KR20190034209A - A photosensitive resin composition, a cured product, an interlayer insulating film, a TFT active matrix substrate, and an image display device - Google Patents

Abstract

The photosensitive resin composition of the present invention comprises (a) a zirconium dioxide particle, (b) a dispersant, (c) a solvent, (d) a binder resin, (e) a polymerizable monomer, and (f) ) Binder resin contains at least one of an epoxy (meth) acrylate resin having a repeating unit structure represented by the following formula (I) and an epoxy (meth) acrylate resin having a partial structure represented by the following formula (II). (Wherein R ¹ , R ² , R ³ , R ⁴ , and * are each the same as defined in the specification)

Description

A photosensitive resin composition, a cured product, an interlayer insulating film, a TFT active matrix substrate, and an image display device

The present invention relates to a photosensitive resin composition, a cured product, an interlayer insulating film, a TFT active matrix substrate, and an image display device.

At present, the active matrix type liquid crystal display device is progressing in high definition for high definition and low power consumption. BACKGROUND ART A liquid crystal display panel called a transverse electric field system or a fringe field switching (FFS) system, which is a type of liquid crystal display, generates an electric field parallel at least in part between a pixel electrode and a counter electrode, The liquid crystal is driven by the electric field to modulate the light transmitted through the liquid crystal layer to display an image. This method has a feature that the viewing angle is remarkably wide, but there is a problem in that it is difficult to increase the head size due to its structure. As one of means for achieving a high aperture ratio in an FFS type liquid crystal display device, there is known a method of using an organic insulating film having a high relative dielectric constant in an interlayer insulating film sandwiched between a planar counter electrode and a line-shaped pixel electrode.

In the FFS method, the storage capacitor Cst is formed of the pixel electrode and the interlayer insulating film, and the charge charge is stably maintained. Here, the capacitance C of the capacitor is represented by the following equation (1).

C =? _R ? ₀ S / d (1)

In the formula (1), C represents capacitance, ∈ _{r represents} relative permittivity, ε ₀ represents permittivity of vacuum, S represents electrode area, and d represents distance between electrodes.

As can be seen from the formula (1), when the pixel electrode area is made small in order to achieve the high definition, in order to keep the auxiliary capacitance constant, an interlayer insulating film having a high dielectric constant and a small film thickness is required. At this time, it is required to suppress the dielectric strength and leakage current in the thin film. In order to maintain the dielectric strength even in a thin film, it is important that the film surface is flat and uniform.

2. Description of the Related Art [0002] There is known a method in which an ink in which inorganic particles with high dielectric constant are dispersed in a resin is applied, dried and cured to obtain an insulating film having high dielectric constant (see, for example, Patent Document 1). In addition, a method of forming a pattern by a photolithography method is known (for example, refer to Patent Documents 2 to 4) when the insulating film is made photosensitive.

Japanese Laid-Open Patent Publication No. 2009-235359 Japanese Laid-Open Patent Publication No. 2011-116943 Japanese Laid-Open Patent Publication No. 2013-237804 Japanese Laid-Open Patent Publication No. 2009-249411

Since it is necessary to form a contact hole for connecting the active element and the pixel electrode to the interlayer insulating film, it is required that the contact hole is opened by the photolithography method without residue. However, when the content of the inorganic particles is increased in order to increase the relative dielectric constant, the aggregation of the inorganic particles tends to occur, and it is difficult to achieve good dispersion by completely dissolving the aggregates. Thus, when the interlayer insulating film is patterned by photolithography It is difficult to form a pattern free of residues in the pattern. In addition, minute voids tend to remain between the aggregated inorganic particles, and the leakage current tends to increase.

As a result of a study conducted by the present inventors, it has been found that titania or barium titanate is used as an inorganic particle having a high dielectric constant. Specifically, the composition disclosed in Patent Documents 1 to 3 has a high dielectric constant but a large leakage current, Insufficient, and practical problems.

On the other hand, in Patent Document 4, since bisphenol A type epoxy acrylate resin is used as the binder resin, hole resolution is exhibited in high resolution patterning, but minute residues are generated on the glass substrate, .

It is an object of the present invention to provide a photosensitive resin composition capable of forming a fixed pattern by photolithography while suppressing leakage current even if it is a thin film and has a high dielectric constant .

The inventors of the present invention have conducted intensive studies and have found out that zirconium dioxide particles are used and that a specific epoxy (meth) acrylate resin is used as a binder resin to solve the above problems, and the present invention has been reached. That is, the gist of the present invention is as follows.

[1] A photosensitive resin composition comprising (a) a zirconium dioxide particle, (b) a dispersant, (c) a solvent, (d) a binder resin, (e) a polymerizable monomer, and (f) Wherein the binder resin contains at least one of an epoxy (meth) acrylate resin having a repeating unit structure represented by the following formula (I) and an epoxy (meth) acrylate resin having a partial structure represented by the following formula Resin composition.

[Chemical Formula 1]

(In the formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a divalent hydrocarbon group which may have a substituent. The benzene ring of the formula (I) may be further substituted by an arbitrary substituent * Indicates a combined hand.)

(2)

(In the formula (II), R ³ represents, independently of each other, a hydrogen atom or a methyl group, and R ⁴ represents a divalent hydrocarbon group having an aliphatic cyclic group as a side chain.

[2] The photosensitive resin composition according to [1], wherein the content of the binder resin (d) is 5% by mass or more based on the total solid content.

[3] The photosensitive resin composition according to [1] or [2], wherein the content ratio of the zirconium dioxide particles (a) in the total solid content is 50% by mass or more.

[4] The photosensitive resin composition according to any one of [1] to [3], wherein the polymerization initiator (f) contains an oxime ester compound.

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the polymerizable monomer (e) comprises a (meth) acrylate compound represented by the following formula (III)

(3)

(Formula (III) of, R ⁵ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. R ⁶ it is, represents an alkylene group which may optionally each independently have a substituent. R ^7, each independently , A hydrogen atom or a methyl group, k and l each independently represent an integer of 1 to 20.)

[6] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [5].

[7] An interlayer insulating film comprising the cured product according to [6].

[8] A TFT active matrix substrate comprising the interlayer insulating film according to [7].

[9] An image display device comprising a TFT active matrix substrate according to [8].

According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a fixed pattern by photolithography while suppressing a leakage current even if it is a thin film and has a high dielectric constant.

Hereinafter, the embodiments of the present invention will be described in detail, but the following description is only an example of the embodiments of the present invention, and the present invention is not limited to these embodiments.

In the present invention, "(meth) acrylic acid" includes both acrylic acid and methacrylic acid, and "(meth) acrylate" and "(meth) acryloyl" have the same meaning. In addition, "(poly)" is prefixed to the name of the monomer means the monomer and the polymer.

In the present invention, " total solid content " means all components of the photosensitive resin composition of the present invention except for the solvent.

In the present invention, " mass " has the same meaning as " weight ".

<Photosensitive resin composition>

The photosensitive resin composition of the present invention contains a zirconium dioxide particle, (b) a dispersant, (c) a solvent, (d) a binder resin, (e) a polymerizable monomer, and (f) a polymerization initiator.

First, (a) zirconium dioxide particles will be described in detail.

[(a) Zirconium dioxide particles]

The photosensitive resin composition of the present invention contains (a) zirconium dioxide particles (hereinafter occasionally referred to as &quot; zirconia particles &quot;). By containing the zirconium dioxide particles (a), it becomes possible to obtain an organic insulating film having a high relative dielectric constant and a suppressed leakage current.

Particles of the compound having the Group 4 element of the long period type periodic table, in particular, the oxide having the Group 4 element of the long period type periodic table have a high dielectric constant and are suitable for use in an organic insulating film having a high dielectric constant. Among them, the zirconium dioxide particles have a low relative dielectric constant, and it is necessary to increase the content ratio of the particles in order to set the relative dielectric constant of the obtained organic insulating film to a desired value. The zirconium dioxide particles are densely Packed so that the hygroscopicity of the coating film is reduced, and it is considered that the leakage current can be suppressed.

The average particle diameter of the primary particles of the zirconium dioxide particles (a) is usually 100 nm or less, preferably 80 nm or less, more preferably 70 nm or less, further preferably 60 nm or less. It is usually 1 nm or more. When the particle diameter is less than the upper limit value, there is no surface roughness and the patterning property tends to be good. If the lower limit is more than the lower limit, the dispersibility tends to be improved.

The average particle size of the primary particles of the zirconium dioxide particles (a) is measured by a transmission electron microscope (TEM) or a scanning electron microscope (SEM), by directly measuring the size of primary particles from the electron micrograph . Specifically, the primary particle diameter of each particle is calculated from the circle equivalent diameter. The measurement is carried out for all the particles within a range of 100 to 500 nm square and within the range. The particle diameters of a total of 200 to 1000 primary particles are measured several times in different ranges, and the average particle size is obtained by taking the number average thereof. The measurement of the primary particle diameter can be performed, for example, on a single zirconium dioxide particle, a dispersion thereof, or a cured film of a resin composition. When preparing the measurement sample, (a) the zirconium dioxide particles should be uniformly present in the sample. In the case of the dispersion, the dispersion is used immediately after the dispersion and the solvent is volatilized before measurement. Further, in the case of a cured film, measurement is carried out by preparing a cured film using a photosensitive resin composition in which particles are uniformly dispersed, cutting the film in the thickness direction of the film, and observing its cross section.

The shape of the zirconium dioxide particles (a) is not particularly limited, but is, for example, spherical, hollow, porous, rod-like, platy, fibrous or irregular.

The content of the (a) zirconium dioxide particles is usually 50 mass% or more, preferably 55 mass% or more, more preferably 60 mass% or more, and still more preferably 65 mass% or more in the total solid content of the photosensitive resin composition More preferably 90 mass% or less, further preferably 85 mass% or less, even more preferably 80 mass% or less, still more preferably 70 mass% or more, Particularly preferably not more than 75% by mass. The dielectric film having a high relative dielectric constant tends to be obtained by setting it to the lower limit value or more, and when it is not more than the above-mentioned upper limit value, the patterning property tends to be good.

[(b) Dispersing agent]

The photosensitive resin composition of the present invention comprises (b) a dispersant. (b) a dispersant, the (a) zirconium dioxide particles can be stably dispersed in the photosensitive resin composition.

As the dispersant (b), a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxyl group; Phosphate group; Sulfonic acid group; Or a base thereof; A primary, secondary or tertiary amino group; Quaternary ammonium salt group; And a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine. Among them, a primary, secondary or tertiary amino group; Quaternary ammonium salt group; A polymer dispersant having a basic functional group such as a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine is particularly preferable.

Examples of the polymer dispersing agent include a urethane dispersant, an acrylic dispersant, a polyethyleneimine dispersant, a polyallyl amine dispersant, a dispersant comprising a monomer having an amino group and a macromonomer, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene Diester dispersants, polyether phosphoric acid dispersants, polyester phosphoric acid dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

Specific examples of such a dispersant include, but are not limited to, EFKA (manufactured by EFKA), DISPERBYK (manufactured by BICKEMISA), DIPERRON (manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE ), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyowa Chemical Industry Co., Ltd.) and Ajisper (manufactured by Ajinomoto Co., Ltd.). These polymer dispersants may be used singly or in combination of two or more.

The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1,000 or more, and usually 100,000 or less, preferably 50,000 or less.

Among them, a dispersant having an amine value of 60 mgKOH / g or less and / or a dispersant having a phosphoric acid group is preferable from the viewpoint of affinity with a developing solution. When having an amino group, those having an ether bond such as polyester amine, polyether amine and the like are preferable. Herein, the term amine value refers to the amine value in terms of effective solid content, and is a value expressed by the mass of KOH in terms of the amount of the basic group per 1 g of the solid content of the dispersant.

The dispersant having a phosphoric acid group preferably has a polyether structure in view of the patterning property. The polyether structure tends to enable patterning at a higher resolution because it has a polyether structure as a moiety having a function of improving the affinity with the developing solution and improving the dispersibility.

The chemical structure of the dispersing agent having a phosphoric acid group is not particularly limited, but preferably has a chemical structure represented by the following general formula (X) from the viewpoint of compatibility between the patterning property and the dispersibility.

[Chemical Formula 4]

In the formula (X), R ^A represents an alkyl group which may have a substituent,? Represents a polyether structure, and? Represents a direct bond or polyester structure. Also, n represents an integer of 1 to 3.

R ^A is an alkyl group which may have a substituent, but the number of carbon atoms thereof is not particularly limited and is usually 1 or more, preferably 20 or less, more preferably 15 or less, further preferably 10 or less, Is 5 or less. Within the above range, the compatibility with the developer is improved and the patterning property tends to be good.

Examples of the substituent which the alkyl group in R ^A may have include a sulfonyl group, a carboxyl group, a benzyl group, and a benzoyl group, but from the viewpoint of ease of synthesis, it is preferable that the substituent is indeterminate.

? represents a polyether structure, but a polyethylene glycol structure, a polypropyl ether structure, a polyisopropyl ether structure and a butanyl ether structure are preferable, a polyethylene glycol structure is more preferable, and a polyethylene glycol structure represented by the following formula (X-1).

[Chemical Formula 5]

In the formula (X-1), R ^B represents an alkylene group which may have a substituent. The number of carbon atoms is not particularly limited and is usually 1 or more, preferably 2 or more, more preferably 10 or less, and still more preferably 5 or less. Within the above range, the patterning property tends to be good.

Examples of the substituent that the alkylene group in R ^B may have include a sulfonyl group, a carboxyl group, a benzyl group, and a benzoyl group, but from the viewpoint of ease of synthesis, the substituent is preferably indeterminate.

