E), the amine compound of the component (F), the surfactant of the component (G), and other additives may be contained as desired.

Among them, a preferred example of the positive photosensitive resin composition of the present invention is as follows.

[1] The component (A) is a heat-crossing compound having 1 to 80 parts by mass of a vinyl ether group based on 100 parts by mass of an alkali-soluble resin having a functional group capable of undergoing a thermosetting reaction with the compound of the component (B). And the heat-crosslinking body of the (A) component contains 0.5 to 80 parts by mass of the component (B) and 0.2 to 80 parts by mass of the component (C), and the components are dissolved. A positive photosensitive resin composition formed by the solvent (D).

[2] The composition of the above [1], further comprising a positive photosensitive resin composition of the component (E).

[3] The composition of the above [1] or [2] further comprising a positive photosensitive resin having a (F) component of 0.005 to 5 parts by mass based on 100 parts by mass of the thermally crosslinked body of the component (A). Things.

[4] The composition of the above [1], [2] or [3] further contains 0.2% by mass or less of the positive photosensitive resin composition of the component (G).

The ratio of the solid content in the positive photosensitive resin composition of the present invention is not particularly limited, and is, for example, 1 to 80% by mass, or for example, 5 to 60% by mass, or 10 to 10, in the case where the respective components are uniformly dissolved in the solvent. 50% by mass. Here, the solid component means a solvent (D) is removed from all components of the positive photosensitive resin composition.

The method for preparing the positive photosensitive resin composition of the present invention is not particularly limited, and as the preparation method, for example, (A) component (thermally crosslinked body) and (B) component (two or more molecules in one molecule are embedded) a method of mixing a compound of the isocyanate group), a component (C) (a photoacid generator, and a component (G) (a surfactant) in a predetermined ratio in a solvent (D) to form a homogeneous solution, or the method At the appropriate stage, a method of mixing (F) component (amine compound), (E) component (alkali-soluble resin), and/or other additives may be added as needed.

A preparation of a positive photosensitive resin composition suitable for the present invention, (D) a solution of a specific copolymer obtained by polymerization in a solvent may be used as it is, in which case the solution of the specific copolymer has a vinyl ether When a component (B) or a component (C) which is the same as the above is added to a solution of the component (A) in the reaction of the compound to form a homogeneous solution, it may be further added for the purpose of adjusting the concentration. (D) Solvent. In this case, the (D) solvent used to adjust the concentration of the solvent used in the formation of the specific copolymer and the positive photosensitive resin composition may be the same or different.

Further, the solution of the adjusted positive photosensitive resin composition is preferably used after filtration using a filter having a pore size of about 0.2 μm.

<Coating film and hardened film>

The positive photosensitive resin composition of the present invention is applied to a semiconductor substrate by spin coating, shower coating, roll coating, slit coating, spin coating of a continuous slit, inkjet coating, or the like ( For example, a crucible/cerium oxide substrate, a tantalum nitride substrate, a metal substrate such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, an ITO substrate, or the like is coated, and then dried in advance by a hot plate or an oven. , a coating film can be formed.

As the conditions of the heat treatment, for example, a heating temperature and a heating time which are appropriately selected in 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 the heating time are preferably from 80 ° C to 140 ° C for a period of from 0.5 to 10 minutes.

Further, the film thickness of the positive photosensitive resin film formed from the positive photosensitive resin composition is, for example, 0.1 to 50 μm, or for example, 0.3 to 30 μm, and for example, 0.5 to 10 μm.

Therefore, the positive-type photosensitive resin film formed is further thermally crosslinked by a functional group capable of crosslinking reaction with a vinyl ether group in the thermal crosslinked body of the component (A) due to heat treatment at the time of formation. It becomes a film which is hard to dissolve in an alkali developing solution. In this case, when the heating temperature is lower than the lower limit of the above temperature range, thermal crosslinking is insufficient, and film formation is reduced in the unexposed portion. Further, when the heating temperature is excessively higher than the upper limit of the above temperature range, the formed thermal cross-linking portion is again cut, resulting in a decrease in the film in the unexposed portion.

