KR20120081949A - Positive photosensitive resin composition, method for forming cured film, cured film, organic el display device, and liquid crystal display device - Google Patents

Abstract

The present invention provides a positive photosensitive resin composition which is excellent in applicability and can prevent precipitation during refrigeration and storage.
(Component A) The copolymer which contains structural unit A and structural unit B represented by following General formula (1), and has a weight average molecular weight of 1,000-10,000, and (component B) the weight average molecular weight represented by following General formula (2) This 1,000-50,000 polymer has a structural unit which has an acid-decomposable group which decomposes | dissolves with (component C) acid, and produces | generates a carboxyl group or phenolic hydroxyl group, and a functional group which can react with a carboxyl group or phenolic hydroxyl group, and can form a covalent bond. It contains resin which has a structural unit, (component D) photoacid generator, and (component E) solvent, content of the said component A is 0.001-1.00 mass%, and content of the said component B is 0.001-1.00 mass%. A positive photosensitive resin composition characterized by the above-mentioned.

Description

POSITIVE PHOTOSENSITIVE RESIN COMPOSITION, METHOD FOR FORMING CURED FILM, CURED FILM, ORGANIC EL DISPLAY DEVICE, AND LIQUID CRYSTAL DISPLAY DEVICE}

The present invention relates to a positive photosensitive resin composition, a method of forming a cured film, a cured film, an organic EL display device, and a liquid crystal display device.

The organic EL display device, the liquid crystal display device, or the like is provided with a patterned interlayer insulating film. In the formation of this interlayer insulating film, the number of steps for obtaining the required pattern shape is small, and sufficient flatness is obtained, so that the photosensitive resin composition is widely used.

Japanese Patent Application Laid-Open No. 2009-98616 discloses (A) a structural unit having an acid dissociable group and a structural unit having a functional group capable of reacting a carboxyl group to form a covalent bond, and is an alkali insoluble group and an alkali poorly soluble. A positive photosensitive resin composition is described which contains a resin which becomes alkali-soluble when the acid dissociable group dissociates, and (B) a compound which generates an acid by irradiation with actinic light or radiation.

As described in Japanese Unexamined Patent Publication No. 2009-98616, the applicability of a composition containing a resin having an acid dissociable group is hardly studied.

On the other hand, it is known that the positive photosensitive resin composition has a problem of particle precipitation at the time of refrigeration (Japanese Patent No. 2584311, Japanese Patent No. 3929648, Japanese Patent No. 4181760). Since the structure of the photosensitive resin composition described in this document presupposes application | coating to a small board | substrate, applicability to a large board | substrate is not considered. However, in the positive type chemically amplified photosensitive resin composition for large LCDs, it is difficult to attain both the application suitability of the composition containing the resin having an acid dissociable group and the precipitation of particles during cold storage in view of the characteristic change during cryopreservation. It is the current situation that is not.

The problem to be solved by this invention is providing the positive photosensitive resin composition which is excellent in applicability and can prevent precipitation at the time of cold storage.

The present inventors have found that the composition has a specific effect by using a fluorine-based surfactant of a specific structure in combination with a surfactant containing a silicon atom of a specific structure, and completed the present invention.

That is, this invention has the following structures.

[1] (Component A) A copolymer having a structural unit A and a structural unit B represented by the following General Formula (1) and having a weight average molecular weight of 1,000 to 10,000, (component B) represented by the following General Formula (2) A polymer having a weight average molecular weight of 1,000 to 50,000, a structural unit having an acid-decomposable group that is decomposed by the (component C) acid to generate a carboxyl group or a phenolic hydroxyl group, and can react with a carboxyl group or a phenolic hydroxyl group to form a covalent bond. It contains resin which has a structural unit which has a functional group, (component D) photoacid generator, and (component E) solvent, content of the said component A is 0.001-1.00 mass%, and content of the said component B is 0.001-1.00 mass. It is%, The positive type photosensitive resin composition.