In the above formula (X-1), x represents an integer of 5 to 30.

x is preferably 10 or more, and more preferably 25 or less. When it is more than the lower limit value, affinity to the developer tends to be improved. In addition, when the content is lower than the upper limit, storage stability tends to be improved. The R ^B contained in a plurality of R molecules in one molecule may be the same or different and may be an alkylene group having a different number of carbon atoms, for example, a butylene group and a pentylene group.

In the formula (X),? Represents a direct bond or a polyester structure, more preferably a structure represented by the following formula (X-2).

[Chemical Formula 6]

In the formula (X-2), R ^C represents an alkylene group which may have a substituent, and y represents an integer of 0 to 10.

R ^C is an alkylene group which may have a substituent, but the number of carbon atoms thereof is not particularly limited and is usually 1 or more, preferably 2 or more, more preferably 4 or more, further preferably 15 or less, Is 10 or less, more preferably 8 or less. The storage stability tends to be improved by the above-mentioned lower limit value, and when it is not more than the above-mentioned upper limit value, the patterning property tends to be good.

Examples of the substituent that the alkylene group in R ^C may have include a sulfonyl group, a carboxyl group, a benzyl group, and a benzoyl group, but from the viewpoint of ease of synthesis, the substituent is preferably indeterminate.

y is an integer of 0 to 10, but is preferably 1 or more, more preferably 2 or more, further preferably 7 or less, and still more preferably 5 or less, from the viewpoint of compatibility between storage stability and patterning property. The storage stability tends to be improved by the above-mentioned lower limit value. Further, when the thickness is less than the upper limit, the patterning property tends to be good. When y is an integer of 2 or more, the R ^c included in two or more of the molecules may be the same or different and may be an alkylene group having a different number of carbon atoms, such as a butylene group and a pentylene group.

The weight average molecular weight (Mw) of the dispersant having a phosphoric acid group is not particularly limited, but is preferably 1,000 or more, more preferably 5,000 or more, still more preferably 40,000 or less, and still more preferably 30,000 or less. The above-mentioned lower limit value tends to improve the dispersibility, and when it is lower than the upper limit value, the patterning property tends to become better.

As the dispersing agent having a phosphoric acid group, a commercially available dispersant may be used. For example, DISPERBYK (registered trademark, hereinafter the same) -102, 110, 111, 140, 142, 145, 180, 2001 ED-251 (manufactured by Kusumoto Chemical Co., Ltd.), TEGO (registered trademark) Dispers 628, 655 (manufactured by Evonik), and the like.

The content of the dispersing agent (b) is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and preferably 10% by mass or more based on the total solid content of the photosensitive resin composition % Or less, more preferably 7 mass% or less, further preferably 5 mass% or less. The above-mentioned lower limit value tends to improve the stability of the photosensitive resin composition, and when it is not more than the upper limit value, the patterning property tends to be improved.

The content of the dispersant having a phosphoric acid group in the dispersant (b) is not particularly limited, but is preferably 50 mass% or more, more preferably 70 mass% or more, and usually 100 mass% or less By mass is 100% by mass. The patterning property tends to be improved by setting it to the lower limit value or more.

The amount of the dispersant (b) is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, further preferably 8 parts by mass or less, relative to 100 parts by mass of the zirconium dioxide particles (a) , Further preferably 1 part by mass or more, and more preferably 3 parts by mass or more. When the ratio is not less than the lower limit, the dispersibility tends to be good, and when it is not more than the upper limit, the patterning property tends to be good.

[(c) Solvent]

The photosensitive resin composition of the present invention contains (c) a solvent.

The solvent (c) is not particularly limited as long as it can dissolve and disperse the respective components and has good handling properties. Specific examples of the solvent include methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA" Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, chloroform, dichloromethane, ethyl acetate, methyl lactate, ethyl lactate, 3-methoxymethylpropionate, 3-ethoxyethyl propionate Propanol, butanol, tetrahydrofuran, diethylene glycol dimethyl ether, methoxybutylacetic acid ester, Solvesso (hereinafter, referred to as &quot; PGME &quot;), propylene glycol monomethyl ether ), And organic solvents such as carbitol. Of these, glycol alkyl ether acetates and glycol monoalkyl ethers are preferable, and glycol alkyl ether acetates are more preferable from the viewpoints of coating properties and solubility of the constituent components in the composition. The glycol alkyl ether acetates may be used alone or in combination with other solvents. As the solvent to be used in combination, glycol monoalkyl ethers are particularly preferable. Among them, propylene glycol monomethyl ether is particularly preferable in view of the solubility and dispersibility of the constituent components in the composition. When the solvent is selected, the high polarity inhibits the dispersibility, and if the solvent has a high boiling point, the solvent does not completely blow away even in reduced-pressure drying (VCD) at the time of film formation, and the patterning characteristics tend to deteriorate significantly. Further, a residual solvent is generated even after the coat film is fired, which tends to cause a significant deterioration in electrical characteristics.

When a dielectric film is formed by a photolithography method, it is preferable to select a solvent having a boiling point of 100 to 200 DEG C (under the condition of a pressure of 1013.25 [hPa], the same applies to all boiling points). More preferably, it has a boiling point of 120 to 170 ° C. By setting the ratio to be equal to or higher than the lower limit, there is a tendency to suppress generation of aggregation of particles due to abrupt drying and generation of defects due to bubble traces. By setting the content at or below the upper limit, the drying time can be shortened, which tends to be advantageous in terms of power consumption and production speed. Among the above solvents, glycol alkyl ether acetates are preferred from the viewpoints of a good balance of coatability, surface tension and the like, and relatively high solubility of the components in the composition.

The solvent may be used alone or in combination of two or more. As a combination of solvents to be used in combination, for example, PGMEA may be a mixture of at least one solvent selected from diethylene glycol dimethyl ether, methoxybutylacetic ester, sorbose and carbitol.

In the mixed solvent, the blending ratio of at least one solvent selected from diethylene glycol dimethyl ether, methoxybutylacetic ester, sorbose and carbitol is usually at least 10% by mass, preferably at least 10% by mass, 30 mass% or more, and usually 80 mass% or less, preferably 70 mass% or less.

In addition, among the above mixed solvents, the mixed solvent of PGMEA and methoxybutylacetic ester is preferable for flattening the unevenness of the substrate because it causes a suitable fluidity of the coating film in the coating and drying step.

The content of the solvent (c) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, 99 mass% or less, preferably 90 mass% or less, and more preferably 85 mass% or less. By making the amount fall within the above range, sufficient amounts of components such as (a) the zirconium dioxide particles and (d) the binder resin can be contained, and the coating properties also tend to be improved.

[(d) Binder Resin]

The photosensitive resin composition of the present invention comprises (d) a binder resin. (d) a binder resin, a homogeneous film can be obtained.

(d) The kind of the binder resin is not particularly limited, but a resin containing a carboxyl group or a hydroxyl group is preferable from the viewpoint of solubility in an alkali developing solution. For example, an epoxy (meth) acrylate resin, an acrylic resin, Epoxy resin, urethane resin containing carboxyl group, novolac resin, polyvinyl phenol resin and the like. These may be used singly or in combination of plural kinds.

(Meth) acrylate resin having a repeating unit structure represented by the following formula (I) and an epoxy (meth) acrylate resin having a partial structure represented by the following formula (II) as the binder resin (d) And at least one of acrylate resin and acrylate resin. The epoxy (meth) acrylate resin has a good patterning property at a high sensitivity, a small number of skeletons, and a good substrate adhesion at a point where the dissolution rate is mild. In addition, unlike the acrylic resin, it is believed that the leakage current can be suppressed in that it has a rigid skeleton and is easily crosslinked three-dimensionally and is densely crosslinked by taking an arrangement structure at the time of curing.

Particularly, those having a repeating unit structure represented by the following formula (I) and those having a partial structure represented by the following formula (II) have a bulky and rigid skeleton at the center thereof. Therefore, It is considered that the portion develops outwardly and the developability becomes good.

(7)

(In the formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a divalent hydrocarbon group which may have a substituent. The benzene ring of the formula (I) may be further substituted by an arbitrary substituent * Indicates a combined hand.)

[Chemical Formula 8]

(In the formula (II), R ³ represents, independently of each other, a hydrogen atom or a methyl group, and R ⁴ represents a divalent hydrocarbon group having an aliphatic cyclic group as a side chain.

The epoxy (meth) acrylate resin means an alkali-soluble resin of the following (d1) and / or (d2) and also means that another carboxyl group is further reacted with the compound. This epoxy (meth) acrylate resin has no epoxy group in its chemical structure and is not limited to "(meth) acrylate", but epoxy resin is a raw material and "(meth) acrylate" Because it is a representative example.

&Quot; Alkali-soluble resin (d1) &quot;

An alkali-soluble resin obtained by adding an?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or a carboxyl group to an epoxy resin and further reacting the polybasic acid and / or an anhydride thereof.

&Quot; Alkali-soluble resin (d2) &quot;

Unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or a carboxyl group in an epoxy resin and further reacting with an alcohol, a polybasic acid and / or an anhydride thereof, Soluble resin.

&Quot; Epoxy (meth) acrylate resin (d-1) &quot;

Next, an epoxy (meth) acrylate resin having a repeating unit structure represented by the above formula (I) (hereinafter abbreviated as "epoxy (meth) acrylate resin (d-1)") will be described in detail.

[Chemical Formula 9]

(In the formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a divalent hydrocarbon group which may have a substituent. The benzene ring of the formula (I) may be further substituted by an arbitrary substituent * Indicates a combined hand.)

(R ² )

In the above formula (I), R ² represents a divalent hydrocarbon group which may have a substituent.

Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, and a group having at least one divalent aliphatic group and at least one divalent aromatic ring group linked to each other.

Examples of the divalent aliphatic group include linear, branched, and cyclic ones, and those linked to each other. Of these, a linear type is preferable from the viewpoint of development solubility, and a cyclic type is preferable from the viewpoint of reducing penetration of the developer into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, further preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the thickness is not less than the lower limit value, a strong film tends to be obtained, surface roughness hardly occurs, adhesion to the substrate and electric characteristics tend to be good. It tends to be suppressed and the resolution is improved.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group and an n-heptylene group. Among them, a methylene group is preferable in view of rigidity of the skeleton.

Specific examples of the divalent branched chain aliphatic group include an iso-propylene group, a sec-butylene group, a tert-butylene group, and an iso-amylene group. Of these, tert-butylene group is preferable from the viewpoint of rigidity of the skeleton.

The number of rings of the bivalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the thickness is not less than the above lower limit, the film becomes a strong film and tends to improve the substrate adhesion and electric characteristics. On the other hand, when it is not more than the above upper limit, deterioration of the surface smoothness and sensitivity of the film tends to be improved and resolution is improved. Specific examples of the bivalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborane ring, an adamantane ring, a cyclododecane ring, etc. And a group obtained by removing two hydrogen atoms from the ring of R &lt; 2 &gt; Among them, from the viewpoint of the rigidity of the skeleton, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable.

Examples of the substituent which the divalent aliphatic group may have include a hydroxyl group; An alkoxy group having 1 to 5 carbon atoms such as methoxy group and ethoxy group; A hydroxyl group; A nitro group; Cyano; A carboxyl group and the like. Among these, from the viewpoint of easiness of synthesis, it is preferable that it is indeterminate.

Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic ring group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, further preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. When the thickness is not less than the lower limit value, a strong film tends to be obtained, surface roughness hardly occurs, adhesion to the substrate and electric characteristics tend to be good. It tends to be suppressed and the resolution is improved.

The aromatic hydrocarbon ring in the bivalent aromatic hydrocarbon ring group may be either monocyclic or condensed. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring , A triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

The aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be either a monocyclic or a condensed ring. Examples of the divalent aromatic heterocyclic group include groups having two free valences such as a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring , Indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, A pyrimidine ring, a pyrimidine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cyano ring, a quinoxaline ring, a phenanthridine ring, a benzoimidazole ring, A ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. Of these, benzene rings or naphthalene rings having two free valences are preferred, and benzene rings having two free valences are more preferred from the viewpoint of patterning properties.

Examples of the substituent which the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. Of these, non-substitution is preferable from the viewpoint of development solubility and hygroscopicity.

Examples of the group connecting at least one bivalent aliphatic group and at least one bivalent aromatic ring group include groups in which one or more of the above-mentioned bivalent aliphatic groups are linked to one or more of the above-mentioned bivalent aromatic ring groups.

The number of the bivalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, more preferably 3 or less. When the thickness is not less than the lower limit value, a strong film tends to be obtained, surface roughness hardly occurs, adhesion to the substrate and electric characteristics tend to be good. It tends to be suppressed and the resolution is improved.

The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the thickness is not less than the lower limit value, a strong film tends to be obtained, surface roughness hardly occurs, adhesion to the substrate and electric characteristics tend to be good. It tends to be suppressed and the resolution is improved.

Specific examples of the group linking at least one bivalent aliphatic group and at least one bivalent aromatic ring group include the groups represented by the following formulas (I-A) to (I-E). Among them, a group represented by the following formula (I-A) is preferable from the viewpoints of rigidity of the skeleton and hydrophobicity of the film.

[Chemical formula 10]

As described above, the benzene ring in formula (I) may be further substituted by an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. The number of substituents is not particularly limited and may be one or two or more.

Among these, from the viewpoint of the patterning property, it is preferable that it is indefinite, and on the other hand, it is preferable that the methyl group is substituted at the ortho position from the viewpoint of electric characteristics.