The positive photosensitive resin film formed from the positive photosensitive resin composition of the present invention is exposed to light such as ultraviolet rays, ArF, KrF, or F ₂ laser light by using a mask having a predetermined pattern. The action of the acid generated by the photoacid generator (PAG) of the component (C) contained in the positive photosensitive resin film is such that the exposed portion of the film is soluble in the alkaline developer.

Then, the positive photosensitive resin film is subjected to heating (PEB) after exposure. As the heating conditions in this case, for example, a heating temperature and a heating time which are appropriately selected in the range of a temperature of 80 ° C to 150 ° C and a time of 0.3 to 60 minutes are employed.

Then, development was carried out using an alkaline developer. Thereby, in the positive photosensitive resin film, the exposed portion is removed, and irregularities such as a pattern are formed.

As the alkaline developing solution to be used, for example, an aqueous solution of an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, an aqueous solution of tetramethylammonium hydroxide, tetraethylammonium hydroxide or quaternary ammonium, and an ethanolamine. An alkaline aqueous solution such as an aqueous amine solution such as propylamine or ethylenediamine. Further, a surfactant may be added to these developing solutions.

In the above, an aqueous solution of 0.1 to 2.38 mass% of tetraethylammonium hydroxide is generally used as a developing solution for a photoresist, and the alkaline developing solution is also used in the positive photosensitive resin composition of the present invention, and does not cause swelling. The problem can be well developed.

Further, as a method of development, for example, any of a liquid coating method, a dipping method, and a shaking dipping method can be used. The development time at this time is usually 15 to 180 seconds.

After the development, the positive photosensitive resin film is washed with running water for, for example, 20 to 90 seconds, and then the moisture on the substrate is removed by using compressed air or compressed nitrogen or by air drying to obtain a patterned film.

Then, such a patterned film is subjected to post-baking for heat hardening, specifically by heating using a hot plate, an oven, or the like, thereby obtaining heat resistance, transparency, flatness, low water absorption, and chemical resistance. A film that is excellent and has a good uneven pattern.

As the post-stage baking, the heating temperature is generally selected from the range of 140 ° C to 250 ° C, the case on the hot plate is 5 to 30 minutes, and the case in the oven is 30 to 90 minutes.

Further, by such post-stage baking, a cured film having a good pattern shape can be obtained.

As described above, the positive photosensitive resin composition of the present invention has a sufficiently high sensitivity and does not substantially obviate the film thickness of the unexposed portion during development, and a coating film having a fine pattern can be formed.

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

Further, when such a cured film is used for, for example, an array planarizing film for a liquid crystal display, in the subsequent step, metal vapor deposition may be exposed to a higher temperature (for example, 250 ° C) heating, depending on the case. When the film is fired at a high temperature (for example, 230 ° C) for a long period of time or after the photoresist is removed after the etching, it may be placed under contact with a photoresist stripping solution of an aqueous amine solution such as monoethanolamine (MEA). Therefore, in such a cured film, high-temperature firing (or long-time firing) or high-resistance treatment of a photoresist stripping solution (amine-based solution) is required.

The cured film obtained by the present invention is treated by high-temperature baking (or long-time firing) or photoresist peeling liquid (amine-based solution) to have a very small decrease in transmittance, maintain high transparency, and have a large film thickness. A cured film which is also low in heat resistance and excellent in chemical resistance, so it is suitable not only for an array flattening film of a TFT type liquid crystal element but also various films for liquid crystal or organic EL display, such as an interlayer insulating film, a protective film, and an insulating film. The use of the film or the uneven film on the lower side of the reflective film can be applied to the microlens by selecting the shape of the cured film.

Example

The invention will be described in more detail below by way of examples, but the invention is not limited thereto.

[Abbreviation used in the embodiment]

The meanings of the abbreviations used in the following examples are as follows.