(In general formula (1), R <^1> and R <^3> represents a hydrogen atom or a methyl group each independently, R <^2> represents a C1-C4 linear alkylene group, R <^4> represents a hydrogen atom or an alkyl group, and L is An alkylene group having 3 to 6 carbon atoms is represented, p and q are mass percentages indicating the polymerization ratio of structural unit A and structural unit B, p represents 10 to 80 mass%, q represents 20 to 90 mass%, r represents an integer of 1 to 18, n represents an integer of 1 to 10)

(In general formula (2), R <^5> -R <^12> is respectively independently an amino group, a hydroxyl group, a carboxyl group, a glycidyl group, a thiol group, the alkyl group and alkylene group which can also take the repeating structure of a C1-C20 linear or cyclic structure. , Aralkyl group and alkoxy group, m and n represent a mass percentage indicating the polymerization ratio of the dimethylsiloxane structural unit and the modified siloxane structural unit)

[2] In the above [1], at least one of the R ⁵ , R ⁷ , R ⁹ and R ¹¹ in the general formula (2) is a polyethyleneoxy group, an unsubstituted alkyl group or an alicyclic group substituted with a polypropyleneoxy group. Positive type photosensitive resin composition characterized by the above-mentioned epoxy group substituted alkyl group, glycidyl group substituted alkyl group, and aralkyl group.

[3] The positive photosensitive resin composition according to the above [1] or [2], wherein L is a branched alkylene group represented by the following General Formula (3).

(In General Formula (3), R ¹³ represents an alkyl group having 1 to 4 carbon atoms.)

[4] The positive photosensitive resin composition according to the above [3], wherein R ¹³ is an ethyl group.

[5] The compound C according to any one of the above [1] to [4], wherein the component C is at least one compound selected from the group consisting of styrene derivatives, maleimide derivatives, (meth) acrylic acid and hydroxyl-containing (meth) acrylate compounds Positive type photosensitive resin composition characterized by further having a structural unit derived.

[6] The acid-decomposable group of component C according to any one of [1] to [5], represented by the following general formula (Ia), general formula (Ib), general formula (IIa) or general formula (IIb). The positive photosensitive resin composition characterized by the above-mentioned.

(In general formula (Ia), general formula (Ib), general formula (IIa), and general formula (IIb), R <^21> represents an alkyl group or a cycloalkyl group each independently, R <^22> represents an alkyl group each independently, and R ²¹ and R ²² may form a ring, R ²³ represents a tertiary alkyl group, R ²⁴ represents a tertiary alkyl group or tert-butoxycarbonyl group, and Ar ¹ and Ar ² each independently represent a divalent aromatic group Broken line indicates a coupling point with another structure)

[7] The positive photosensitive resin composition according to any one of [1] to [6], which includes at least one of an oxiranyl group and an oxetanyl group as the functional group of the component C.

[8] The positive photosensitive resin composition according to any one of [1] to [8], wherein the functional group of the component C is an oxetanyl group.

[9] The positive photosensitive resin composition according to any one of [1] to [9], wherein the component D is an oxime sulfonate compound.

[10] The positive type photosensitive resin according to any one of [1] to [9], wherein the component E is a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof. Composition.

[11] (1) An application step of applying the positive photosensitive resin composition according to any one of the above [1] to [10] on a substrate; (2) Solvent removal for removing the solvent from the applied positive photosensitive resin composition. The manufacturing method of the cured film containing the process, (3) the exposure process exposed by actinic light, (4) the developing process developed by the aqueous developing solution, and (5) the post-baking process which thermosets.

[12] A cured film produced by the method for producing a cured film according to the above [11].

[13] The cured film according to the above [12], which is an interlayer insulating film.

[14] An organic EL display device or liquid crystal display device comprising the cured film according to the above [12] or [13].

(Effects of the Invention)

According to this invention, the positive photosensitive resin composition which is excellent in applicability and can prevent precipitation at the time of refrigeration, and the formation method of the cured film using the same can be provided.

1 shows a configuration conceptual diagram of an example of an organic EL display device. Typical sectional drawing of the board | substrate in a bottom emission type organic electroluminescence display is shown, and it has the planarization film 4. As shown in FIG.
2 shows a configuration conceptual diagram of an example of a liquid crystal display device. Typical sectional drawing of the active-matrix board | substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.
1, TFT is a thin film transistor, 2 is wiring, 3 is an insulating film, 4 is a planarization film, 5 is a first electrode, 6 is a glass substrate, 7 is a contact hole, 8 is an insulating film. 10 is a liquid crystal display device, 12 is a backlight unit, 14 is a glass substrate, 16 is a TFT, 17 is a cured film, 18 is a contact hole, 19 is an ITO transparent electrode, and 20 is a liquid crystal. And 22 represents a color filter, respectively.

