JP4753040B2 - Negative photosensitive resin composition containing a compound having a polymerizable group - Google Patents

Description

  The present invention relates to a negative photosensitive resin composition and a cured film obtained therefrom. More specifically, the present invention relates to a negative photosensitive resin composition having high transparency even after high-temperature baking, a cured film thereof, and various materials using the cured film. This negative photosensitive resin composition is particularly suitable as an interlayer insulating film and a color filter material in liquid crystal displays, EL displays, and solid-state imaging devices.

  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, a color filter, 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 transparency is obtained. Have been widely used.

  These films described above have excellent process resistance such as low dielectric constant, heat resistance and solvent resistance, good adhesion to the substrate, and various process conditions according to the purpose of use. Various characteristics such as having a wide process margin capable of forming a pattern, high sensitivity and high transparency, and less film unevenness after development are required. Therefore, from the viewpoint of such required characteristics, conventionally, as the photosensitive resin composition, a resin containing a compound having an unsaturated double bond and a photoradical initiator has been widely used (for example, Patent Documents). 1).

  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 enables a significant reduction in production time in industrial production of display elements and the like. For this reason, in the present situation where the demand for liquid crystal displays is remarkably increasing, the sensitivity is one of the most important characteristics required for this type of photosensitive resin material.

  So far, several developments have been made for the purpose of increasing the sensitivity of the photosensitive resin material. For example, a chemically amplified photosensitive resin composition comprising an alkali-soluble resin, a photoacid generator, and a crosslinking agent that reacts with an acid has been proposed (see, for example, Patent Documents 1 and 2).

  On the other hand, these photosensitive resin compositions have a problem that they are colored at the time of curing and baking because of the combined use of an alkali-soluble resin and a photoacid generator, and high transparency cannot be obtained. In particular, coloring when using a nonionic photoacid generator used in the ghi line is remarkable.

Under such circumstances, a photosensitive resin composition suitable as a material for forming a patterned insulating film used for a liquid crystal display element, an organic EL display element, etc., specifically, a pattern having high transparency A chemically amplified photosensitive resin composition capable of easily forming an insulating film with high accuracy and high throughput has been desired.
JP-A-62-164045 Japanese Patent Laid-Open No. 2005-024970

The present invention has been made based on the above circumstances, and the problem to be solved is that a pattern insulating film having high transparency can be easily formed with high accuracy and high throughput. The object is to provide a chemically amplified negative photosensitive resin composition.

  The present invention also relates to a cured film or a color filter obtained using such a negative photosensitive resin composition, which is excellent in heat resistance and chemical resistance and maintains high transparency. It is an object of the present invention to provide a filter and various elements and materials made using such a cured film or a color filter.

That is, as a first aspect, a negative photosensitive resin composition containing the following component (A), component (B), component (C), component (D), and solvent (E).
(A) component: having at least one organic group selected from the group consisting of a phenolic hydroxy group, a carboxyl group, and a group that generates a carboxylic acid or a phenolic hydroxy group by the action of heat or acid, and An alkali-soluble resin having a number average molecular weight of 2,000 to 50,000,
(B) component: a compound having two or more polymerizable groups,
(C) component: photoacid generator,
(D) component: a crosslinking agent that reacts with an acid,
(E) Solvent.
The negative photosensitive resin composition as described in a 1st viewpoint whose (A) component is an acrylic polymer as a 2nd viewpoint.
As a third aspect, the negative photosensitive resin composition according to the first aspect, wherein the component (A) is a styrene polymer.
The negative photosensitive resin composition as described in a 1st viewpoint whose (A) component is a polyimide precursor or a polyimide as a 4th viewpoint.
As a fifth aspect, as described in any one of the first to fifth aspects, the component B) is a compound having two or more organic groups selected from the group consisting of acrylate groups, methacrylate groups, and allyl groups. Negative photosensitive resin composition.
As a sixth aspect, the negative photosensitive resin composition according to any one of the first aspect to the fifth aspect, wherein the photoacid generator of component (C) is a sulfonic acid ester compound.
As a seventh aspect, the negative photosensitive resin composition according to any one of the first aspect to the sixth aspect, which further contains a surfactant as the component (F).
As an eighth aspect, a coating film obtained using the negative photosensitive resin composition according to any one of the first aspect to the seventh aspect.
As a ninth aspect, a cured film obtained using the negative photosensitive resin composition according to any one of the first aspect to the seventh aspect.
As a tenth aspect, a color filter obtained using the negative photosensitive resin composition according to the first aspect to the seventh aspect.
A display element having the cured film according to the ninth aspect as an eleventh aspect.
As a twelfth aspect, a liquid crystal display device having the cured film according to the ninth aspect.
As a thirteenth aspect, a solid-state imaging device having the color filter according to the tenth aspect.