MAA: Methacrylic acid MMA: Methyl methacrylate HEMA: 2-hydroxyethyl methacrylate CHMI: N-cyclohexyl maleimide imide ST: Styrene NHPMA: N-hydroxyphenylmethacryl oxime Amine PEMA: mono-2-(methacryloxy)ethyl phthalate AIBN: azobisisobutyronitrile PGMEA: propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether PAG1: Chiba special chemistry ( CGI1397 (trade name) PVE1: Tris(4-ethyleneoxy)butyl trimellitate PVE2: 1,4-cyclohexane dimethanol vinyl ether NCO1: VESTAGON (registered trademark) manufactured by Degussa AG B 1065 (trade name) R30: MEGAFAC R-30 (trade name) manufactured by Dainippon Ink Chemical Industry Co., Ltd. GT4: GT-401 (trade name) manufactured by DAICEL Chemical Industry Co., Ltd. MPTS: γ-methyl propylene oxime Propyltrimethoxydecane P200: P-200 (trade name) manufactured by Toyo Seiki Co., Ltd. from 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1methylethyl Photosensitive agent synthesized by condensation reaction of phenyl]ethylidene]bisphenol 1 molar with 1,2-naphtholphthale-2-diazide-5-sulfonyl chloride 2 molar

[Measurement of number average molecular weight and weight average molecular weight]

The number average molecular weight and the weight average molecular weight of the specific copolymer obtained by the following synthesis examples and the specific crosslinked body were determined by using a GPC apparatus (Shodex (registered trademark) column KF803L and KF804L) manufactured by JASCO Corporation. Tetrahydrofuran was measured by flowing at a flow rate of 1 ml/min in a column (column temperature of 40 ° C) and dissolving it. Further, 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 copolymers] <Synthesis Example 1>

MAA 15.5g, CHMI 35.3g, HEMA 25.5g, MMA 23.7g were used as the monomer component constituting the specific copolymer, and AIBN 5g was used as the radical polymerization initiator, and these were in the solvent PGMEA 200g at a temperature of 60 ° C to 100 ° The polymerization reaction was carried out at ° C to obtain a solution P1 (concentration of a specific copolymer: 27.5 mass%) of a specific copolymer having Mn of 4,100 and Mw of 7,600.

<Synthesis Examples 2 to 4>

The monomer component and the solvent described in each of the columns of Synthesis Examples 2 to 4 in Table 1 below were used, and the polymerization reaction was carried out in the same order and conditions as in Synthesis Example 1, in place of the monomer component and solvent used in Synthesis Example 1. A solution (P2 to P4) of each specific copolymer was obtained.

The Mn and Mw of each of the obtained specific copolymers (P1 to P4) were measured.

These results are shown in Table 1.

[Synthesis of specific crosslinked bodies] <Synthesis Example 5>

100 g of the solution P1 of the specific copolymer prepared by the synthesis example 1 of the specific copolymer component constituting the specific crosslinked body of the component (A), and 1.38 g of PVE2 (CHDVE) as a polyfunctional vinyl ether compound, and The solvent PGMEA 18g was mixed and reacted at a temperature of 50 ° C for 16 hours to obtain a solution C1 of Mn (4,900) and Mw of 14,400 (A) component (specific crosslinked body) (concentration of specific crosslinked body: 25.0% by mass) ).

<Synthesis Example 6 to Synthesis Example 9>

The solution of the specific copolymer described in each of the columns of Synthesis Example 6 to Synthesis Example 9 in the following Table 2, the polyfunctional vinyl ether compound, and the solvent were reacted in the same order and conditions as in Synthesis Example 5. A solution (C2 to C5) of each specific crosslinked body was obtained.

The above results are shown in Table 2.

[Modulation of Positive Photosensitive Resin Composition] <Examples 1 to 5>

According to the composition shown in Table 3 below, a predetermined ratio of the components (B), (C), (D), and (G) are mixed in a solution of the specific crosslinked product of the component (A) at room temperature. The mixture was stirred for 3 hours to obtain a homogeneous solution, and the positive photosensitive resin composition of each example was prepared.