Hereinafter, the positive photosensitive resin composition of this invention is demonstrated in detail.

[Positive-type photosensitive resin composition]

The positive photosensitive resin composition (henceforth "photosensitive resin composition") of this invention contains structural unit A and structural unit B represented by following General formula (1) (component A), and a weight average molecular weight is 1,000-10,000 Phosphorus copolymer, (component B) The polymer whose weight average molecular weight represented by following General formula (2) is 1,000-50,000, The structural unit which has an acid-decomposable group which decomposes | dissolves with (component C) acid and produces | generates a carboxyl group or phenolic hydroxyl group. And a resin having a structural unit having a functional group capable of reacting with a carboxyl group or a phenolic hydroxyl group to form a covalent bond, a (component D) photoacid generator and a (component E) solvent, wherein the content of the component A is 0.001? It is 1.00 mass%, and content of the said component B is 0.001-1.00 mass%, It is characterized by the above-mentioned.

(In general formula (1), R <^1> and R <^3> represents a hydrogen atom or a methyl group each independently, R <^2> represents a C1-C4 linear alkylene group, R <^4> represents a hydrogen atom or an alkyl group, and L is An alkylene group having 3 to 6 carbon atoms is represented, p and q are mass percentages indicating the polymerization ratio of structural unit A and structural unit B, p represents 10 to 80 mass%, q represents 20 to 90 mass%, r represents an integer of 1 to 18, n represents an integer of 1 to 10)

(In general formula (2), R <^5> -R <^12> is respectively independently an amino group, a hydroxyl group, a carboxyl group, a glycidyl group, a thiol group, the alkyl group and alkylene group which can also take the repeating structure of a C1-C20 linear or cyclic structure. , Aralkyl group and alkoxy group, m and n represent a mass percentage indicating the polymerization ratio of the dimethylsiloxane structural unit and the modified siloxane structural unit)

By such a structure, it is excellent in applicability and the precipitation at the time of refrigeration storage can be prevented.

Moreover, in the more preferable aspect of the positive photosensitive resin composition of this invention, it is further more preferable that the cured film which is small in pixel defect and excellent in planarity is obtained.

Hereinafter, the photosensitive resin composition of this invention is demonstrated.

The photosensitive resin composition of this invention is a positive photosensitive resin composition.

Moreover, it is preferable that the positive photosensitive resin composition of this invention is a chemically amplified positive photosensitive resin composition (chemical amplification positive photosensitive resin composition).

It is preferable that the photosensitive resin composition of this invention does not contain a 1, 2- quinonediazide compound as a photo-acid generator sensitive to actinic light. 1,2-quinonediazide compounds generate carboxyl groups by sequential fluorescence chemistry, but the quantum yield is necessarily 1 or less.

On the other hand, the photoacid generator (component D) used in the present invention acts as a catalyst for the deprotection of the acid group protected by the acid generated in response to actinic light, so that the acid produced by the action of one photon is depleted. Contributing to the protective reaction, the quantum yield exceeds 1, becomes a large value, for example, a power of 10, and high sensitivity is obtained as a result of so-called chemical amplification.

Hereinafter, each component represented by these (component A) etc. is made into "component A", etc., respectively.

(Component A)

The photosensitive resin composition of this invention contains structural unit A and structural unit B represented by following formula (1), and has a weight average molecular weight of 1,000-10,000 or less with respect to the total mass of the photosensitive resin composition. It contains 1.00 mass%.

In formula (1), R <^1> and R <^3> respectively independently represents a hydrogen atom or a methyl group, R <^2> represents a C1-C4 linear alkylene group, R <^4> represents a hydrogen atom or an alkyl group, and L Is an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages indicating the polymerization ratios of the structural unit A and the structural unit B, p represents a numerical value of 10 mass% or more and 80 mass% or less, q Represents the numerical value of 20 mass% or more and 90 mass% or less, r represents the integer of 1 or more and 18 or less, n represents the integer of 1 or more and 10 or less.