The negative photosensitive resin composition of the present invention has a sufficiently high sensitivity even after high-temperature baking, and can form a pattern film excellent in photocuring and solvent resistance. In particular, the conventional chemical amplification type photosensitive resin composition already contains a cross-linking agent (component (D)) that reacts with an acid, so its use was not studied at all. Addition of (polyfunctional acrylate) prevents coloring at the time of curing and baking resulting from the combined use of alkali-soluble resin (component (A)) and photoacid generator (component (C)), which has been considered a problem in the past. A cured film having transparency can be obtained.
The composition is suitable as a material for forming a patterned insulating film used for a liquid crystal display element, an organic EL display element, a solid-state imaging element, a color filter material, and the like, and has high transparency. An insulating film can be easily formed with high accuracy and high throughput.

The negative photosensitive resin composition of the present invention comprises an alkali-soluble resin as the following component (A), a compound having two or more polymerizable groups as the component (B), a photoacid generator as the component (C), (D) A composition containing a component cross-linking agent and (E) a solvent, and each optionally containing a component (F) surfactant, and in detail, the above-mentioned chemically amplified negative photosensitive resin composition It is.
Hereinafter, details of each component will be described.

<(A) component>
The component (A) of the present invention has at least one organic group selected from the group consisting of a phenolic hydroxy group, a carboxyl group, and a group that generates a carboxylic acid or a phenolic hydroxy group by the action of heat or acid. And a polyimide precursor or polyimide having a number average molecular weight of 2,000 to 50,000.
The polyimide precursor or polyimide of the component (A) is not particularly limited as long as it is an alkali-soluble resin having such a structure, and the type of the main chain skeleton and side chain of the polymer constituting the resin.

However, the polyimide precursor or polyimide as the component (A) has a number average molecular weight in the range of 2,000 to 50,000. If the number average molecular weight exceeds 50,000, the development residue is likely to be generated, and the sensitivity is greatly reduced. On the other hand, if the number average molecular weight is less than 2,000, the development is insufficient. At this time, there is a case where a considerable amount of film loss occurs in the exposed portion, resulting in insufficient curing.

(A) Ingredient is a polyimide precursor or polyimide.

Moreover, in this invention, the polyimide precursor or polyimide which consists of a copolymer (henceforth a specific copolymer) obtained by superposing | polymerizing a multiple types of monomer can also be used as (A) component. In this case, the polyimide precursor or polyimide of the component (A) may be a blend of a plurality of types of specific copolymers.

  That is, the specific copolymer is selected from the group consisting of monomers that exhibit alkali solubility, that is, carboxyl groups, phenolic hydroxy groups, and groups that generate carboxylic acids or phenolic hydroxy groups by the action of heat or acid. A copolymer formed as an essential constituent unit of a monomer having at least one monomer and at least one monomer selected from the group of monomers copolymerizable with these monomers, the number average molecular weight of which is a copolymer 2,000 to 50,000.

The above “monomer having at least one selected from the group consisting of a carboxyl group, a phenolic hydroxy group, and a group that generates a carboxylic acid or a phenolic hydroxy group by the action of heat or acid” is a monomer having a carboxyl group , A monomer having a phenolic hydroxy group, and a monomer having a group that generates a carboxylic acid or a phenolic hydroxy group by the action of heat or an acid, and also a carboxylic acid by the action of these carboxyl group, phenolic hydroxy group, heat or an acid Or the monomer which has 2 or more types of group of the group which produces | generates a phenolic hydroxy group is contained. These monomers are not limited to those having a carboxyl group, a phenolic hydroxy group, or one carboxylic acid or phenolic hydroxy group by the action of heat or acid, but may have a plurality of monomers.

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 group that generates a carboxylic acid or a phenolic hydroxy group by the action of heat or an acid include, for example, tert-butyl methacrylate, tert-butyl acrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8- Tricyclodecyl methacrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, 8-ethyl-8 -Tricyclodecyl methacrylate, 2-methyl-2-adamantyl methacrylate, tert-butyl-4-vinylphenyl carbamate and the like.

  Further, the following formula (1)

(Wherein R ₁ , R ₂ and R ₃ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ₄ represents an alkyl group having 1 to 10 carbon atoms, or , R ₃ and R ₄
May be bonded to each other to form a ring. An acrylate or methacrylate having a carboxyl group protected with an organic group represented by

  As a monomer copolymerizable with a monomer having at least one selected from the group consisting of a carboxyl group, a phenolic hydroxy group, and a group that generates a carboxylic acid or a phenolic hydroxy group by the action of heat or acid, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxyl-6-lactone, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 5-methacryloyloxy-6- Hydroxynorbornene-2-carboxyl-6-lactone, 2-aminoethyl acrylate, 2-aminomethyl methacrylate and the like can be mentioned.