The repeating unit structure represented by the formula (I) is preferably a repeating unit structure represented by the following formula (I-1) from the viewpoint of simplicity of synthesis.

(11)

(I) wherein R ¹ and R ² have the same meanings as those of the formula (I), R ^X represents a hydrogen atom or a residue of a polybasic acid, -1) may be further substituted by an arbitrary substituent.

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or an anhydride thereof. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, Acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and the like.

Among them, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid and biphenyltetracarboxylic acid are preferable from the viewpoint of the patterning property, Is tetrahydrophthalic acid, biphenyltetracarboxylic acid.

Epoxy (meth) acrylate resin (d-1) a repeating unit structure represented by the above formula (I-1) contained in a molecule is, the least one member, and may be two or more kinds, for example, R ^X is hydrogen And R ^x may be a polybasic acid residue.

The number of repeating unit structures represented by the formula (I) contained in one molecule of the epoxy (meth) acrylate resin (d-1) is not particularly limited, but is preferably 1 or more, more preferably 3 or more , Further preferably 20 or less, more preferably 15 or less. When the content is not less than the lower limit value, a strong film tends to be obtained, surface roughness hardly occurs, and electrical characteristics tend to be improved. When the content is not more than the upper limit, deterioration of the surface smoothness and sensitivity of the film can be easily suppressed, There is a tendency that the property is improved.

The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (d-1) measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but is preferably 1,000 or more, More preferably 2,000 or more, still more preferably 3,000 or more, still more preferably 30,000 or less, still more preferably 20,000 or less, still more preferably 10,000 or less, still more preferably 8,000 or less, and most preferably 5,000 or less Particularly preferred. When the ratio is more than the lower limit, the residual film ratio of the photosensitive resin composition tends to be good. When the content is lower than the upper limit, the resolution tends to be improved.

The acid value of the epoxy (meth) acrylate resin (d-1) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, and more preferably 40 mgKOH / g or more G or less, more preferably 50 mgKOH / g or more, particularly preferably 150 mgKOH / g or less, more preferably 130 mgKOH / g or less, still more preferably 100 mgKOH / g or less, MgKOH / g or less is particularly preferable. The above-mentioned lower limit value tends to improve the solubility in developing and improve the resolution. On the other hand, when the content is lower than the upper limit, the residual film ratio of the curable resin composition tends to be improved.

Specific examples of the epoxy (meth) acrylate resin (d-1) are given below.

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

&Quot; Epoxy (meth) acrylate resin (d-2) &quot;

Next, the epoxy (meth) acrylate resin having a partial structure represented by the above formula (II) (hereinafter abbreviated as "epoxy (meth) acrylate resin (d-2)") will be described in detail.

[Chemical Formula 17]

(In the formula (II), R ³ represents, independently of each other, a hydrogen atom or a methyl group, and R ⁴ represents a divalent hydrocarbon group having an aliphatic cyclic group as a side chain.

(R ⁴ )

In the formula (II), R ⁴ represents a divalent hydrocarbon group having a aliphatic cyclic group as a side chain.

The number of rings of the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is not less than the lower limit value, a strong film tends to be obtained, surface roughness hardly occurs, and electrical characteristics tend to be improved. When the content is not more than the upper limit, deterioration of the surface smoothness and sensitivity of the film can be easily suppressed, There is a tendency that the property is improved.

The number of carbon atoms in the aliphatic cyclic group is usually at least 4, preferably at least 6, more preferably at least 8, further preferably at most 40, more preferably at most 30, even more preferably at most 20, Or less is particularly preferable. When the content is not less than the lower limit value, a strong film tends to be obtained, surface roughness hardly occurs, and electrical characteristics tend to be improved. When the content is not more than the upper limit, deterioration of the surface smoothness and sensitivity of the film can be easily suppressed, There is a tendency that the property is improved.

Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborane ring, an adamantane ring, a cyclododecane ring, etc. . Of these, adamantane rings are preferred from the viewpoint of the residual film ratio and resolution of the photosensitive resin composition.

The divalent hydrocarbon group in the divalent hydrocarbon group having an aliphatic cyclic group as a side chain is not particularly limited. For example, a divalent aliphatic group, a divalent aromatic ring group, at least one divalent aliphatic group and at least one divalent group And a group connecting an aromatic ring group.

Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Of these, a linear type is preferable from the viewpoint of development solubility, and a cyclic type is preferable from the viewpoint of reducing penetration of the developer into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, further preferably 25 or less, more preferably 20 or less, still more preferably 15 or less. When the thickness is not less than the lower limit value, a strong film tends to be obtained, surface roughness hardly occurs, adhesion to the substrate and electric characteristics tend to be good. It tends to be suppressed and the resolution is improved.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group and an n-heptylene group. Among them, a methylene group is preferable in view of rigidity of the skeleton.

Specific examples of the divalent branched chain aliphatic group include an iso-propylene group, a sec-butylene group, a tert-butylene group, and an iso-amylene group. Of these, tert-butylene group is preferable from the viewpoint of rigidity of the skeleton.

The number of rings of the bivalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the thickness is not less than the above lower limit, the film becomes a strong film and tends to improve the substrate adhesion and electric characteristics. On the other hand, when it is not more than the above upper limit, deterioration of the surface smoothness and sensitivity of the film tends to be improved and resolution is improved. Specific examples of the bivalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborane ring, an adamantane ring, a cyclododecane ring, etc. And a group obtained by removing two hydrogen atoms from the ring of R &lt; 2 &gt; Among them, from the viewpoint of the rigidity of the skeleton, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable.

Examples of the substituent which the divalent aliphatic group may have include a hydroxyl group; An alkoxy group having 1 to 5 carbon atoms such as methoxy group and ethoxy group; A hydroxyl group; A nitro group; Cyano; A carboxyl group and the like. Among these, from the viewpoint of easiness of synthesis, it is preferable that it is indeterminate.

Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic ring group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, further preferably 30 or less, more preferably 20 or less, still more preferably 15 or less. When the thickness is not less than the lower limit value, a strong film tends to be obtained, surface roughness hardly occurs, adhesion to the substrate and electric characteristics tend to be good. It tends to be suppressed and the resolution is improved.

The aromatic hydrocarbon ring in the bivalent aromatic hydrocarbon ring group may be either a monocyclic or condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring , A triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

The aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be either monocyclic or condensed. Examples of the divalent aromatic heterocyclic group include groups having two free valences such as a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring , Indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, A pyrimidine ring, a pyrimidine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cyano ring, a quinoxaline ring, a phenanthridine ring, a benzoimidazole ring, A ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.

Among them, a benzene ring or a naphthalene ring having two free valences from the viewpoint of patterning property is preferable, and a fluorene ring having a divalent free valence is more preferable.

Examples of the substituent which the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. Of these, non-substitution is preferable from the viewpoint of development solubility and hygroscopicity.

Examples of the group connecting at least one bivalent aliphatic group and at least one bivalent aromatic ring group include groups in which one or more of the above-mentioned bivalent aliphatic groups are linked to one or more of the above-mentioned bivalent aromatic ring groups.

The number of the bivalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, more preferably 3 or less. When the thickness is not less than the lower limit value, a strong film tends to be obtained, surface roughness hardly occurs, adhesion to the substrate and electric characteristics tend to be good. It tends to be suppressed and the resolution is improved.

The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the thickness is not less than the lower limit value, a strong film tends to be obtained, surface roughness hardly occurs, adhesion to the substrate and electric characteristics tend to be good. It tends to be suppressed and the resolution is improved.

Specific examples of the group linking at least one divalent aliphatic group and at least one divalent aromatic ring group include the groups represented by the above formulas (I-A) to (I-E). Among them, the group represented by the formula (I-A) is preferable from the viewpoints of rigidity of the skeleton and hydrophobicity of the film.

The bonding state of the aliphatic cyclic group as a side chain with respect to these bivalent hydrocarbon groups is not particularly limited. For example, a mode in which one hydrogen atom in a divalent aliphatic group or a bivalent aromatic cyclic group is substituted with a side chain thereof, And an aliphatic cyclic group which is a side chain including one of the carbon atoms constituting the divalent aliphatic group.

The partial structure represented by the formula (II) is preferably a partial structure represented by the following formula (II-1) from the viewpoint of hole resolution.

[Chemical Formula 18]

(Wherein (II-1), R ³ is the formula (II are as defined). R ^α is a monovalent aliphatic ring which may have a substituent. N is an integer of 1 or more. In the formula (II- The benzene ring in 1) may be further substituted by an arbitrary substituent.

Further, in the formulas in the present specification, * denotes a binding hand.

(R ^? )

In the formula (II-1), R ^? Represents a monovalent aliphatic cyclic group which may have a substituent.

The number of rings of the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less. When the thickness is more than the lower limit, a strong film tends to be obtained, surface roughness hardly occurs, and electrical characteristics tend to be good. When the thickness is not more than the upper limit, the patterning property tends to be good.

The number of carbon atoms in the aliphatic cyclic group is usually at least 4, preferably at least 6, more preferably at least 8, further preferably at most 40, more preferably at most 30, even more preferably at most 20, Or less is particularly preferable. When the thickness is more than the lower limit, a strong film tends to be obtained, surface roughness hardly occurs, and electrical characteristics tend to be good. When the thickness is not more than the upper limit, the patterning property tends to be good.

Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborane ring, an adamantane ring, a cyclododecane ring, etc. . Of these, adamantane rings are preferable from the viewpoints of strong film properties and electrical characteristics.

Examples of the substituent which the aliphatic ring group may have include a hydroxyl group; An alkoxy group having 1 to 5 carbon atoms such as methoxy group and ethoxy group; A hydroxyl group; A nitro group; Cyano; A carboxyl group and the like. Of these, from the viewpoint of easiness of synthesis, unsubstituted is preferable.

n represents an integer of 1 or more, but is preferably 2 or more, and is preferably 3 or less. The film hardening degree and the residual film ratio tends to be improved by setting it at the above-mentioned lower limit value, and the hole hardening tendency tends to be improved by setting it to the above-mentioned upper limit value.

Among these, it is preferable that R ^? Is an adamantyl group in view of a strong film hardening degree and electrical characteristics.

As described above, the benzene ring in the formula (II-1) may be further substituted by an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. The number of substituents is not particularly limited and may be one or two or more.

Among these, from the viewpoint of the patterning characteristic, it is preferable that it is irregular.

Specific examples of the partial structure represented by the formula (II-1) are shown below.

[Chemical Formula 19]

[Chemical Formula 20]

The partial structure represented by the formula (II) is preferably a partial structure represented by the following formula (II-2) from the viewpoints of skeletal rigidity and film hydrophobicity.

[Chemical Formula 21]

(II-2), R ³ has the same meaning as in formula (II), and R ^β represents a divalent aliphatic cyclic group which may have a substituent. And may be further substituted by an arbitrary substituent.)

(R ^? )

In the formula (II-2), R ^? Represents a divalent aliphatic cyclic group which may have a substituent.

The number of rings of the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the content is not less than the lower limit value, a strong film tends to be obtained, surface roughness hardly occurs, and electrical characteristics tend to be improved. When the content is not more than the upper limit, deterioration of the surface smoothness and sensitivity of the film can be easily suppressed, There is a tendency that the property is improved.

The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 40 or less, more preferably 35 or less, still more preferably 30 or less. When the amount is not less than the lower limit, the film roughness at the time of development tends to be suppressed and the electrical characteristics tend to be good. When the content is not more than the upper limit, deterioration of the surface smoothness and sensitivity of the film is easily suppressed, have.

Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborane ring, an adamantane ring, a cyclododecane ring, etc. . Of these, adamantane rings are preferable from the viewpoint of storage stability.

Examples of the substituent which the aliphatic ring group may have include a hydroxyl group; An alkoxy group having 1 to 5 carbon atoms such as methoxy group and ethoxy group; A hydroxyl group; A nitro group; Cyano; A carboxyl group and the like. Of these, from the viewpoint of simplicity of synthesis, unsubstituted is preferable.

Among these, from the viewpoints of storage stability and electrical characteristics, it is preferable that R ^? Is a divalent adamantane ring group.

As described above, the benzene ring in the formula (II-2) may be further substituted by an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. The number of substituents is not particularly limited and may be one or two or more.

Among these, from the viewpoint of the patterning characteristic, it is preferable that it is irregular.

Specific examples of the partial structure represented by the formula (II-2) are shown below.

[Chemical Formula 22]

(23)

&Lt; EMI ID =

On the other hand, the partial structure represented by the formula (II) is preferably a partial structure represented by the following formula (II-3) from the viewpoints of the coating film remaining ratio and the patterning property.

(25)

(In the formula (II-3), R ³ and R ⁴ have the same meanings as in the formula (II)), and R ^Z represents a hydrogen atom or a polybasic acid residue.

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or an anhydride thereof. In addition, polybasic acid moieties, is still a further one OH group is removed from the polybasic acid or an anhydride thereof, and may be shared with the R ^Z according to different molecules represented by the formula (II-3), that is, via a R ^Z plurality (II-3) of Fig.

Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, Acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and the like.

Among them, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid and biphenyltetracarboxylic acid are preferable from the viewpoint of the patterning property, Is tetrahydrophthalic acid, biphenyltetracarboxylic acid.

Epoxy (meth) acrylate resin (d-2) a partial structure represented by the above formula (II-3) contained in a molecule is, the least one member, and may be two or more kinds, for instance, R ^Z is a hydrogen atom And R ^Z is a polybasic acid residue.