<Comparative Examples 1 to 4>

According to the composition shown in Table 3 below, a solution of the component (A) is replaced with a solution of a specific copolymer (P1 to P3), and it is combined with a vinyl ether compound, (B) component, (C) component, (D). The solvent and the component (G) were mixed at a predetermined ratio, and stirred at room temperature for 3 hours to obtain a uniform solution, and a positive photosensitive resin composition of each comparative example was prepared.

<Comparative Example 5>

20 g of the solution (P1) of the specific copolymer obtained in Synthesis Example 1 was used as a solution of the substituted (A) component, and P200 of the 1,2-quinonediazide compound was used as the component (C), and 1.1 g of the epoxy was used. GT4 which is a crosslinkable compound, substituted (B) component, 0.0039g of R30 as a surfactant of (G) component, 0.25g of MPT as an adhesion adjuvant, and 10.6g of PGMEA as a solvent, and mix|blend, The mixture was stirred at room temperature for 8 hours to obtain a homogeneous solution, and the positive photosensitive resin composition of Comparative Example 5 was prepared.

Each of the positive photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 5 was subjected to sensitivity, film thinning (unexposed portion), light transmittance after high-temperature firing (transparency), and MEA. Each item of the light transmittance, the MEA resistance, and the dimensional accuracy after the treatment was evaluated in the following order.

Further, when the cured film was obtained from the positive photosensitive resin composition, Comparative Example 5 was subjected to photobleaching at the stage before the post-baking after development, and on the other hand, Examples 1 and 2 and Comparative Examples 1 to 4 were not carried out. Photobleaching, post-exposure, and post-exposure heating (PEB), the order of evaluation of the two, as described below.

[Evaluation of sensitivity] <Examples 1 to 5, Comparative Examples 1 to 4>

The positive photosensitive resin composition was applied to a crucible using a spin coater.

After the wafer was placed on a hot plate at a temperature of 110 ° C for 120 seconds, prebaking was carried out to form a coating film having a film thickness of 2.5 μm. The film thickness was measured using F20 manufactured by FILMETRICS. The coating film was irradiated with ultraviolet light of a light intensity of 5.5 mW/cm ² at 365 nm for a certain period of time by a Canon ultraviolet light irradiation apparatus PLA-600FA, and then placed on a hot plate at a temperature of 110 ° C for 120 seconds to perform post-exposure heating. (PEB). Then, it was immersed in a 0.4% by mass aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 60 seconds, and after development, it was washed with ultrapure water for 20 seconds. The minimum exposure amount (mJ/cm ² ) which does not remain in the exposure portion is taken as the sensitivity.

<Comparative Example 5>

The positive photosensitive resin composition was applied onto a tantalum wafer using a spin coater, and then placed on a hot plate at a temperature of 110 ° C for 120 seconds, and prebaked to form a coating film having a film thickness of 2.5 μm. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was irradiated with ultraviolet light of 365 nm light intensity of 5.5 mW/cm ² for a predetermined period of time by a Canon ultraviolet light irradiation apparatus PLA-600FA. Then, it was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds, and after development, it was washed with ultrapure water for 20 seconds. The minimum exposure amount (mJ/cm ² ) which does not remain in the exposure portion is taken as the sensitivity.

[Evaluation of film thinning]

The positive photosensitive resin composition was applied onto a tantalum wafer using a spin coater, and then placed on a hot plate at a temperature of 110 ° C for 120 seconds, and prebaked to form a coating film having a film thickness of 2.5 μm. The film was immersed in a 0.4% by mass aqueous solution of TMAH for 60 seconds, and then washed with running water for 20 seconds in ultrapure water. Then, by measuring the film thickness of the film, the degree of film thinning of the unexposed portion due to development was evaluated. The film thickness of this evaluation was measured by F20 manufactured by FILMETRICS.