In addition, the specific copolymer may be a copolymer formed with monomers other than the above-described monomers (hereinafter referred to as other monomers) as constituent units.
Other monomers specifically include a carboxyl group, a phenolic hydroxy group, and
A monomer having at least one selected from the group consisting of a group that generates a carboxylic acid or a phenolic hydroxy group by the action of heat or an acid, and a monomer copolymerizable with the monomer. There is no particular limitation as long as the characteristics 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, from the group consisting of a carboxyl group, a phenolic hydroxy group, and a group that generates a carboxylic acid or a phenolic hydroxy group by the action of heat or acid. In a solvent, at least one monomer appropriately selected from the group of monomers having at least one selected, a monomer copolymerizable with the monomer, optionally other monomers other than the above monomers, and optionally a polymerization initiator in a solvent The polymerization reaction is carried out at a temperature of 50 to 110 ° C. In that case, the solvent used will not be specifically limited if the monomer which comprises a specific copolymer, and a specific copolymer are melt | dissolved. As a specific example, the solvent described in (E) solvent mentioned later is mentioned.
The specific copolymer thus obtained is usually in the form of a solution in which the specific copolymer is dissolved in a solvent.

In addition, the solution of the specific copolymer obtained as described above is re-precipitated by stirring with stirring such as diethyl ether or water, and the generated precipitate is filtered and washed, and then under normal pressure or reduced pressure. Thus, the powder of the specific copolymer can be obtained by drying at room temperature or by heating. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If sufficient purification cannot be achieved by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
In the present invention, the powder of the specific copolymer may be used as it is, or the powder may be redissolved in a solvent (E) described later and used as a solution.

In addition, as the polyimide precursor or polyimide of the component (A), polyamic acid, polyamic acid ester, polyimide precursor such as partially imidized polyamic acid, and polyimide such as carboxylic acid group-containing polyimide can be used. Can be used without particular limitation as long as they are alkali-soluble.

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

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

The diamine compound (b) is not particularly limited, and examples thereof include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1 , 3-benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis (4-amino-3-carboxyphenyl) ether, bis (4-amino-3,5-dicarboxyphenyl) ether, Bis (4-amino-3-carboxyphenyl) sulfone, bis (4-amino-3,5-dicarboxyphenyl) sulfone, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′- Diamino-3,3′-dicarboxy-5,5′-dimethylbiphenyl, 4,4′-diamino-3,3′-dicarboxy-5,5′-dimethoxybiphenyl, 1,4-bis 4-amino-3-carboxyphenoxy) benzene, 1,3-bis (4-amino-3-carboxyphenoxy) benzene, bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone, bis [4- (4-amino-3-carboxyphenoxy) phenyl] propane, 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] hexafluoropropane, 2,4-diaminophenol, 3,5-diamino Phenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis (3-amino-4-hydroxyphenyl) ether, bis (4-amino-3-hydroxyphenyl) ether, bis (4-amino-3,5-dihydroxyphenyl) ether, bis (3-amino No-4-hydroxyphenyl) methane, bis (4-amino-3-hydroxyphenyl) methane, bis (4-amino-3,5-dihydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) sulfone, Bis (4-amino-3-hydroxyphenyl) sulfone, bis (4-amino-3,5-dihydroxyphenyl) sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2 -Bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3,5-dihydroxyphenyl) hexafluoropropane, 4,4'-diamino-3,3'-dihydroxy Biphenyl, 4,4′-diamino-3,3′-dihydroxy-5,5′-dimethylbiphenyl, 4,4′-dia -3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4-bis (3-amino-4-hydroxyphenoxy) benzene, 1,3-bis (3-amino-4-hydroxyphenoxy) benzene 1,4-bis (4-amino-3-hydroxyphenoxy) benzene, 1,3-bis (4-amino-3-hydroxyphenoxy) benzene, bis [4- (3-amino-4-hydroxyphenoxy) phenyl ] Phenolic hydroxy groups such as sulfone, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] propane, 2,2-bis [4- (3-amino-4-hydroxyphenoxy) phenyl] hexafluoropropane, etc. Diamine compound, 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene 1,4-diamino-2-mercaptobenzene, bis (4-amino-3-mercaptophenyl) ether, 2,2-bis (3-amino-4-mercaptophenyl) hexafluoropropane and the like having a thiophenol group Diamine compound, 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis (4-aminobenzene-3-sulfonic acid) ) Ether, 4,4′-diaminobiphenyl-3,3′-disulfonic acid, 4,4′-diamino-3,3′-dimethylbiphenyl-6,6′-disulfonic acid and other diamine compounds having a sulfonic acid group Can be mentioned. P-phenylenediamine, m-phenylenediamine, 4,4′-methylene-bis (2,6-ethylaniline), 4,4′-methylene-bis (2-isopropyl-6-methylaniline), 4, 4'-methylene-bis (2,6-diisopropylaniline), 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, o- Tolidine, m-tolidine, 3,3 ′, 5,5′-tetramethylbenzidine, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] Propane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 4,4 ′ Diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 2,2-bis (4-anilino) hexafluoropropane, 2,2-bis (3-anilino) hexafluoropropane, 2,2- Bis (3-amino-4-toluyl) hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) Phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2′-bis (tri And diamine compounds such as (fluoromethyl) benzidine.
These may be used alone or in combination of two or more compounds.