The number of partial structures represented by the formula (II) contained in one molecule of the epoxy (meth) acrylate resin (d-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, It is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. When the content is not less than the lower limit value, a strong film tends to be obtained, surface roughness hardly occurs, and electrical characteristics tend to be improved. When the content is not more than the upper limit, deterioration of the surface smoothness and sensitivity of the film can be easily suppressed, There is a tendency that the property is improved.

The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (d-2) in terms of polystyrene measured by gel permeation chromatography (GPC) is not particularly limited but is preferably 1,000 or more, More preferably 2,000 or more, still more preferably 30,000 or less, still more preferably 20,000 or less, still more preferably 10,000 or less, particularly preferably 5,000 or less. When the thickness is more than the lower limit, the patterning property tends to be good. When the thickness is less than the upper limit, a strong film tends to be obtained, and surface roughness tends not to occur.

The acid value of the epoxy (meth) acrylate resin (d-2) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, and more preferably 40 mgKOH / g or more G, more preferably at least 60 mgKOH / g, particularly preferably at least 80 mgKOH / g, more preferably at most 200 mgKOH / g, even more preferably at most 150 mgKOH / g, gKOH / g or less is more preferable. When the content is more than the above lower limit, a strong film tends to be obtained and electric characteristics tend to be improved. When the content is lower than the upper limit, development solubility tends to be improved and resolution is improved.

Preparation of "epoxy (meth) acrylate resins (d-1) and (d-2)"

The epoxy (meth) acrylate resins (d-1) and (d-2) are obtained by reacting an epoxy resin having a structure corresponding to the formula (I) Unsaturated monocarboxylic acid ester having a carboxylic acid or a carboxyl group, and further reacting a polybasic acid and / or an anhydride thereof, or (ii) reacting an?,? - unsaturated monocarboxylic acid or a carboxyl group Unsaturated monocarboxylic acid ester having an unsaturated carboxylic acid and / or a polyhydric alcohol, and further reacting with a polyhydric alcohol and / or a polybasic acid and / or an anhydride thereof.

As the raw material epoxy resin, for example, a phenol novolak type epoxy resin (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152", "EP- EOCN-1020 &quot;, &quot; EOCN-104S &quot;, manufactured by Nippon Kayaku Co., Ltd.), dicyclopentadiene (For example, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.) glycidylated phenol resin by the reaction of phenol, an epoxy resin represented by the following general formulas (D1) to (D3) Can be used. Concretely, "XD-1000" manufactured by Nippon Yakusha Co., Ltd. and "NC-3000" manufactured by Nippon Yakuhin Co., Ltd. as an epoxy resin represented by the following general formula (D2) .

(26)

In the general formula (D1), a is an average value and represents a number of 0 to 10. R ¹¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. The plurality of R &lt; ¹¹ &gt; existing in one molecule may be the same or different.

(27)

In the general formula (D2), b is an average value and represents a number of 0 to 10. R ²¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. Further, a plurality of R &lt; ²¹ &gt; residing in one molecule may be the same or different.

(28)

In the general formula (D3), X represents a linking group represented by the following general formula (D3-1) or (D3-2). However, it includes at least one adamantane structure in the molecular structure. and c represents an integer of 2 or 3.

[Chemical Formula 29]

In the general formula (D3-1) and ^{(D3-2), R 31 ~ R} 34 and R ³⁵ ~ R ³⁷ is O, which may each independently have a substituent group however, may have a hydrogen atom, an optionally substituted An alkyl group having 1 to 12 carbon atoms, or a phenyl group which may have a substituent.

Among them, it is preferable to use epoxy resins represented by the general formulas (D1) to (D3).

Examples of the?,? - unsaturated monocarboxylic acid ester having an?,? -unsaturated monocarboxylic acid or a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- (meth) acryloyloxyethyl succinic acid, (Meth) acryloyloxypropyl succinic acid, 2 (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (Meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (Meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutyl (Meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid (meth), acrylic acid with? -Caprolactone,? -Propiolactone,? -Butyrolactone, (anhydrous) phthalic acid, (maleic anhydride) maleic anhydride, and (meth) acrylic acid are added to a monomer which is obtained by adding lactones such as δ-valerolactone or hydroxyalkyl (meth) acrylate, pentaerythritol tri (Meth) acrylic acid dimer, and the like.

Of these, (meth) acrylic acid is particularly preferable in terms of sensitivity.

As a method for adding an?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or a carboxyl group to an epoxy resin, a known technique may be used. For example, an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having an α, β-unsaturated monocarboxylic acid or a carboxyl group can be reacted with an epoxy resin at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst . Examples of the esterification catalyst used herein include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride Etc. may be used.

The α, β-unsaturated monocarboxylic acid ester having an epoxy resin, α, β-unsaturated monocarboxylic acid or carboxyl group, and the esterification catalyst may be used singly or in combination of two or more You can.

The amount of the?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of the epoxy group in the epoxy resin, more preferably 0.7 To 1.1 equivalents. If the amount of the?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or a carboxyl group is within the above range, the amount of the unsaturated group introduced is sufficient and the reaction with the polybasic acid and / There is a tendency to disappear.

Examples of the polybasic acid and / or anhydride thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, Hydroxycarboxylic acid, hydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof, and the like.

Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides thereof. Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, anhydrous tetrahydrophthalic acid, or biphenyltetracarboxylic acid dianhydride.

With respect to the addition reaction of a polybasic acid and / or an anhydride thereof, a known method can be used, and an addition reaction of an alpha, beta -unsaturated monocarboxylic acid ester having an alpha, beta -unsaturated monocarboxylic acid or a carboxyl group to an epoxy resin and Under the same conditions, the target product can be obtained by continuous reaction. The addition amount of the polybasic acid and / or the anhydride component thereof is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth) acrylate resin is in the range of 10 to 150 mgKOH / g, more preferably 20 to 140 mg KOH / g. &Lt; / RTI &gt; When the acid value of the carboxyl group-containing epoxy (meth) acrylate resin is within the above range, the alkaline developability and the curing performance tend to be improved.

In addition, multifunctional alcohols such as trimethylolpropane, pentaerythritol, and dipentaerythritol may be added during the addition reaction of the polybasic acid and / or anhydride thereof to introduce a multibranched structure.

The carboxyl group-containing epoxy (meth) acrylate resin is usually prepared by reacting a reaction product of an epoxy resin and an?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or carboxyl group with a polybasic acid and / Or by mixing a reaction product of an epoxy resin and an?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or a carboxyl group with a polybasic acid and / or an anhydride thereof and a polyfunctional alcohol Followed by heating. In this case, the mixing order of the polybasic acid and / or the anhydride thereof and the polyfunctional alcohol is not particularly limited. By heating, a polybasic acid and / or a polybasic acid may be added to any hydroxyl groups present in a mixture of an epoxy resin and a reaction product of an alpha, beta -unsaturated monocarboxylic acid ester having an alpha, beta -unsaturated monocarboxylic acid or a carboxyl group and a polyfunctional alcohol The anhydride undergoes addition reaction.

"Other binder resins"

The binder resin (d) contained in the photosensitive resin composition of the present invention is preferably an epoxy (meth) acrylate resin having a repeating unit structure represented by the formula (I) and an epoxy having a partial structure represented by the formula (II) ) Acrylate resin, but may contain other binder resin (hereinafter abbreviated as &quot; other binder resin &quot;).

Examples of the other binder resin include an acrylic resin, a carboxyl group-containing epoxy resin, a carboxyl group-containing urethane resin, a novolac resin, a polyvinylphenol resin, etc. These resins may be used singly, A plurality of species may be mixed and used.

The content of the binder resin (d) in the photosensitive resin composition of the present invention is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, Is usually 15 mass% or more, and usually 50 mass% or less, preferably 45 mass% or less, more preferably 35 mass% or less, particularly preferably 25 mass% or less. When the thickness is more than the lower limit value, a strong film tends to be obtained, surface roughness hardly occurs, adhesion to the substrate tends to be good, and the penetration of the developer into the light- The surface smoothness of the film and the deterioration of the sensitivity tend to be easily suppressed.

The content of the epoxy (meth) acrylate resin in the (d) binder resin is not particularly limited, but is preferably 5 mass% or more, more preferably 30 mass% or more, further preferably 50 mass% or more, , Usually not more than 100 mass%, particularly preferably not more than 100 mass%. The above-mentioned lower limit value tends to result in better patterning characteristics and substrate adhesion.

The epoxy (meth) acrylate resin having a repeating unit structure represented by the above formula (I) and the epoxy (meth) acrylate resin having a partial structure represented by the following formula (II) The content ratio of one side is not particularly limited, but is preferably 5 mass% or more, more preferably 30 mass% or more, further preferably 50 mass% or more, and usually 100 mass% or less, 100% by mass. When the content is above the lower limit, water resistance is improved and the coating film surface tends to be uniform.

[(e) Polymerizable monomer]

The photosensitive resin composition of the present invention contains (e) a polymerizable monomer. (e) By containing a polymerizable monomer, a film having high curability can be obtained.

In the photosensitive resin composition of the present invention, among the polymerizable monomers (e), a compound having an ethylenic unsaturated group (hereinafter sometimes abbreviated as "ethylenic unsaturated compound") is preferable.

The ethylenically unsaturated compound means a compound having at least one ethylenic unsaturated bond in the molecule. The photosensitive resin composition of the present invention preferably contains a compound having two or more ethylenic unsaturated groups.

Examples of the compound having one ethylenic unsaturated bond include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid and citraconic acid, and alkyl esters thereof (Meth) acrylonitrile, (meth) acrylamide, and styrene.

Examples of the compound having two or more ethylenic unsaturated bonds in the molecule include esters of an unsaturated carboxylic acid and a polyhydroxy compound, phosphates containing a (meth) acryloyloxy group, hydroxy (meth) acryl Urethane (meth) acrylates of a late compound and a polyisocyanate compound, and epoxy (meth) acrylates of a (meth) acrylic acid or a hydroxy (meth) acrylate compound and a polyepoxy compound.

These may be used singly or in combination of two or more.

(e-1) esters of an unsaturated carboxylic acid and a polyhydroxy compound

Examples of the ester of an unsaturated carboxylic acid and a polyhydroxy compound (hereinafter sometimes abbreviated as &quot; ester (meth) acrylate &quot;) include specifically the following compounds.

Examples of the sugar alcohol include ethylene glycol, polyethylene glycol (adduct number 2 to 14), propylene glycol, polypropylene glycol (adduct number 2 to 14), trimethylene glycol, Tetramethylene glycol, hexamethylene glycol, trimethylol propane, glycerol, pentaerythritol, dipentaerythritol and the like.

Reaction products of the unsaturated carboxylic acid and the alkylene oxide adduct of the sugar alcohol: The sugar alcohol may be the same as described above. Examples of the alkylene oxide adducts include ethylene oxide adducts and propylene oxide adducts.

Reaction products of the unsaturated carboxylic acid and alcohol amine: Examples of the alcohol amines include diethanolamine, triethanolamine, and the like.

As the esters of the above unsaturated carboxylic acid and polyhydroxy compound, more specifically, the following compounds can be exemplified.

Acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide adduct tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, and the same crotonate, isocroton Nate, maleate, itaconate, citraconate, and the like.

Examples of the esters of unsaturated carboxylic acids and polyhydroxy compounds include aromatic polyhydroxy compounds such as the above unsaturated carboxylic acids and hydroquinone, resorcin, pyrogallol, bisphenol F, and bisphenol A, And a reaction product of adducts. Specific examples thereof include bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], and bisphenol A bis [glycidyl ether (meth) acrylate].

Examples of the esters of the unsaturated carboxylic acid and the polyhydroxy compound include a reaction product of the unsaturated carboxylic acid and a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate . Specific examples thereof include di (meth) acrylate and tri (meth) acrylate of tris (2-hydroxyethyl) isocyanurate.

Further, as the esters of the unsaturated carboxylic acid and the polyhydroxy compound, there may be mentioned a reaction product of the above unsaturated carboxylic acid, polyvalent carboxylic acid and polyhydroxy compound. Specific examples thereof include a condensation product of (meth) acrylic acid, phthalic acid and ethylene glycol, a condensation product of (meth) acrylic acid and maleic acid and diethylene glycol, a condensation product of (meth) acrylic acid, terephthalic acid and pentaerythritol, Methacrylic acid, adipic acid, butanediol and glycerin condensate.

(meth) acrylates of the (e-2) hydroxy (meth) acrylate compound and the polyisocyanate compound

Examples of the hydroxy (meth) acrylate compound include hydroxy (meth) acrylates such as hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and tetramethylol ethane tri Acrylate compounds.

As the polyisocyanate compound, for example,

Aliphatic polyisocyanates such as hexamethylene diisocyanate and 1,8-diisocyanate-4-isocyanate methyloctane;

Alicyclic polyisocyanates such as cyclohexane diisocyanate, dimethyl cyclohexane diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, and bicycloheptane triisocyanate;

Aromatic polyisocyanates such as 4,4-diphenylmethane diisocyanate and tris (isocyanate phenyl) thiophosphate;

Heterocyclic polyisocyanates such as isocyanurate and the like;

Allophanate-modified polyisocyanurates prepared by the method described in Japanese Patent Application Laid-Open No. 2001-260261;

And polyisocyanate compounds such as polyisocyanate compounds.

Among the urethane (meth) acrylates of the hydroxy (meth) acrylate compound and the polyisocyanate compound, urethane (meth) acrylates containing the above-mentioned allophanate-modified polyisocyanurate are preferable. The urethane (meth) acrylates containing allophanate-modified polyisocyanurate have low viscosity and excellent solubility in solvents, and are also excellent in adhesiveness to a substrate and hardness of a film by photocuring and / or thermosetting It is preferable in that it is effective for improvement.