[Evaluation of light transmittance (transparency) after high-temperature firing] <Examples 1 to 5, Comparative Examples 1 to 4>

The positive photosensitive resin composition was applied onto a quartz substrate using a spin coater, and then placed on a hot plate at a temperature of 110 ° C for 120 seconds, and prebaked to form a coating film having a film thickness of 2.5 μm. The coating film was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds, and then washed with running water for 20 seconds in ultrapure water. Then, by heating at 230 ° C for 30 minutes, the post-baking was carried out to form a cured film having a film thickness of 1.9 μm. The cured film was measured for transmittance at a wavelength of 400 nm using an ultraviolet-visible spectrophotometer (SHIMADSU UV-2550 model manufactured by Shimadzu Corporation). The coating film was further heated at 250 ° C for 30 minutes, and the transmittance at a wavelength of 400 nm was measured. The film thickness of this evaluation was measured by F20 manufactured by FILMETRICS.

<Comparative Example 5>

The positive photosensitive resin composition was applied onto a quartz substrate using a spin coater, and then placed on a hot plate at a temperature of 110 ° C for 120 seconds, and prebaked to form a coating film having a film thickness of 2.4 μm. The coating film was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds, and then washed with running water for 20 seconds in ultrapure water. The coating film was irradiated with ultraviolet light (photobleaching) of 800 mJ/cm ² at a light intensity of 5.5 mW/cm ² at 365 nm by a Canon ultraviolet light irradiation apparatus PLA-600FA, and then heated at 230 ° C for 30 minutes. The latter stage was baked to form a cured film having a film thickness of 1.9 μm. The cured film was measured for transmittance at a wavelength of 400 nm using an ultraviolet-visible spectrophotometer (SHIMADSU UV-2550 model manufactured by Shimadzu Corporation). The coating film was further heated at 250 ° C for 30 minutes, and the transmittance at a wavelength of 400 nm was measured. The film thickness of this evaluation was measured by F20 manufactured by FILMETRICS.

[Evaluation of light transmittance and MEA resistance after MEA treatment] <Examples 1 to 5, Comparative Examples 1 to 4>

The positive photosensitive resin composition was applied onto a quartz substrate using a spin coater, and then placed on a hot plate at a temperature of 110 ° C for 120 seconds, and prebaked to form a coating film having a film thickness of 2.5 μm. The coating film was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds, and then washed with running water for 20 seconds in ultrapure water. Then, by heating at 230 ° C for 30 minutes, the post-baking was carried out to form a cured film having a film thickness of 1.9 μm. The coating film was immersed in monoethanolamine heated to 60 ° C for 20 minutes, and washed with pure water for 20 seconds. Then, the plate was dried on a hot plate at a temperature of 180 ° C for 10 minutes, and the film thickness was measured and the transmittance at a wavelength of 400 nm was measured using an ultraviolet-visible spectrophotometer (SHIMADSU UV-2550 model manufactured by Shimadzu Corporation). The film thickness of this evaluation was measured by F20 manufactured by FILMETRICS. The film thickness after the post-baking and the MEA treatment and the film thickness after drying did not change, and the MEA resistance was ○, and the decrease was ×.

<Comparative Example 5>

The positive photosensitive resin composition was applied onto a quartz substrate using a spin coater, and then placed on a hot plate at a temperature of 110 ° C for 120 seconds, and prebaked to form a coating film having a film thickness of 2.4 μm. The coating film was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds, and then washed with running water for 20 seconds in ultrapure water. The coating film was irradiated with ultraviolet light (photobleaching) of 800 mJ/cm ² at a light intensity of 5.5 mW/cm ² at 365 nm by a Canon ultraviolet light irradiation apparatus PLA-600FA, and then heated at 230 ° C for 30 minutes. The latter stage was baked to form a cured film having a film thickness of 1.9 μm. The coating film was immersed in monoethanolamine heated to 60 ° C for 20 minutes, and washed with pure water for 20 seconds. Then, the plate was dried on a hot plate at a temperature of 180 ° C for 10 minutes, and the film thickness was measured and the transmittance at a wavelength of 400 nm was measured using an ultraviolet-visible spectrophotometer (SHIMADSU UV-2550 model manufactured by Shimadzu Corporation). The film thickness of this evaluation was measured by F20 manufactured by FILMETRICS. The film thickness after the post-baking and the MEA treatment and the film thickness after drying did not change, and the MEA resistance was ○, and the decrease was ×.