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

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

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

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

  The solution containing the polyamic acid thus obtained can be used as it is for the preparation of a negative photosensitive resin composition. Further, the polyamic acid may be precipitated and isolated in a poor solvent such as water, methanol, ethanol, etc. and recovered for use.

Moreover, arbitrary polyimide can also be used as (A) component. The polyimide used in the present invention is obtained by chemically or thermally imidizing 50% or more of a polyimide precursor such as polyamic acid.
The polyimide used in the negative photosensitive resin composition of the present invention has a carboxyl group, a phenolic hydroxy group, or a group that generates a carboxylic acid or a phenolic hydroxy group by the action of heat or acid in order to impart alkali solubility. It is preferable to have.
The method of introducing a carboxyl group or a phenolic hydroxy group into polyimide is a method using a monomer having a carboxyl group or a phenolic hydroxy group, a method of sealing an amine terminal with an acid anhydride having a carboxyl group or a phenolic hydroxy group, Alternatively, a method of setting the imidization rate to 99% or less when imidizing a polyimide precursor such as polyamide acid is used.
In addition, a method of introducing a carboxylic acid or a phenolic hydroxy group that generates a carboxylic acid or a phenolic hydroxy group into the polyimide by the action of heat or an acid is a method using a monomer that generates a carboxyl group or a phenolic hydroxy group by the action of heat or an acid. There is a method in which a carboxyl group, a phenolic hydroxy group, or a carboxylic acid residue after imidization is reacted with a group that is dissociated by the action of heat or acid.
Such a polyimide can be obtained by synthesizing a polyimide precursor such as the above-mentioned polyamic acid and then performing chemical imidization or thermal imidization.
As a method of chemical imidization, generally, a method of adding excess acetic anhydride and pyridine to a polyimide precursor solution and reacting at room temperature to 100 ° C. is used. As a method for thermal imidization, generally, a method in which a polyimide precursor solution is heated while being dehydrated at a temperature of 180 ° C. to 250 ° C. is used.

<(B) component>
The component (B) of the present invention is a compound having two or more polymerizable groups. In the present specification, the “compound having two or more polymerizable groups” means a compound having two or more polymerizable groups in one molecule and having these polymerizable groups at the molecular ends. The polymerizable group refers to at least one organic group selected from the group consisting of an acrylate group, a methacrylate group, and an allyl group.

  The compound having two or more polymerizable groups as the component (B) has good compatibility with each component in the solution of the negative photosensitive resin composition of the present invention and does not affect the developability. From the viewpoint, a compound having a weight average molecular weight of 1,000 or less is preferable.

Specific examples of such compounds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, penta Erythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylo Rupropane trimethacrylate, 1,3,5-triacryloyl hexahydro-S-triazine, 1,3,5-trimethacryloyl hexahydro-S-triazine, tris (hydroxyethylacryloyl) isocyanurate, tris (hydroxyethylmethacryloyl) Isocyanurate, triacryloyl formal, trimethacryloyl formal, 1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethanediol diacrylate, ethanediol dimethacrylate, 2 -Hydroxypropanediol diacrylate, 2-hydroxypropanediol dimethacrylate, diethylene glycol diacrylate , Diethylene glycol dimethacrylate, isopropylene glycol diacrylate, isopropylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, N, N′-bis (acryloyl) cysteine, N, N′-bis (methacryloyl) cysteine Thiodiglycol diacrylate, thiodiglycol dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F dimethacrylate, bisphenol S diacrylate, bisphenol S dimethacrylate, bisphenoxyethanol full orange acrylate, bis Phenoxyethanol full orange methacrylate, diallyl ether Scan phenol A, o-diallyl bisphenol A, diallyl maleate, triallyl trimellitate and the like.