As the urethane (meth) acrylates in the present invention, commercially available ones can be used. Specifically, for example, "U-4HA", "UA-306A", "UA-MC340H", "UA-MC340H", "U6LPA" manufactured by Shin Nakamura Chemical Co., &Quot; AGROR 4060 &quot;

As the urethane (meth) acrylates in the present invention, from the viewpoint of sensitivity, urethane bond [-NH- (meth) acrylate] is preferably added in an amount of 4 or more (preferably 6 or more, more preferably 8 or more) CO-O-], and compounds having four or more (preferably six or more, and more preferably eight or more) (meth) acryloyloxy groups are preferable. Such a compound can be obtained, for example, by reacting the following compound (i) with the following compound (ii).

(i) a compound having at least 4 urethane bonds in one molecule

E.g,

A compound obtained by reacting a compound having four or more hydroxyl groups in a molecule such as pentaerythritol, polyglycerin and the like with a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate or the like i-1);

or,

Dyuranate 24A-100 &quot;, Dyuranate 22A-75PX &quot;, Dyuranate 21S-75E &quot;, Dylanate 21S-75E &quot;, and &quot; Dyuranate &quot;, manufactured by Asahi Chemical Industry Co., Ltd. were added to a compound having two or more hydroxyl groups in one molecule such as ethylene glycol Duartate E-402-90T &quot; and copper &quot; Dyuranate E-405-80T &quot; and the like, A compound (i-2) obtained by reacting a compound having three or more isocyanate groups in one molecule;

or,

(I-3) obtained by polymerizing or copolymerizing isocyanatoethyl (meth) acrylate and the like;

.

As such a compound, a commercially available product can be used. For example, "Dyuranate ME20-100" manufactured by Asahi Chemical Industry Co., Ltd. may be mentioned.

(ii) a compound having at least 4 (meth) acryloyloxy groups per molecule

(Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol (Meth) acryloyloxy group, and a compound having two or more, preferably three or more, (meth) acryloyloxy groups in one molecule, such as trimethylolpropane triacrylate and lithol hexaacrylate.

The molecular weight of the compound (i) is preferably 500 to 200,000, particularly preferably 1,000 to 150,000. The molecular weight of the urethane (meth) acrylates is preferably 600 to 150,000.

Such urethane (meth) acrylates can be produced by, for example, reacting the compound of (i) and the compound of (ii) in an organic solvent such as toluene or ethyl acetate at 10 to 150 ° C for 5 minutes, For about 3 hours. In this case, the molar ratio of the former isocyanate group to the latter hydroxyl group is preferably from 1/10 to 10/1, and if necessary, a catalyst such as n-butyl tin dilaurate is preferably used.

(e-3) Epoxy (meth) acrylates of a (meth) acrylic acid or a hydroxy (meth) acrylate compound with a polyepoxy compound

As the polyepoxy compound, for example,

(Poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (Poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, Aliphatic polyepoxy compounds such as ether;

Aromatic polyepoxy compounds such as phenol novolac polyepoxy compounds, brominated phenol novolac polyepoxy compounds, (o-, m-, p-) cresol novolak polyepoxy compounds, bisphenol A polyepoxy compounds, and bisphenol F polyepoxy compounds;

Heterocyclic polyepoxy compounds such as sorbitan polyglycidyl ether, triglycidyl isocyanurate and triglycidyl tris (2-hydroxyethyl) isocyanurate; And the like.

Examples of epoxy (meth) acrylates which are reactants of (meth) acrylic acid or hydroxy (meth) acrylate compounds and polyepoxy compounds include polyepoxy compounds such as those described above and (meth) acrylic acid or hydroxy Acrylate compounds, and the like.

(e-4) Other ethylenically unsaturated compounds

Other ethylenically unsaturated compounds include, for example, allyl esters such as (meth) acrylamides such as ethylenebis (meth) acrylamide and diallyl phthalate, and vinyl group-containing compounds such as divinyl phthalate Ether linkage-containing ethylenically unsaturated compounds are sulfated with sulfur pentasulfide to convert them into thioether linkages, thereby improving the crosslinking rate.

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

In the present invention, the ethylenically unsaturated compound preferably contains a compound having two or more ethylenic unsaturated groups in the molecule, from the viewpoints of polymerizability, crosslinkability, and the like. Among them, esters (meth) acrylates, (meth) acryloyloxy group-containing phosphates or urethane (meth) acrylates are preferable, and ester (meth) acrylates are more preferable. Among these ester (meth) acrylates, aromatic poly (meth) acrylates such as bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate] and bisphenol A bis [glycidyl ether Hydroxy compounds, or their reactants with ethylene oxide adducts, are particularly preferred.

In the ethylenically unsaturated compounds according to the present invention, those containing no aromatic ring or containing a phenyl group having a substituent at an unsubstituted or p (para) position may be discolored by heat treatment of the interlayer insulating film Red coloring) is suppressed. Examples of such ethylenically unsaturated compounds include aliphatic polyfunctional (meth) acrylates and (meth) acrylate compounds of polyhydric alcohols having a bisphenol A or fluorene skeleton.

Among them, epoxy (meth) acrylates of a (e-3) (meth) acrylic acid or a hydroxy (meth) acrylate compound and a polyepoxy compound are preferable as the polymerizable monomer (e) from the viewpoint of balance between the curability and the resolution. (Meth) acrylate compound represented by the following formula (III) is preferably used.

(30)

(Formula (III) of, R ⁵ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. R ⁶ it is, represents an alkylene group which may optionally each independently have a substituent. R ^7, each independently , A hydrogen atom or a methyl group, k and l each independently represent an integer of 1 to 20.)

(R ⁵⁾

In the above formula (III), R ⁵ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.

Examples of the cyclic hydrocarbon group include an aliphatic cyclic group and an aromatic cyclic group.

The number of rings of the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less. When the amount is above the lower limit, there is a tendency that the coating film becomes a strong coating film and the residual film ratio tends to be good. When it is not more than the upper limit value, development solubility is improved and the patterning property tends to be good.

The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 30 or less, more preferably 25 or less, still more preferably 20 or less, Or less is particularly preferable. When the amount is above the lower limit, there is a tendency that the coating film becomes a strong coating film and the residual film ratio tends to be good. When it is not more than the upper limit value, development solubility is improved and the patterning property tends to be good.

Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborane ring, an adamantane ring, a cyclododecane ring, etc. . Of these, adamantane rings are preferable from the viewpoints of a strong film quality and a patterning property.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 6 or less and 4 or less. When the content is above the lower limit, there is a tendency that the film quality and the substrate adhesion property are strengthened. When the content is lower than the upper limit value, development solubility is improved and the patterning property tends to be good.

Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic ring group. The number of carbon atoms in the aromatic ring group is usually at least 4, preferably at least 6, more preferably at least 8, even more preferably at least 10, particularly preferably at least 12, even more preferably at most 30, More preferably 25 or less, further preferably 20 or less, and particularly preferably 15 or less. The above-mentioned lower limit value tends to make the adhesion of the substrate better, and when it is lower than the upper limit value, the patterning property tends to become better.

Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring and a fluorene ring. Among them, a benzene ring is preferable from the viewpoint of development solubility.

In the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, the divalent hydrocarbon group is not particularly limited. For example, a divalent aliphatic group, a divalent aromatic ring group, at least one divalent aliphatic group, and at least one 2 And a group in which an aromatic ring group of the following formula is connected.

Examples of the divalent aliphatic group include linear, branched, cyclic, and combinations thereof. Of these, a linear type is preferable from the viewpoint of development solubility, and a cyclic type is preferable from the viewpoint of reducing penetration of the developer into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, further preferably 30 or less, more preferably 20 or less, still more preferably 15 or less. When the thickness is not less than the lower limit value, a strong film tends to be obtained, surface roughness hardly occurs, adhesion to the substrate and electric characteristics tend to be good. It tends to be suppressed and the resolution is improved.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group and an n-heptylene group. Among them, a methylene group is preferable in view of rigidity of the skeleton.

Specific examples of the divalent branched chain aliphatic group include an iso-propylene group, a sec-butylene group, a tert-butylene group, and an iso-amylene group. Of these, tert-butylene group is preferable from the viewpoint of rigidity of the skeleton.

The number of rings of the bivalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the thickness is not less than the above lower limit, the film becomes a strong film and tends to improve the substrate adhesion and electric characteristics. On the other hand, when it is not more than the above upper limit, deterioration of the surface smoothness and sensitivity of the film tends to be improved and resolution is improved. Specific examples of the bivalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborane ring, an adamantane ring, a cyclododecane ring, etc. And a group obtained by removing two hydrogen atoms from the ring of R &lt; 2 &gt; Among them, from the viewpoint of the rigidity of the skeleton, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable.

Examples of the substituent which the divalent aliphatic group may have include a hydroxyl group; An alkoxy group having 1 to 5 carbon atoms such as methoxy group and ethoxy group; A hydroxyl group; A nitro group; Cyano; A carboxyl group and the like. Among these, from the viewpoint of easiness of synthesis, it is preferable that it is indeterminate.

Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic ring group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, further preferably 40 or less, more preferably 35 or less, still more preferably 30 or less. When the thickness is not less than the lower limit value, a strong film tends to be obtained, surface roughness hardly occurs, adhesion to the substrate and electric characteristics tend to be good. It tends to be suppressed and the resolution is improved.

The aromatic hydrocarbon ring in the bivalent aromatic hydrocarbon ring group may be either a monocyclic or condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring , A triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

The aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be either monocyclic or condensed. Examples of the divalent aromatic heterocyclic group include groups having two free valences such as a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring , Indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, A pyrimidine ring, a pyrimidine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cyano ring, a quinoxaline ring, a phenanthridine ring, a benzoimidazole ring, A ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. Of these, benzene rings or naphthalene rings having two free valences are preferable from the viewpoint of patterning property, and benzene rings having a divalent free valence are more preferable.

Examples of the substituent which the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. Of these, non-substitution is preferable from the viewpoint of development solubility and hygroscopicity.

Examples of the group connecting at least one bivalent aliphatic group and at least one bivalent aromatic ring group include groups in which one or more of the above-mentioned bivalent aliphatic groups are linked to one or more of the above-mentioned bivalent aromatic ring groups.

The number of the bivalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, more preferably 3 or less. When the thickness is not less than the lower limit value, a strong film tends to be obtained, surface roughness hardly occurs, adhesion to the substrate and electric characteristics tend to be good. It tends to be suppressed and the resolution is improved.

The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the thickness is not less than the lower limit value, a strong film tends to be obtained, surface roughness hardly occurs, adhesion to the substrate and electric characteristics tend to be good. It tends to be suppressed and the resolution is improved.

Specific examples of the group linking at least one divalent aliphatic group and at least one divalent aromatic ring group include the groups represented by the above formulas (I-A) to (I-E). Among them, the group represented by the formula (I-A) is preferable from the viewpoints of rigidity of the skeleton and hydrophobicity of the film.

The bonding state of the cyclic hydrocarbon group as a side chain to these bivalent hydrocarbon groups is not particularly limited. For example, a mode in which one hydrogen atom in a divalent aliphatic group or a bivalent aromatic ring group is substituted with a side chain thereof , And an embodiment in which a ring-shaped cyclic hydrocarbon group including one of the carbon atoms constituting the divalent aliphatic group is constituted.

(R ⁶⁾

In the formula (III), each R ⁶ independently represents an alkylene group which may have a substituent.

Examples of the alkylene group include linear, branched, and cyclic groups, and combinations thereof. Of these, a linear type is preferred from the viewpoint of solubility at the time of development. The number of carbon atoms is usually 1 or more, preferably 2 or more, more preferably 6 or more, further preferably 10 or more, further preferably 30 or less, more preferably 25 or less, still more preferably 20 or less . The above-mentioned lower limit value tends to improve the adhesion of the substrate and the hole resolution. On the other hand, when the thickness is less than the upper limit value, the residue of the unexposed portion tends to be reduced.

Specific examples of the alkylene group include an ethylene group, an n-propylene group, an iso-propylene group, a sec-butylene group, a tert-butylene group and a cyclohexylene group. Among them, an ethylene group is preferable from the viewpoint of development solubility.

Examples of the substituent which the alkylene group may have include a hydroxyl group, a methoxy group, an ethoxy group, a sulfone group, a sulfonyl group, a carboxyl group, a benzyl group and the like. Among them, from the viewpoint of exposure sensitivity, unsubstituted is preferable, and hydroxyl group is preferable from the viewpoint of developing solubility.

In the formula (III), k and 1 each independently represent an integer of 1 to 20. Preferably 2 or more, more preferably 3 or more, and is preferably 15 or less, and more preferably 13 or less. When the thickness is more than the lower limit value, the patterning property tends to be good. When the thickness is less than the upper limit value, a strong coating film tends to be obtained and the residual film ratio tends to be good.

Among the (meth) acrylate compounds represented by the above formula (III), the (meth) acrylate compounds represented by the following formula (III-1) are preferable from the viewpoint of high resolution.

(31)

Of (formula (III-1), R ^6, R ^7, k and l, is the equation (meaning the same as the III). R ^γ is a monovalent cyclic hydrocarbon group which may have a substituent group. M is The benzene ring in the formula (III-1) may be further substituted by an arbitrary substituent.)

(R ^? )

In the above formula (III-1), R ^? Represents a monovalent cyclic hydrocarbon group which may have a substituent.

Examples of the cyclic hydrocarbon group include an aliphatic cyclic group and an aromatic cyclic group.