[Dimensional accuracy] <Examples 1 to 5, Comparative Examples 1 to 4>

The positive photosensitive resin composition was applied onto a tantalum wafer using a spin coater, and then placed on a hot plate at a temperature of 110 ° C for 120 seconds, and prebaked to form a coating film having a film thickness of 2.5 μm. The film thickness was measured using F20 manufactured by FILMETRICS. The coating film was irradiated with a 40 mJ/cm ² ultraviolet light having a light intensity of 5.5 mW/cm ² at 365 nm by a Canon-made ultraviolet irradiation device PLA-600FA through a mask having a line of 8 μm lines and spaces, and then The temperature was placed on a hot plate at 110 ° C for 120 seconds, and post-exposure heating (PEB) was performed. Then, the coating film was immersed in a 0.4% by mass aqueous TMAH solution for 60 seconds, and then washed with ultrapure water for 20 seconds. Then, the post-baking was carried out by heating 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. If the width of the pattern is maintained at 8 μm, it is ○, and if the width of the pattern is wide or narrow, and it is not possible to maintain 8 μm, it is ×.

<Comparative Example 5>

The positive photosensitive resin composition was applied onto a tantalum wafer using a spin coater, and then placed on a hot plate at a temperature of 110 ° C for 120 seconds, and prebaked to form a coating film having a film thickness of 2.5 μm. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was irradiated with ultraviolet rays of 200 mJ/cm ² at a light intensity of 5.5 mW/cm ² at 365 nm by a Canon-made ultraviolet irradiation device PLA-600FA through a mask of a line of 8 μm lines and spaces. Then, the coating film was immersed in a 0.4% by mass aqueous TMAH solution for 60 seconds, and then washed with ultrapure water for 20 seconds. Then, the post-baking was carried out by heating 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. If the width of the pattern is maintained at 8 μm, it is ○, and if the width of the pattern is wide or narrow, and it is not possible to maintain 8 μm, it is ×.

[Save stability] <Examples 1 to 5, Comparative Examples 1 to 4>

The positive photosensitive resin composition was stored at 23 ° C for one month, and then visually evaluated. The evaluation was ○ in the absence of gelation and × in the gelation.

[Results of evaluation]

The results of the above evaluations are shown in Table 4 below.

It is judged from the results shown in Table 4 that any of Examples 1 to 5 has a high sensitivity, and the measurement result actually does not observe film thinning of the unexposed portion, at 250 ° C (or 230 ° C) for 30 minutes. After high-temperature firing, the decrease in light transmittance is small, high transparency is maintained, and the light transmittance is reduced by MEA treatment, and the MEA resistance and dimensional accuracy are excellent, and the storage stability is also good.

On the contrary, in Comparative Examples 1 to 3, since the patterned film was reflowed at 230 ° C for 30 minutes, the pattern of the desired shape and size could not be obtained. Further, the film having no pattern was formed, and after baking at 230 ° C for 30 minutes, the film was thinned by treatment with MEA. The film thickness after MEA treatment was reduced by about 25% compared to the film thickness before MEA treatment. Further, the "transmittance after the MEA treatment" in Table 4 is the value of the film in which the film is thinned after the MEA treatment.

In Comparative Example 4, film dissolution disappeared due to development.