The above compound can be easily obtained as a commercial product, and specific examples thereof include, for example, KYARAD T-1420, DPHA, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, R-526, NPGDA, PEG400DA, MANDA, R-167, HX-220, HX620, R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, RP-1040 (Nippon Kayaku Co., Ltd.), Aronix M-210, M-240, M-6200, M-309, M-400, M-400 402, M-405, M-450, M-7100, M-8030, M-8060, M-1310, M-1600, M-1960, M-8100, M-8 8530, M-8560, M-9050 (above, manufactured by Toagosei Co., Ltd.), Biscote 295, 300, 360, GPT, 3PA, 400, 260, 312, 335HP (above) , Osaka Organic Chemical Industry Co., Ltd.).
Moreover, these compounds can be used 1 type or in combination of 2 or more types.

  The proportion of component (B) used is preferably 0.5 to 70 parts by weight, more preferably 1 to 60 parts by weight, and particularly preferably 3 to 50 parts by weight per 100 parts by weight of component (A). Part by mass. When this ratio is too small, the transmittance in the visible light region is lowered, and when this ratio is too large, the developability of the unexposed portion is lowered and a residual film may be generated between the patterns. .

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

  Examples of the photoacid generator (C) include sulfonic acid compounds and other sulfonic acid derivatives, diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, nitrobenzyl compounds, benzoin tosylate compounds, iron arenes. Examples include complexes, halogen-containing triazine compounds, acetophenone derivative compounds, and cyano group-containing oxime sulfonate compounds. Any conventionally known or conventionally used photoacid generator can be applied in the present invention without any particular limitation.

  Although the specific example of a photo-acid generator is shown below, these are examples and are not limited to these compounds.

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

In the present invention, the photoacid generator of component (C) can be used alone or in combination of two or more. The introduction amount is selected in the range of 0.5 to 80 parts by mass, preferably 1 to 30 parts by mass with respect to 100 parts by mass of the component (A). (C) When the usage-amount of the photo-acid generator of a component is less than the minimum of the said range, the bridge | crosslinking which reacts with the polyimide precursor or polyimide of (A) component and the acid of (D) component in the case of exposure In some cases, the crosslinking of the agent does not proceed sufficiently, resulting in a large decrease in the film thickness at the exposed portion or the formation of a pattern. On the other hand, if the amount of the photoacid generator used as the component (C) is too much to exceed the upper limit of the above range, the storage stability of the negative photosensitive resin composition will be poor.

<(D) Crosslinking agent that reacts with acid>
The component (D) is a crosslinking agent that reacts with an acid. This is because the acid (sulfonic acid, carboxylic acid, etc.) generated from the photoacid generator (component (C)) upon irradiation with light used for exposure becomes a catalyst, and crosslinks with the polyimide precursor or polyimide of component (A). If it is a compound which reacts, the kind, structure, etc. will not be specifically limited.

(D) As a crosslinking agent which reacts with the acid of a component, the compound which has two or more nitrogen atoms substituted by the hydroxymethyl group or the alkoxymethyl group is mentioned, for example.
Specific examples of such compounds include compounds such as methoxymethylated glycoluril, methoxymethylated benzoguanamine and methoxymethylated melamine, such as hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,
6-tetrakis (butoxymethyl) glycoluril, 1,3,4,6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) Urea, 1,1,3,3-tetrakis (methoxymethyl) urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4 , 5-dimethoxy-2-imidazolinone and the like. In addition, a methoxymethyl type melamine compound (trade name Cymel 300, Cymel 301, Cymel 303, Cymel 350) manufactured by Nippon Cytec Industries Co., Ltd. (former Mitsui Cytec Co., Ltd.), butoxymethyl type melamine compound (trade name My Coat 506, Mycoat 508), compounds such as glycoluril compounds (trade names Cymel 1170, Powder Link 1174), methylated urea resins (trade names UFR65), butylated urea resins (trade names UFR300, U-VAN10S60, U-VAN10R, U -VAN11HV), urea / formaldehyde resin (high-condensation type, trade name becamine J-300S, becamine P-955, becamine N) manufactured by Dainippon Ink & Chemicals, Inc.

  Further, it may be a compound obtained by condensing a melamine compound, urea compound, glycoluril compound and benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. The high molecular weight compound manufactured from the melamine compound (trade name Cymel 303) and the benzoguanamine compound (trade name Cymel 1123) described in No. 6323310 can also be mentioned.

Furthermore, as a crosslinking agent that reacts with the acid of component (D), hydroxymethyl group or alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, etc. Polymers produced using substituted acrylamide or methacrylamide compounds can also be used.
Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethylmethacrylamide. And a copolymer of benzyl methacrylate and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate. The weight average molecular weight of such a polymer is, for example, 1000 to 500,000, or, for example, 2000 to 200000, 3000 to 150,000, or 3000 to 50000.