The number of rings of the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less. When the amount is above the lower limit, permeation of the developer into the exposed portion is suppressed to a low level, and the surface smoothness and sensitivity of the film tend to be inhibited from deteriorating. When the amount is below the upper limit value, alkali solubility of the unexposed portion can be secured, There is a tendency that the property is improved.

The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 30 or less, more preferably 25 or less, still more preferably 20 or less, Or less is particularly preferable. When the amount is above the lower limit, permeation of the developer into the exposed portion is suppressed to a low level, and the surface smoothness and sensitivity of the film tend to be inhibited from deteriorating. When the amount is below the upper limit value, alkali solubility of the unexposed portion can be secured, There is a tendency that the property is improved.

Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborane ring, an adamantane ring, a cyclododecane ring, etc. . Of these, an adamantane ring is preferable from the viewpoint of suppressing the penetration of the developer into the exposed portion and suppressing the surface smoothness and the deterioration of the sensitivity of the film.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 6 or less and preferably 5 or less. When the amount is above the lower limit, permeation of the developer into the exposed portion is suppressed to a low level, and the surface smoothness and sensitivity of the film tend to be inhibited from deteriorating. When the amount is below the upper limit value, alkali solubility of the unexposed portion can be secured, There is a tendency that the property is improved.

Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic ring group. The number of carbon atoms in the aromatic ring group is usually 6 or more, preferably 8 or more, more preferably 10 or more, further preferably 40 or less, more preferably 35 or less, still more preferably 30 or less. When the amount is above the lower limit, permeation of the developer into the exposed portion is suppressed to a low level, and the surface smoothness and sensitivity of the film tend to be inhibited from deteriorating. When the amount is below the upper limit value, alkali solubility of the unexposed portion can be secured, There is a tendency that the property is improved.

Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, a biphenyl ring, a triphenylene ring, a phenanthrene ring and a fluorene ring. Of these, fluorene rings are preferable from the viewpoints of permeation characteristics of the developer and assurance of resolution.

Examples of the substituent which the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec- An alkyl group having 1 to 5 carbon atoms such as methyl, ethyl or propyl; An alkoxy group having 1 to 5 carbon atoms such as methoxy group and ethoxy group; A hydroxyl group; A nitro group; Cyano; A carboxyl group and the like. Among these, from the viewpoint of ease of synthesis, unsubstituted is preferable.

m represents an integer of 1 or more, but is preferably 2 or more, and is preferably 3 or less. When the amount is above the lower limit, permeation of the developer into the exposed portion is suppressed to a low level, and the surface smoothness and sensitivity of the film tend to be inhibited from deteriorating. When the amount is below the upper limit value, alkali solubility of the unexposed portion can be secured, There is a tendency that the property is improved.

Among these, R ^? Is preferably a monovalent aliphatic cyclic group, and more preferably an adamantyl group, from the viewpoint of securing the moisture absorption property of the coating film and the alkali solubility of the unexposed portion.

As described above, the benzene ring in the formula (III-1) may be further substituted by an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. The number of substituents is not particularly limited and may be one or two or more.

Among these, from the viewpoint of the patterning characteristic, it is preferable that it is irregular.

Specific examples of the (meth) acrylate compound represented by the formula (III-1) are shown below.

(32)

(33)

The (meth) acrylate compound represented by the formula (III) is preferably a (meth) acrylate compound represented by the formula (III-2) shown below from the viewpoint of the hygroscopicity of the coating film and the alkali solubility of the non- .

(34)

In the formula (III-2), R ⁶ , R ⁷ , k and l have the same meanings as in the formula (III), and R ⁸ represents a divalent cyclic hydrocarbon group which may have a substituent. -2) may be further substituted by an arbitrary substituent.

(R ^δ)

In the formula (III-2), R ^? Represents a divalent cyclic hydrocarbon group which may have a substituent.

Examples of the cyclic hydrocarbon group include an aliphatic cyclic group and an aromatic cyclic group.

The number of rings of the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the thickness is not less than the lower limit, the coating film becomes a strong coating film and the residual film ratio tends to be improved. When the thickness is less than the upper limit, the patterning property tends to be improved.

The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 30 or less, more preferably 25 or less, still more preferably 20 or less. When the ratio is not less than the lower limit, film hydrophobicity is improved and adhesion to the substrate tends to be improved. In addition, when it is not more than the upper limit, the patterning property tends to be improved by increasing the developing solubility in unexposed state.

Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborane ring, an adamantane ring, a cyclododecane ring, etc. . Of these, adamantane rings are preferred from the standpoint of substrate adhesion.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 6 or less and 4 or less. When the thickness is not less than the lower limit, the coating film becomes a strong coating film and the residual film ratio tends to be improved. When the thickness is less than the upper limit, the patterning property tends to be improved.

Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic ring group. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, still more preferably 30 or less, still more preferably 25 or less, Or less, and particularly preferably 15 or less. When the amount is above the lower limit, the coating film becomes hydrophobic and the adhesion of the substrate tends to be improved. When the amount is less than the upper limit, development solubility can be ensured and the patterning property tends to be improved.

Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring and a fluorene ring. Of these, a fluorene ring is preferable from the viewpoint of substrate adhesion by hydrophobicization of a coating film.

Examples of the substituent which the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec- An alkyl group having 1 to 5 carbon atoms such as methyl, ethyl or propyl; An alkoxy group having 1 to 5 carbon atoms such as methoxy group and ethoxy group; A hydroxyl group; A nitro group; Cyano; A carboxyl group and the like. Among these, from the viewpoints of development solubility and exposure sensitivity, unsubstituted is preferable.

Among these, R &lt; ⁸ &gt; is preferably a divalent aliphatic ring group, more preferably a divalent adamantane ring group, from the viewpoint of storage stability and electrical characteristics.

On the other hand, from the viewpoints of the low hygroscopicity and the patterning property of the coating film, it is preferable that R ^delta is a divalent aromatic ring group, more preferably a divalent fluorene ring group.

As described above, the benzene ring in the formula (III-2) may be further substituted by an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. The number of substituents is not particularly limited and may be one or two or more.

Among these, from the viewpoint of the patterning characteristic, it is preferable that it is irregular.

Specific examples of the (meth) acrylate compound represented by the formula (III-2) are shown below.

(35)

(36)

(37)

In the photosensitive resin composition of the present invention, the content of the polymerizable monomer (e) is usually 1% by mass or more, preferably 3% by mass or more, and usually 20% by mass or less based on the total solid content , Preferably not more than 18 mass%, more preferably not more than 15 mass%, further preferably not more than 12 mass%, particularly preferably not more than 10 mass%. The film hardening property tends to be improved by setting it to the above-mentioned lower limit value. On the other hand, if it is not more than the above upper limit, film roughness on the surface of the coating film tends to be suppressed.

The content of the (meth) acrylate compound represented by the formula (III) is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, More preferably 2 mass% or more, further preferably 15 mass% or less, more preferably 10 mass% or less, further preferably 8 mass% or less. The above-mentioned lower limit value tends to improve the electrical characteristics and the hole resolution. On the other hand, when the content is lower than the upper limit value, film roughness on the surface of the coating film tends to be suppressed.

[(f) Polymerization initiator]

The photosensitive resin composition of the present invention contains (f) a polymerization initiator. (f) Photo-curing by exposure proceeds by containing a polymerization initiator. Any known polymerization initiator can be used, and a compound capable of generating radicals capable of polymerizing an ethylenic unsaturated group from ultraviolet rays by visible light can be mentioned.

Specific examples of the polymerization initiator usable in the present invention are listed below.

(trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, and other halomethylated triazine derivatives.

(ii) halomethylated oxadiazole derivatives, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) Imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methylphenyl) -4,5- Imidazole derivatives such as 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer and the like.

(iii) benzoin alkyl ethers such as benzoin methyl ether, benzoin isobutyl ether and benzoin isopropyl ether.

(iv) Anthraquinone derivatives such as 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone and 1-chloro anthraquinone.

(v) Benzanthrone derivatives.

(vi) benzophenone such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, derivative.

(vii) at least one compound selected from the group consisting of 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1-methyl-1- (p-dodecylphenyl) ketone, 2-methyl- (4 '- (methylthio) phenyl) -2-morpholino -1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, and other acetophenone derivatives.

(viii) at least one compound selected from the group consisting of thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, Thioxanthone derivatives such as 4-diisopropylthioxanthone.

(ix) benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

(x) acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine and the like.

(xi) a phenazine derivative such as 9,10-dimethylbenzphenazine.

(xii) dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bisphenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl, Dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl, dicyclopentadienyl- Ti-2,6-difluorophenyl, dicyclopentadienyl-Ti-2,4-difluorophenyl, dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoro Di-cyclopentadienyl-Ti-bis-2,6-difluorophenyl, dicyclopentadienyl-Ti-2,6-difluoro-3- Lt; / RTI &gt;

(xiii) 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisobutyl benzoate, Ethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, Amino-alkylphenone compounds such as 3- (4-diethylaminobenzoyl) coumarin and 4- (diethylamino) chalcone.

(xiv) Acylphosphine oxide-based compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.

(xv) Synthesis of 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O- benzoyloxime), ethanone- 1- [ 9H-carbazol-3-yl] -1- (O-acetyloxime)

(xvi) JP-A 2000-80068, JP-A 2001-233842, JP-A 2001-235858, JP-A 2005-182004, WO 2002/00903, Oxime ester compounds represented by the compounds described in Japanese Patent Application Laid-Open No. 2007-041493.

Among the polymerization initiators, oxime ester compounds are preferable from the viewpoints of patterning characteristics and transparency, (xv) and (xvi) are more preferable, and compound Y having the following structure is particularly preferably used.

(38)

These polymerization initiators may be used singly or in combination. Examples of the combination include, for example, Japanese Patent Laid-Open Nos. 53-12802, 1-279903, 2-48664, 4-164902, And a combination of polymerization initiators described in Patent Publication No. Hei 6-75373.

The content of the polymerization initiator in the photosensitive resin composition of the present invention is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, Is usually 2 mass% or more, particularly preferably 3 mass% or more, and usually 40 mass% or less, preferably 30 mass% or less, more preferably 20 mass% or less, further preferably 10 mass% , Particularly preferably not more than 7 mass%. When the content is above the lower limit value, the curability tends to be sufficient and the film strength tends to be prevented from lowering. When the content is lower than the upper limit, the degree of heat shrinkage tends to be reduced and cracks and cracks after thermal curing can be suppressed.

[(g) Surfactant]

The photosensitive resin composition according to the present invention can be used in various applications such as a nonionic, anionic, cationic, amphoteric surfactant, or anionic surfactant for the purpose of improving the applicability of the composition as a coating liquid and the developing property of the photosensitive resin composition layer. Or a surfactant such as a fluorine-based or silicone-based surfactant.

The nonionic surfactant includes, for example, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitan fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, Esters, and polyoxyethylene sorbit fatty acid esters. Examples of commercially available products thereof include polyoxyethylene surfactants such as "EMALGEN 104P" and "EMALGENT A60" manufactured by Kao Corporation.

Examples of the anionic surfactant include alkylsulfonic acid salts, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, polyoxyethylene alkyl ether sulfonic acid salts, alkylsulfuric acid salts, alkylsulfuric acid ester salts, and higher alcohol sulfuric acid ester salts , Aliphatic alcohol sulfuric acid ester salts, polyoxyethylene alkyl ether sulfuric acid salts, polyoxyethylene alkylphenyl ether sulfuric acid salts, alkyl phosphoric acid ester salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, special high molecular weight And an activator. Of these, a special polymer type surfactant is preferable, and a special polycarboxylic acid type polymer type surfactant is more preferable.

As the anionic surfactant, a commercially available product can be used. For example, alkyl sulfates such as "Emal 10" manufactured by Kao Corp., alkyl naphthalenesulfonates such as "Pelex NB-L" manufactured by Kao Corporation Quot; Homogenol L-18 &quot;, &quot; Homogenol L-100 &quot;, etc., manufactured by Kao Corporation, and the like can be mentioned as special polymer surfactants.

Examples of the cationic surfactant include quaternary ammonium salts, imidazoline derivatives, amine salts, and the like. Examples of the amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazoline Amino acids, and the like. Of these, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred. Commercially available ones include, for example, "Acetamine (registered trademark) 24" manufactured by Kao Corporation in the case of alkylamine salts and "Kotamine (registered trademark; hereinafter the same) 24P" manufactured by Kao Corp. in the quaternary ammonium salts, Kotamine 86W &quot; and the like.

On the other hand, as the fluorine-based surfactant, a compound having a fluoroalkyl group or fluoroalkylene group in at least any of the terminal, main chain and side chain is preferable.

Specific examples thereof include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether , Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di 1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,1,2,2- , 2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, and the like.

BM-1000 "and" BM-1100 "manufactured by BM Chemie," Megapack (registered trademark; hereinafter the same) F142D "," Megapack F172 "," Megapack F173 " , "Megafac F183", "Megafac F470", "Megapack F475", "FC430" and "FC4432" manufactured by 3M Company, and "DFX-18" manufactured by Neos Co.,

Examples of the silicone surfactants include "Toorresilicon DC3PA", "Dong SH7PA", "Copper DC11PA", "Dong SH21PA", "Dong SH28PA", "Dong SH29PA" TSF-4440 "," TSF-4445 "," TSF-4460 ", and" TSF-4440 "manufactured by Momentive Performance Materials, 4452 "manufactured by Shin-Etsu Chemical Co., Ltd.," KP341 "manufactured by Silicone Co., Ltd., BYK323 manufactured by BICKEMISA, BYK330 and the like.

Of these surfactants, a fluorine-based surfactant and a silicone-based surfactant are preferable from the viewpoint of the uniformity of the coating film thickness.