Further, in Comparative Example 5, the amount of film thinning of the unexposed portion at the time of development was 0.2 μm. After baking at 230 ° C for 30 minutes, the transmittance of the film was 92%, and when it was further baked at 250 ° C for 30 minutes, the transmittance of the film was lowered to 85%. Further, after baking at 230 ° C for 30 minutes, if the MEA treatment was performed, the transmittance of the film was lowered from 92% to 86%.

[Industrial use possibility]

The positive-type photosensitive resin composition of the present invention is suitable as a material for forming a cured film such as a protective film for a thin film transistor (TFT) liquid crystal display device or an organic EL device, a planarizing film, or an insulating film, and is particularly suitable. A material such as an interlayer insulating film of a TFT-type liquid crystal element, a protective film for a filter, an array flattening film, an uneven film on the lower side of a reflective film of a reflective display, an insulating film of an organic EL element, or the like is suitable as a micro Various electronic materials such as lens materials.

Claims (16)

A positive photosensitive resin composition comprising the following components (A), (B), (C), and (D) a solvent; wherein the component (A) has a component (B) a matrix polymer having a functional group for hardening a film by a thermosetting reaction between compounds, containing two or more formulas (1) derived from a polyfunctional vinyl ether compound The thermally crosslinked body formed by bonding the chemical structures of the thermal crosslinking groups to each other, and having a weight average molecular weight of 10,000 to 250,000, and (B) component: having two or more in one molecule a segment isocyanate group-containing compound; (C) component: photoacid generator; (D) solvent. The positive photosensitive resin composition of the first aspect of the invention, wherein the functional group for curing the film is at least one functional group selected from the group consisting of a hydroxyl group other than a phenolic hydroxyl group and an amine group of an active hydrogen. The positive photosensitive resin composition of claim 1 or 2, wherein the thermal crosslinked body of the component (A) further contains a functional group capable of thermal crosslinking reaction and a vinyl ether group. The positive photosensitive resin composition of claim 3, wherein the functional group for the thermal crosslinking reaction is at least one functional group selected from the group consisting of a carboxyl group and a phenolic hydroxyl group. The positive photosensitive resin composition of claim 1, wherein the component (A) is an alkali-soluble resin having a functional group having a heat-crosslinkable reaction and having a number average molecular weight of 2,000 to 30,000 and one molecule Two or more vinyl ether-based compounds are thermally crosslinked by a thermal crosslinking reaction. The positive photosensitive resin composition of claim 5, wherein the component (A) is thermally crosslinked by 1 to 80 parts by mass of the vinyl ether group-containing compound based on 100 parts by mass of the alkali-soluble resin. The thermal crosslinks formed by the reaction. The positive photosensitive resin composition of the first aspect of the invention, wherein the thermally crosslinked body based on the component (A) is contained in an amount of 0.5 to 80 parts by mass of the component (B) and 0.2 to 80% by mass. (C) ingredients. The positive photosensitive resin composition of claim 1, wherein an alkali-soluble resin is further contained as the component (E). The positive-type photosensitive resin composition of the eighth aspect of the invention, wherein the alkali-soluble resin of the component (E) is an alkali-soluble resin other than the alkali-soluble resin of the thermal crosslinked product of the component (A). The positive-type photosensitive resin composition of the first aspect of the invention, wherein the thermal crosslinked product based on the component (A) is 100 parts by mass, and further contains 0.0005 to 5 parts by mass of an amine compound as the component (F). The positive photosensitive resin composition of the first aspect of the invention, wherein the positive photosensitive resin composition further contains 0.2% by mass or less of a surfactant as the component (G). A cured film obtained by using a positive photosensitive resin composition according to any one of claims 1 to 11. A liquid crystal display element comprising: a cured film according to item 12 of the patent application. An array flattening film element for a liquid crystal display, which is characterized in that it is made of a cured film as in claim 12 of the patent application. An interlayer insulating film comprising: a cured film as disclosed in claim 12 of the patent application. A microlens characterized by being formed of a cured film as in claim 12 of the patent application.