In the present invention, the above component (D) may be used alone or in combination of two or more. Moreover, the usage-amount is 1 to 80 mass parts with respect to 100 mass parts of (A) component, Preferably it is used in the ratio of 3 to 50 mass parts. When the amount of component (D) used is an excessive amount less than the lower limit of the above range, crosslinking with the polyimide precursor or polyimide of component (A) does not proceed sufficiently during exposure, and the film loss at the exposed area is large. Or a pattern cannot be formed. On the other hand, when the amount of the crosslinking agent that reacts with the acid of the component (C) is excessively larger than the upper limit of the above range, the storage stability of the negative photosensitive resin composition becomes poor.

<(E) Solvent>
The (E) solvent used in the present invention dissolves the (A) component to the (D) component and dissolves the (F) component, which will be added as desired, and has such a dissolving ability. If it is a solvent, the kind and structure thereof are not particularly limited.

Examples of such a solvent (E) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol. Monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethoxyacetic acid Ethyl, hydroxyethyl acetate, 2-hydroxy-3-methyl Methyl tannate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, lactic acid Examples include butyl, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.
These solvents can be used singly or in combination of two or more.

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

<(F) component>
Component (F) is a surfactant. The negative 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 as the component (F) 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.

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

  When a 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 negative photosensitive resin composition. Even if the amount of the surfactant used as the component (F) is set to an amount exceeding 0.2% by mass, the effect of improving the coating property becomes dull and not economical.

<Other additives>
Furthermore, the negative photosensitive resin composition of the present invention may be used as necessary, as long as the effects of the present invention are not impaired, as a rheology modifier, an adhesion aid such as a silane coupling agent, a pigment, a dye, or a storage stabilizer. , Antifoaming agents, or dissolution accelerators such as polyphenols and polycarboxylic acids.

<Negative photosensitive resin composition>
The negative photosensitive resin composition of the present invention comprises (A) component polyimide precursor or polyimide , (B) component compound having two or more polymerizable groups, (C) component photoacid generator, (D The composition comprises a crosslinking agent that reacts with the acid of the component) and the solvent (E), and may further contain one or more of the surfactant of the component (F) and other additives as desired. .

Especially, the preferable example of the negative photosensitive resin composition of this invention is as follows.
[1]: Based on 100 parts by weight of component (A), 0.5 to 70 parts by weight of component (B), 0.5 to 80 parts by weight of component (C), and 1 to 80 parts by weight of ( A negative photosensitive resin composition containing the component D) and having these components dissolved in the solvent (E).
[2]: A negative photosensitive resin composition further containing 0.2% by mass or less of component (F) in the composition of [1] above.
[3]: A negative photosensitive resin composition further containing at least one selected from other additives in the composition of [1] or [2].

  The ratio of the solid content in the negative 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, 5 to 60% by mass, or 8 to 50% by mass. Here, solid content means what remove | excluded the (E) solvent from all the components of the negative photosensitive resin composition.

  Although the preparation method of the negative photosensitive resin composition of this invention is not specifically limited, As the preparation method, (A) component is melt | dissolved in (E) solvent, for example, (B) component thru | or ( D) component and optionally (F) component are mixed at a predetermined ratio to make a uniform solution, or, at an appropriate stage of this preparation method, other additives are further added as necessary and mixed. The method of doing is mentioned.

  In the preparation of the negative photosensitive resin composition of the present invention, (E) a solution of a specific copolymer obtained by a polymerization reaction in a solvent can be used as it is. In this case, the solution of the component (A) In the same manner as described above, when the components (B) to (D) 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 adjusting the concentration when preparing the negative photosensitive resin composition may be the same, May be different.

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

<Coating film and cured film>
The negative 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 negative 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 negative photosensitive resin film formed from the negative photosensitive resin composition is, for example, 0.1 to 30 μm, for example, 0.2 to 10 μm, and further, for example, 0.2 to 5 μm. It is.

  Then, the solvent is removed from the formed negative photosensitive resin film by heat treatment during formation. In this case, when the temperature of the heat treatment is lower than the lower limit of the above temperature range, a large amount of solvent may remain in the film and the target pattern may not be formed. If the temperature of the heat treatment exceeds the upper limit of the above temperature range and is too high, crosslinking of the unexposed area may progress and cause poor development.

When the negative photosensitive resin film formed from the negative photosensitive resin composition of the present invention is exposed to light such as ultraviolet rays, ArF, KrF, and F ₂ laser light using a mask having a predetermined pattern, Due to the action of the acid generated from the photoacid generator (PAG) of component (C) contained in the negative photosensitive resin film, the exposed portion of the film becomes insoluble in the alkaline developer.