The surfactant may be a combination of two or more types, and examples thereof include a combination of a silicone surfactant / fluorine surfactant, a silicone surfactant / a special polymer surfactant, and a fluorinated surfactant / a special polymer surfactant. Of these, silicone surfactants / fluorine surfactants are preferred.

For example, "TSF4460" manufactured by Momentive Performance Materials Co., Ltd. / "DFX-18" manufactured by Neos Co., "BYK-300" manufactured by BICKEMISA or "BYK- F-478 &quot; or &quot; F-475 &quot; manufactured by Dainippon Ink &quot;, SH7PA manufactured by Toray Dow Corning Incorporated, FC4432 "manufactured by Mitsubishi Chemical Corporation," L-77 "manufactured by Nippon Unicar Co., Ltd.," FC4430 "manufactured by 3M Company, and the like.

When the photosensitive resin composition of the present invention contains a surfactant, the content of the surfactant in the photosensitive resin composition is preferably 10 mass% or less, more preferably 0.01 to 5 mass%, of the total solid content.

[Other components]

The photosensitive resin composition of the present invention may further contain additives such as a heat crosslinking agent, an adhesion promoter, a curing agent, and an ultraviolet absorber. Examples of these components include those described in International Publication No. 2007/139005 have.

&Lt; Method of producing photosensitive resin composition &gt;

Next, a method for producing the photosensitive resin composition of the present invention will be described.

[Method of producing inorganic particle dispersion]

First, an inorganic particle dispersion is prepared. The inorganic particle dispersion contains (a) zirconium dioxide particles, (b) a dispersant, (c) a solvent, and in some cases, a dispersion resin. By mixing these materials and (c) dispersing the other components in the solvent, an inorganic particle dispersion can be obtained.

The dispersion method is not particularly limited, and examples thereof include a method using a paint shaker, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, and the like.

The mixing order of the respective components is not particularly limited so long as the effect of the present invention is not impaired. (C) After adding the solvent, the zirconium dioxide particles (a), the dispersant (b) , Or vice versa.

As the dispersion resin, those described as the above-mentioned (d) binder resin can be used. A part of the binder resin (d) used in preparing the photosensitive resin composition may be used as a dispersion resin, or a binder resin (d) different from that used in preparing the photosensitive resin composition may be used. When (a) dispersing the zirconium dioxide particles with a sand grinder, glass beads or zirconia beads having a diameter of about 0.05 to 5 mm are preferably used. The dispersion treatment conditions are usually a temperature of 0 ° C to 100 ° C, preferably a temperature of room temperature to 80 ° C.

[Method for preparing photosensitive resin composition]

Next, a method of preparing the photosensitive resin composition of the present invention will be described.

(C) a solvent, (d) a binder resin, (e) a polymerizable monomer and (f) a polymerization initiator, and optionally, a surfactant, which is an optional component, and To obtain a homogeneous solution, whereby a photosensitive resin composition is obtained. The mixing is preferably carried out at room temperature, and is usually carried out under ultraviolet light shielding so as not to initiate the polymerization reaction. In addition, fine dust may be mixed in each step such as mixing. Therefore, it is preferable to filter the obtained photosensitive resin composition with a filter or the like.

&Lt; Method of forming interlayer insulating film &

By applying the photosensitive resin composition of the present invention and curing it, a cured product can be obtained. In particular, the photosensitive resin composition of the present invention can be preferably used as a material for forming an interlayer insulating film. Hereinafter, a method of forming an interlayer insulating film using the photosensitive resin composition of the present invention will be described.

[1-1] Coating process

First, the above-described photosensitive resin composition of the present invention is applied onto a substrate having a TFT array formed thereon by using a coating device such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, or a sprayer. The coating film thickness of the photosensitive resin composition is usually 0.1 to 5 占 퐉.

[1-2] Drying process

And the volatile component is removed (dried) from the coating film to form a dried coating film. For the drying, vacuum drying, hot plate, IR oven, convection oven and the like can be used. Preferable drying conditions are a temperature of 40 to 150 DEG C and a drying time of 10 seconds to 60 minutes.

[1-3] Exposure and development process

Subsequently, a photomask is placed on the dried coating film of the photosensitive resin composition layer, and the image is exposed through the photomask. After exposure, unexposed portions of unexposed light are removed by development to form pixels. In some cases, post exposure, baking is performed for the purpose of improving sensitivity after exposure and before development. For the baking in this case, a hot plate, an IR oven, a convection oven, or the like can be used. The post-exposure bake condition is usually in the range of 40 to 150 DEG C and the drying time is 10 seconds to 60 minutes.

Conventionally, a contact hole for connecting the active element and the pixel electrode is formed in the interlayer insulating film. The contact hole is obtained by patterning and exposing the coating film to development. In the display of fixed three, it is required that a smaller contact hole is opened. For example, an opening of a square hole with one side of 3 to 10 mu m may be required.

Examples of the light source used in the exposure process of the dry film include a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, A laser light source such as a laser, an excimer laser, and a nitrogen laser. When only light of a specific wavelength is used, an optical filter may be used.

The solvent used in the developing treatment is not particularly limited as long as it is a solvent capable of dissolving the coating film of the uncured portion. However, in view of environmental pollution, harmfulness to the human body, fire risk, etc., .

Examples of such an alkaline developing solution include inorganic alkaline compounds such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide and the like or organic solvents such as diethanolamine, Triethanolamine, tetramethylammonium hydroxide, and other organic alkaline compounds.

Further, the alkali developer may contain a surfactant, a water-soluble solvent, a wetting agent, a low-molecular compound having a hydroxyl group or a carboxylic acid group, and the like, if necessary. Examples of the surfactant to be used in the developer include anionic surfactants having a sodium naphthalenesulfonate group, a sodium benzenesulfonate group, nonionic surfactants having a polyalkyleneoxy group, cationic surfactants having a tetraalkylammonium group, etc. .

The method of development processing is not particularly limited, but is usually carried out at a developing temperature of 10 to 50 占 폚, preferably 15 to 45 占 폚 by immersion, paddle development, spraying, brushing, ultrasonic development or the like.

[1-4] Heat treatment process

The photosensitive resin composition film formed by the exposure and development process is then subjected to a heat treatment (hard bake) process to form a cured product (thermosetting film). Further, in order to suppress the generation of outgas during hard bake after development after the hard bake, the front surface exposure may be performed.

When front exposure is performed before hard bake, ultraviolet light or visible light is used as a light source. For example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, And a laser light source such as an argon ion laser, a YAG laser, an excimer laser, or a nitrogen laser.

A hot plate, an IR oven, or a convection oven can be used for the hard bake. The hard-baking condition is usually in the range of 100 to 250 ° C and the drying time is 30 seconds to 90 minutes.

&Lt; TFT active matrix substrate and image display device &gt;

Next, a method of manufacturing an image display apparatus, particularly, a liquid crystal display (panel) according to the present invention will be described. A liquid crystal display device typically includes a TFT (Thin Film Transistor) active matrix substrate.

First, the TFT active matrix substrate is manufactured by forming the aforementioned cured product as an interlayer insulating film on a substrate on which a TFT element array is formed, forming an ITO film thereon, and then forming an ITO wiring by photolithography.

In the liquid crystal display device, the liquid crystal cell is formed by bonding the TFT active matrix substrate with the opposing substrate, liquid crystal is injected into the formed liquid crystal cell, and further the opposing electrode is connected to complete the liquid crystal cell.

As the counter substrate, a color filter substrate having an alignment film is typically used. As the alignment film, a resin film such as polyimide is preferable. The orientation film is usually formed by a gravure printing method and / or a flexo printing method, and the thickness of the alignment film is several tens nm. After curing treatment of the alignment film by thermo-firing, the substrate is subjected to a surface treatment by ultraviolet irradiation or rubbing treatment to be processed into a surface state capable of adjusting the tilt of the liquid crystal. Furthermore, the same interlayer insulating film as above may be formed on the alignment film.

The bonding gap between the TFT active matrix substrate and the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 占 퐉 or more and 8 占 퐉 or less. After joining with the counter substrate, portions other than the liquid crystal injection hole are sealed with a sealing material such as epoxy resin.

As such a sealing material, a material that can be cured by UV irradiation and / or heating is usually used, and the periphery of the liquid crystal cell is sealed. The liquid crystal cell can be injected into the liquid crystal cell by decompressing the sealed liquid crystal cell in a panel unit and then depressurizing it in the vacuum chamber to immerse the liquid crystal injection port in the liquid crystal and return the pressure to atmospheric pressure.

Pressure-road in the liquid crystal cell is typically not less than 1 × 10 ^-2 ㎩, preferably from 1 × 10 ^-3 ㎩ or more, and typically 1 × 10 ^-7 ㎩ or less, preferably 1 × 10 ^-6 ㎩ Or less. It is also preferable to warm the liquid crystal cell at the time of the decompression. The heating temperature is usually 30 占 폚 or higher, preferably 50 占 폚 or higher, and usually 100 占 폚 or lower, preferably 90 占 폚 or lower.

The heating-holding condition at the time of the decompression is usually in the range of not less than 10 minutes and not more than 60 minutes. Thereafter, the liquid crystal cell is immersed in the liquid crystal. In the liquid crystal cell into which the liquid crystal is injected, the UV curable resin is cured to seal the liquid crystal injection port. Thus, the liquid crystal display device (panel) can be completed.

There are no particular restrictions on the type of liquid crystal, and conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds can be used, and either a lyotropic liquid crystal or a thermotropic liquid crystal may be used. Nematic liquid crystals, smectic liquid crystals, and cholesteric liquid crystals are known as thermotropic liquid crystals, and any of them may be used.

Example

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the following embodiments, and can be arbitrarily changed without departing from the gist of the present invention.

The components of the photosensitive resin composition used in the following Examples and Comparative Examples are as follows.

(a) Zirconium dioxide particles (high-permittivity inorganic particles)

1: UEP (Daiichi Chemical Co., Ltd. Preparation key genso ZrO ₂₎

    Primary particle diameter: 10 to 30 nm

(a ') Other high-permittivity inorganic particles

1: T-BTO-020RF (BaTiO ₃ manufactured by Toda Kogyo Co., Ltd.)

    Primary particle diameter: 10 to 30 nm

2: TTO-51N (TiO ₂ manufactured by Ishihara Industries Co., Ltd.)

    Primary particle diameter: 10 to 30 nm

(b) dispersant

DISPERBYK-111 (manufactured by Big Chemical)

(c) Solvent

PGMEA (propylene glycol monomethyl ether acetate)

(d) binder resin

(Synthesis Example 1) Synthesis of adamantyl group-containing epoxy (meth) acrylate resin

[Chemical Formula 39]

50 g of the epoxy compound having the above structure (epoxy equivalent 264), 13.65 g of acrylic acid, 60.5 g of methoxybutyl acetate, 0.936 g of triphenylphosphine and 0.032 g of para-methoxyphenol were placed in a flask equipped with a thermometer, And the mixture was reacted at 90 DEG C with stirring until the acid value became 5 mgKOH / g or less. The reaction required 12 hours to obtain an epoxy acrylate solution.

25 parts by mass of the above epoxy acrylate solution and 0.76 parts by mass of trimethylolpropane (TMP), 3.3 parts by mass of biphenyltetracarboxylic acid dianhydride (BPDA) and 3.5 parts by mass of tetrahydrophthalic anhydride (THPA) The mixture was placed in a flask equipped with a cooling tube, and slowly heated to 105 DEG C with stirring to react.

When the resin solution became transparent, it was diluted with methoxybutyl acetate to prepare a solid content of 70% by mass. The binder resin having an acid value of 115 mgKOH / g and a weight average molecular weight (Mw) of 2,600 in terms of polystyrene measured by GPC (1).

(Synthesis Example 2) Synthesis of biphenyl group-containing epoxy (meth) acrylate resin

400 parts by mass of &quot; NC3000H &quot; (manufactured by Nippon Kayaku Co., Ltd.) (epoxy equivalent 288), 102 parts by mass of acrylic acid, 0.3 parts by mass of p-methoxyphenol, 5 parts by mass of triphenylphosphine and 264 parts by mass of propylene glycol monomethyl ether acetate And the mixture was stirred at 95 캜 until the acid value became 3 mgKOH / g or less. The acid value required 9 hours to reach the target (acid value 2.2 mgKOH / g). Subsequently, 39 parts by mass of succinic anhydride was further added, and the mixture was reacted at 95 DEG C for 4 hours to prepare a solid content of 40% by mass with propylene glycol monomethyl ether acetate (PGMEA). The acid value was 40 mgKOH / g, (2) represented by the following structural formula (wherein m and n are 3 or 4 and the binder resin (2) is a mixture thereof) having a weight average molecular weight (Mw) in terms of polystyrene of 4,000.

(40)

(Synthesis Example 3) Synthesis of fluorene ring-containing epoxy (meth) acrylate resin

(41)

An epoxy resin was synthesized in the same manner as in Synthesis Example 1 except that an epoxy compound was used instead of the epoxy compound in Synthesis Example 1 to obtain an epoxy resin having an acid value of 60 mgKOH / g and a weight average molecular weight (Mw) of 6,500 in terms of polystyrene Of the binder resin (3).

(Synthesis Example 4) Synthesis of bisphenol A type epoxy (meth) acrylate resin

Synthesis was carried out in the same manner as in Synthesis Example 1 except that the epoxy compound was replaced with a bisphenol A type epoxy resin (RE-310S, manufactured by Nippon Kasei Kogyo Co., Ltd.) to obtain an epoxy resin having an acid value of 60 mgKOH / g, a polystyrene- To obtain a binder resin (4) having a weight average molecular weight (Mw) of 8,600.