  Next, post-exposure heating (PEB) is performed on the negative 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. Thereby, the part which is not exposed among negative photosensitive resin films 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 this alkaline developer is also used in the negative photosensitive resin composition of the present invention. It can be used to develop well 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 development, the negative 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, by such post-baking, a target cured film having a good pattern shape can be obtained.

As described above, with the negative photosensitive resin composition of the present invention, a coating film having a fine pattern can be formed with sufficiently high sensitivity and without causing poor development in unexposed areas during development. Can do.
In particular, the conventional chemical amplification type photosensitive resin composition already contains a cross-linking agent (component (D)) that reacts with an acid, so its use was not studied at all. Addition of (polyfunctional acrylate) prevents coloring during curing and firing due to the combined use of a polyimide precursor or polyimide (component (A)) and a photoacid generator (component (C)), which has been considered a problem in the past. A cured film having high transparency can be obtained.

  Therefore, for example, it is suitable for applications such as an array flattening film of a TFT type liquid crystal element, various films in a liquid crystal or an organic EL display, such as an interlayer insulating film, a protective film, an insulating film, and a color filter.

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

[Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
MAA: methacrylic acid MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate CHMI: N-cyclohexylmaleimide CBDA: cyclobutanetetracarboxylic dianhydride ABL: 2,2′-bis (trifluoromethyl) benzidine NMP: N-methylpyrrolidone TA: trimellitic anhydride AIBN: azobisisobutyronitrile PGMEA: propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether P3: VP-8000 (trade name) manufactured by Nippon Soda Co., Ltd., polyvinylphenol Mw 8,000 ( 31.5% PGME solution)
DPHA: KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.
CYM: Nippon Cytec Industries Co., Ltd. CYNEL303 (trade name)
PAG1: CGI1397 (trade name) manufactured by Ciba Specialty Chemicals Co., Ltd.
R30: Mega Japan R-30 (trade name) manufactured by Dainippon Ink & Chemicals, Inc.

[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 and specific cross-linked product obtained in accordance with the following synthesis examples were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation. 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 Example 1>
MAA 19.4 g, CHMI 35.3 g, HEMA 25.5 g, MMA 19.8 g were used as monomer components constituting the specific copolymer, and AIBN 5 g was used as a radical polymerization initiator, and these were used as a solvent PGMEA 212. Polymerization reaction was carried out at a temperature of 60 ° C. to 100 ° C. in 0.5 g to obtain a solution of the component (A) (specific copolymer) (specific copolymer concentration: 32.0% by mass) (P1). Mn of the obtained specific copolymer is 4,10.
0 and Mw were 7,600.

<Synthesis Example 2>
A polyamic acid solution was obtained by reacting 25.0 g of CBDA and 48.0 g of ABL in NMP242.1 at 23 ° C. for 24 hours. To this polyamic acid solution, 8.6 g of TA and 34.6 g of NMP were added and reacted at 23 ° C. for 24 hours to obtain a solution containing polyamic acid with a sealed amine end (specific copolymer concentration: 20.0 mass%). Obtained (P2). The obtained specific copolymer had Mn of 4,000 and Mw of 7,400.

<Example 1-3, Comparative Example 1-3>
According to the composition shown in the following Table 1, the component (A) is mixed with the component (B), the component (C), the component (D), the solvent (E), and the component (F) at a predetermined ratio. The negative photosensitive resin composition of each Example and each Comparative Example was prepared by stirring at room temperature for 3 hours to obtain a uniform solution.

  About each composition of Example 1 thru | or Example 3 and Comparative Example 1 thru | or Comparative Example 3, based on the following procedures, respectively, the light transmittance (transparency) after high temperature baking, the curing rate of an exposed part, and after curing Solvent resistance was measured.

[Evaluation of light transmittance (transparency) after high-temperature firing]
The negative photosensitive resin composition was applied onto a quartz substrate using a spin coater, and then prebaked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 1.5 μm. This coating film was immersed in a 0.4% aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 60 seconds, and then washed with running ultrapure water for 20 seconds. Subsequently, post-baking was performed on a hot plate at a temperature of 230 ° C. for 30 minutes to form a cured film. This cured film was measured for transmittance at a wavelength of 200 nm to 800 nm using an ultraviolet-visible spectrophotometer (SHIMADSU UV-2550 model number, manufactured by Shimadzu Corporation). The transmittance at wavelengths of 400 nm, 500 nm, and 550 nm is shown in Table 2 below, and the measurement results of the transmittance at wavelengths of 350 nm to 600 nm are shown in FIG. 1 (Example 1 and Comparative Example 1) and FIG. Comparative Example 2) and FIG. 3 (Example 3 and Comparative Example 3) are shown.
The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.