(Synthesis Example 5) Synthesis of bisphenol F type epoxy (meth) acrylate resin

Synthesis was conducted in the same manner as in Synthesis Example 1 except that the epoxy compound was replaced with a bisphenol F type epoxy resin (RE-303S-L, manufactured by Nippon Gunpase Co., Ltd.), and the acid value was 60 mgKOH / g. To obtain a binder resin (5) having a weight average molecular weight (Mw) of 10,500 in terms of polystyrene.

(Synthesis Example 6) Synthesis of acrylic resin

And 150 parts by mass of propylene glycol monomethyl ether acetate were stirred while substituting with nitrogen, and the temperature was raised to 120 占 폚. To this was added a mixed solution of 20.0 parts by mass of monomethacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton, 4.0 parts by mass of methyl methacrylate, 37.4 parts by mass of methacrylic acid, and 73.2 parts by mass of cyclohexyl methacrylate Followed by dropwise addition over 3 hours and further stirring at 90 DEG C for 2 hours to obtain a binder resin (6). The weight average molecular weight (Mw) of the obtained binder resin (6) as measured by GPC in terms of polystyrene was 5,800 and the acid value was 60 mgKOH / g.

(e) a polymerizable monomer

1: dipentaerythritol hexaacrylate (DPHA)

2: bisphenol A type epoxy ester; 3000A (manufactured by Kyowa Chemical Industry Co., Ltd.)

3: fluorene group-containing epoxy ester; EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd.)

(f) Polymerization initiator

Oxime ester-based polymerization initiator: Compound Y described in the specification

(e) Additive

Surfactant: F554 (manufactured by DIC Corporation)

Adhesion improver: KAYAMER PM-21 (manufactured by Nippon Kayaku Co., Ltd.)

(Preparation of high-dielectric constant inorganic particle dispersion)

The high-permittivity inorganic particle dispersion was prepared by combining the high-permittivity inorganic particles, the dispersant, the dispersion resin, and the solvent in the following composition in the following manner. First, the solid fraction of the high-permittivity inorganic particles, the dispersant, and the dispersion resin were combined so as to be equal to or less than the solid content. Further, the amount of the following solvents is the total amount including the amount of the solvent contained in the dispersant and the dispersion resin.

High dielectric constant inorganic particles: UEP 100 parts by mass

Dispersant: DISPERBYK-111 (manufactured by BICKEMISA) 5 parts by mass / solid content conversion

Dispersing resin: alkali-soluble resin containing adamantyl group (binder resin (1)) 10 parts by mass / solid content conversion

Solvent: 350 parts by mass of propylene glycol monomethyl ether acetate (PGMEA)

And the mixture was stirred sufficiently.

Next, dispersion treatment was carried out by a paint shaker at 25 to 45 캜 for 6 hours. As the beads, zirconia beads having a diameter of 0.3 mm were used, and 10 g of dispersion and 20 g of beads were added. After completion of the dispersion, the beads and the dispersion liquid were separated by a filter to prepare a high dielectric constant inorganic particle dispersion 1 having a solid content of 25 mass%.

The high dielectric constant inorganic particle dispersions 2 and 3 were prepared in the same manner as above except that the high dielectric constant inorganic particles were replaced by T-BTO-020RF and TTO-51N from UEP.

The evaluation conditions in the examples and comparative examples are as follows.

(Method for Measuring Film Thickness of Photosensitive Resin Composition)

The measurement was carried out using a contact type step system "? -Step IQ" (manufactured by KLA Tencor). The film thickness was measured randomly at two positions, and the average value of the two points was taken as the film thickness. The measurement was 0.7 mm and the scanning speed was 0.5 mm / s.

(Electrical measurement sample production)

An ITO electrode was sputtered on the glass substrate to a total thickness of 70 nm to obtain a conductive substrate. The photosensitive resin composition was coated on the conductive substrate using a spin coater and dried for 90 seconds on a hot plate at 100 占 폚. Thereafter, the entire exposure was performed with an exposure amount of 120 mJ / cm 2 (intensity at a wavelength of 365 nm) with an exposure apparatus MA-1100 (manufactured by Dainippon Ink and Chemicals, Inc.). Next, using a developing device of AD-1200 manufactured by TAKIZAWA INDUSTRIAL CO., LTD., Developing was carried out by immersing in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide as a developing solution for 50 seconds thereafter, washing with water for 20 seconds, Then, the water was blown. Thereafter, the resultant was fired in a clean oven at 230 DEG C for 30 minutes to obtain a dielectric film. The film thickness of the dielectric film was 0.3 탆.

An aluminum electrode was formed on this dielectric film by a vapor deposition method. The aluminum electrode is a circular pattern electrode having a thickness of 60 nm and an area of 3 mm 2. The ITO electrode and the portion sandwiched by the aluminum electrode were measured.

(Measurement of relative dielectric constant)

Electric measurement A terminal was brought into contact with the ITO electrode on the substrate of the sample and one aluminum electrode on the dielectric film to make a circuit and the capacitance at a frequency of 1.0 kHz was measured. From the measured capacitance, the film thickness of the dielectric film, and the area of the aluminum electrode, the relative dielectric constant was calculated using equation (1).

C =? _R ? ₀ S / d (1)

In the above formula (1), C: capacity,? _R : relative dielectric constant,? ₀ : dielectric constant of vacuum (integer), S: electrode area, and d:

For this measurement, an LCR meter 4284A (manufactured by Hewlett Packard) was used.

(Leakage current measurement)

A terminal was brought into contact with the ITO electrode on the substrate of the electrical measurement sample and one aluminum electrode on the dielectric film, and a voltage of 1 V to 50 V was applied at 2 V intervals, and the current at that time was measured. As a value for comparing each photosensitive resin composition, a current value at the time of applying 15 V was used. For this measurement, an ultra high resistance meter R8340A (manufactured by ADVANTEST) was used.

(Developability Evaluation)

The photosensitive resin composition was coated on a glass substrate sputtered with an ITO electrode with a spin coater and dried for 90 seconds on a hot plate at 100 占 폚. Thereafter, patterning exposure was performed using a line-and-space (L / S) mask of 15/15 μm and 50/50 μm with an exposure apparatus MA-1100 (manufactured by Dainippon Ink and Chemicals, Inc.). At this time, the gap between the mask and the substrate was 5 占 퐉, and the exposure dose was 20 to 100 mJ / cm2 (intensity at a wavelength of 365 nm). Next, development was carried out using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide as a developer using a developing apparatus of AD-1200 manufactured by Takizawa Industrial Co., Ltd. The developer was sprayed for 90 seconds at a spray pressure of 0.15 MPa while being rotated at 30 rpm, and then subjected to a washing treatment at 300 rpm for 10 seconds. Thereafter, the resultant was baked at 230 deg. C for 30 minutes in a clean oven to obtain a dielectric film having a film thickness of 300 nm.

The criteria for evaluating developability were as follows.

?: 15/15 占 퐉 line-and-space was opened.

?: Line and space of 15/15 占 퐉 were not opened but line and space of 50/50 占 퐉 were opened.

×: Line and space of 50/50 μm did not open.

(Preparation of photosensitive resin composition)

Each of the components shown in Table 1 were mixed in a glass bottle in the amounts shown in Table 1 to prepare respective photosensitive resin compositions. The values in Table 1 indicate the parts by mass of solids, and a solvent (PGMEA) was used so that the total solid content of each photosensitive resin composition was 20% by mass. As the high-permittivity inorganic particle dispersion, the above-mentioned high-permittivity inorganic particle dispersions 1 to 3 were used. However, in Examples and Comparative Examples using a binder resin other than the binder resin (1), it was confirmed that in the high-dielectric constant inorganic particle dispersion 1, a dispersion resin was prepared from the binder resin (1) instead of the binder resin Were used. The compounding amount of the binder resin in Table 1 represents the total amount including the blending amount of the dispersion resin.

In Example 1, although the zirconium dioxide particles contained a very high proportion of the total solid content of the photosensitive resin composition, the leakage current at the time of 15 V application was low at 10 ^-9 (A / cm 2) order, have. On the other hand, in Comparative Examples 1 and 2, barium titanate particles and titania particles were contained at a high ratio, which increased leakage current and poor developing performance.

Since the zirconium dioxide particles have a small number of surface functional groups, it is considered that the hygroscopicity of the coating film is suppressed and the leakage current is lowered. In addition, the zirconium dioxide particles are in a state of being coated with a dispersant or a resin which is soluble in a solvent because of high dispersibility and easy adsorption with the dispersant and the resin, and it is considered that the zirconium dioxide particles have good developability. On the other hand, barium titanate particles and titania particles are low in dispersibility and inferiority to a resin with a solubility in solvent, so that film roughening occurs at the time of development and the leakage current is considered to be high. Further, the barium titanate particles and titania particles are considered to have a high polarity on the surface of the particles, strong adhesion at the interface with the glass substrate, and insufficient dissolution at the time of development, resulting in dissolved residues.

Further, from the comparison between Examples 1 and 2, it was confirmed that the leakage current suppression and developability were all good regardless of the content ratio of the zirconium dioxide particles.

From the comparison between Examples 1 and 3, it was confirmed that the binder resin had an epoxy (meth) acrylate resin having a repeating unit structure represented by the formula (I) as well as an epoxy (meth) acrylate resin having a partial structure represented by the formula ) Acrylate resin, it was confirmed that both leakage current suppression and developability were good.

When a fluorene ring-containing epoxy (meth) acrylate resin, a bisphenol A-type epoxy (meth) acrylate resin and a bisphenol F-type epoxy (meth) acrylate resin were used as in Comparative Examples 3 to 5, (Meth) acrylate resin having a repeating unit structure represented by the formula (I) and an epoxy (meth) acrylate resin having a partial structure represented by the formula (II) as in Examples 1 to 3 When one side is used, developability is good. This is presumably because the (meth) acryloyl group, which is a hydrophilic group, tends to open outward and the solubility improves because these epoxy (meth) acrylate resins have a bulky and rigid skeleton at the center thereof.

On the other hand, it is considered that the fluorene ring-containing epoxy (meth) acrylate resin is bulky and has high hydrophobicity, resulting in poor developability. Further, since bisphenol A epoxy (meth) acrylate resin or bisphenol F epoxy (meth) acrylate resin has a rotatable skeleton, the sensitivity is improved for a resin having a non-rotatable skeleton, but sensitivity irregularity occurs , And it is considered that the developability is poor in the condition that a hydrophilic part such as in the presence of a low polarity solvent is liable to aggregate.

On the other hand, in the case of using an acrylic resin as in Comparative Examples 6 and 7, the developability is good and the same dielectric constant as in Examples 1 to 3, but the leakage current is large. This is considered to be due to the non-uniformity of the sensitivity in the coating film due to the flexibility of the skeleton of the acrylic resin, the unevenness of the coating film after development, and the increase in the leak current due to the increase in the hygroscopicity of the film. In addition, it is considered that the acrylic resin has low heat resistance, and the acrylic resin decomposes at the time of thermal curing, resulting in pinholes.

From the comparison of Examples 1, 4 and 5, it was confirmed that the leakage current suppression and developability were all good regardless of the type of the polymerizable monomer. Particularly, in Example 1, a bifunctional (meth) acrylate was used as a polymerizable monomer, whereas in Examples 4 and 5, a bifunctional (meth) acrylate was used as a polymerizable monomer, Although the sensitivity was lowered, a rigid film was formed with respect to the alkali phenomenon by being rigid and having a small number of skeletons, resulting in improvement of electrical characteristics.

While the invention has been described in detail with reference to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention. The present application is based on Japanese Patent Application (Japanese Patent Application No. 2016-150610) filed on July 29, 2016, which is incorporated by reference in its entirety.

Claims (9)

A photosensitive resin composition containing zirconium dioxide particles, (b) a dispersant, (c) a solvent, (d) a binder resin, (e) a polymerizable monomer, and (f)
Wherein the binder resin (d) contains at least one of an epoxy (meth) acrylate resin having a repeating unit structure represented by the following formula (I) and an epoxy (meth) acrylate resin having a partial structure represented by the following formula By weight based on the total weight of the photosensitive resin composition.
[Chemical Formula 1]

(In the formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a divalent hydrocarbon group which may have a substituent. The benzene ring of the formula (I) may be further substituted by an arbitrary substituent * Indicates a combined hand.)
(2)

(In the formula (II), R ³ represents, independently of each other, a hydrogen atom or a methyl group, and R ⁴ represents a divalent hydrocarbon group having an aliphatic cyclic group as a side chain. The method according to claim 1,
Wherein the content of the binder resin (d) in the total solid content is 5% by mass or more. 3. The method according to claim 1 or 2,
Wherein the content ratio of the zirconium dioxide particles (a) in the total solid content is 50 mass% or more. 4. The method according to any one of claims 1 to 3,
Wherein the polymerization initiator (f) contains an oxime ester compound. 5. The method according to any one of claims 1 to 4,
Wherein the polymerizable monomer (e) comprises a (meth) acrylate compound represented by the following formula (III).
(3)

(Formula (III) of, R ⁵ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. R ⁶ it is, represents an alkylene group which may optionally each independently have a substituent. R ^7, each independently , A hydrogen atom or a methyl group, k and l each independently represent an integer of 1 to 20.) A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 5. An interlayer insulating film comprising the cured product according to claim 6. 8. A TFT active matrix substrate comprising the interlayer insulating film according to claim 7. An image display device comprising the TFT active matrix substrate according to claim 8.