[Evaluation of photocuring rate]
The negative photosensitive resin composition was applied onto a silicon wafer using a spin coater, and then prebaked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 1.5 μm. This coating film was irradiated with ultraviolet light having a light intensity at 365 nm of 5.5 mW / cm ² for 20 seconds by an ultraviolet irradiation apparatus PLA-600FA manufactured by Canon Inc., and then heated after exposure on a hot plate at 120 ° C. for 120 seconds. PEB). This membrane was immersed in a 0.4% tetramethylammonium hydroxide aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. Subsequently, the film thickness was measured, and (photocuring rate) = (film thickness after immersion) / (film thickness before immersion) was obtained. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.

[Evaluation of solvent resistance]
The negative photosensitive resin composition was applied onto a silicon wafer using a spin coater, and then prebaked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 1.5 μm. This coating film was irradiated with ultraviolet light having a light intensity at 365 nm of 5.5 mW / cm ² for 20 seconds by an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc.
Post exposure heating (PEB) was performed on a hot plate at 20 ° C. for 120 seconds. This film was post-baked on a hot plate at a temperature of 230 ° C. for 30 minutes to form a cured film. The cured film was immersed in PGME for 60 seconds and then washed with pure water for 20 seconds. Thereafter, the cured film was measured, and a film where no film decrease was observed (that is, no film decrease causing a problem in practice) was marked with ◯, and a film with a film decrease observed was marked with x. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.

[Evaluation results]
The results of the above evaluation are shown in the following Table 2 and FIGS. In Table 2, examples using the same component (A) and comparative examples are shown side by side.

As shown in Table 2, in any case of P1 to P3 used as the component (A), the transmittance of the corresponding example was improved as compared with the comparative example. In particular, in P1, a result further surpassing the result of Comparative Example 1 that can be said to be highly sensitive was obtained in Example 1, and an extremely excellent result of 100% transmittance at 550 nm could be obtained.
The difference between the results of these examples and the comparative example becomes more prominent in the graphs shown in FIGS. 1 to 3 clearly show that Examples 1 to 3 containing a polyfunctional acrylate compound (component (B)) have higher transmittance than the comparative example in the wavelength range of 350 nm to 600 nm. .

Moreover, in the photocuring rate and the solvent resistance, good results were obtained that the examples were almost the same as the comparative examples.
In other words, the negative photosensitive resin composition of the present invention can provide a result that shows a remarkable improvement in practical use in terms of transmittance while maintaining the superior performance (photocuring rate and solvent resistance) of conventional products.

  The negative 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 color filter, an array flattening film, a concavo-convex film under a reflective film of a reflective display, an insulating film of an organic EL element, and the like.

FIG. 1 is a graph showing the measurement results of transmittance of Example 1 and Comparative Example 1 at wavelengths of 350 nm to 600 nm. FIG. 2 is a graph showing the measurement results of the transmittance of Example 2 and Comparative Example 2 at wavelengths of 350 nm to 600 nm. FIG. 3 is a graph showing the measurement results of the transmittance of Example 3 and Comparative Example 3 at wavelengths of 350 nm to 600 nm.

Claims (10)

A negative photosensitive resin composition comprising the following component (A), component (B), component (C), component (D) and solvent (E).
Component (A): having at least one group selected from the group consisting of a phenolic hydroxy group, a carboxyl group, and a group that generates a carboxylic acid or a phenolic hydroxy group by the action of heat or acid, and a number Polyimide precursor or polyimide having an average molecular weight of 2,000 to 50,000 ,
(B) component: a compound having two or more polymerizable groups,
(C) component: photoacid generator,
(D) component: a crosslinking agent that reacts with an acid,
(E) Solvent. The negative photosensitive resin composition according to claim 1, wherein the component (B) is a compound having two or more organic groups selected from the group consisting of acrylate groups, methacrylate groups and allyl groups. The negative photosensitive resin composition of Claim 1 or Claim 2 whose photoacid generator of (C) component is a sulfonic acid ester compound. Furthermore, the negative photosensitive resin composition as described in any one of Claims 1 thru | or 3 which contains surfactant as (F) component. The coating film obtained using the negative photosensitive resin composition as described in any one of Claims 1 thru | or 4 . The cured film obtained using the negative photosensitive resin composition as described in any one of Claims 1 thru | or 4 . The color filter obtained using the negative photosensitive resin composition of Claim 1 thru | or 4 . A display element having the cured film according to claim 6 . A liquid crystal display element having the cured film according to claim 6 . A solid-state imaging device having the color filter according to claim 7 .

Images