In addition, the carbon number of said L means all the carbon numbers which comprise the alkylene group which also included the branch part.

Although said L may be a linear alkylene group or a branched alkylene group, it is preferable that it is a branched alkylene group, and it is more preferable that it is an alkylene group represented by following General formula (3).

Herein, R ¹³ represents an alkyl group having 1 to 4 carbon atoms, and in view of compatibility and wettability to the applied surface, an alkyl group having 1 to 3 carbon atoms is preferable, and an alkyl group having 2 or more carbon atoms, that is, an ethyl group desirable.

P and q are the mass percentages indicating the polymerization ratio.

p shows the numerical value of 10 mass% or more and 80 mass% or less, and the numerical value of 20 mass% or more and 60 mass% or less is preferable at the point of hydrophobic-hydrophilic balance.

In addition, q represents the numerical value of 20 mass% or more and 90 mass% or less, and the numerical value of 40 mass% or more and 80 mass% or less is preferable at the point of hydrophobic-hydrophilic balance.

As for said r, the numerical value of 6 or more and 18 or less is preferable. In addition, n is preferably an integer of 6 or more and 10 or less.

It is preferable that said R <^2> is a C1-C2 linear alkylene group, ie, a methylene group or an ethylene group, and it is more preferable that it is an ethylene group.

It is preferable that said R <^4> is a hydrogen atom or a C1-C4 alkyl group, It is more preferable that it is a hydrogen atom or a methyl group, It is further more preferable that it is a hydrogen atom.

The component A may have other structural units other than the said structural unit A and the structural unit B. There is no restriction | limiting in particular as other structural unit, The structural unit derived from a well-known ethylenically unsaturated compound can be illustrated preferably.

It is preferable that the sum total of content of the monomer unit which forms the structural unit A and the monomer unit content which forms the structural unit B among all the monomer units which comprise the component A is 90 mol% or more.

Although A-1A-12 shown below specifically as component A can be illustrated preferably, this invention is not limited to these.

The weight average molecular weight (Mw) of component A is 1,000 or more and 10,000 or less, It is preferable that it is 1,000 or more and 6,000 or less from a viewpoint of applicability (preferably applicability | paintability, the following is the same), It is more preferable that it is 1,000 or more and 3,000 or less, More preferably, it is 1,200 or more and 2,000 or less. Moreover, it is preferable that the weight average molecular weight in this invention is polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC) which uses a tetrahydrofuran (THF) solvent as a carrier.

There is no restriction | limiting in particular as a manufacturing method of component A, It can manufacture by a well-known synthesis method or polymerization method.

Component A can be used individually by 1 type or in mixture of 2 or more types.

The addition amount of the component A in the photosensitive resin composition of this invention is 0.001-1.00 mass% with respect to the total mass of the photosensitive resin composition, It is preferable that it is 0.005-0.20 mass% from an applicability viewpoint, and it is 0.007-0.15 mass%. More preferred. Excellent applicability is obtained by adding component A in an amount in the above range. It is particularly effective for applying slit to large substrates. Here, a large board | substrate refers to the board | substrate of 1m * 1m or more and 5m * 5m or less. Moreover, developability excellent also in a large sized board | substrate is obtained by adding component A in the quantity of the said range. It was also surprisingly found that the effect of good liquid crystal specific resistance can be obtained by adding component A in an amount in the above range.

(Component B)

The photosensitive resin composition of this invention contains 0.001 to 1.00 mass% of the polymer whose weight average molecular weights are 1,000-50,000 represented by following General formula (2) as component B with respect to the total mass of the photosensitive resin composition. By using such component B together with the said component A which is a fluorine-type copolymer, the photosensitive resin composition of this invention can remarkably improve the solvent solubility at low temperature as a synergistic effect, and can suppress the particle generation at low temperature storage.

Component B is represented by following General formula (2).

In general formula (2), R <^5> -R <^12> is respectively independently an amino group, a hydroxyl group, a carboxyl group, a glycidyl group, a thiol group, the alkyl group, alkylene group which can also take the repeating structure of a C1-C20 linear or cyclic structure, Aralkyl group and an alkoxy group are shown.

It is preferable that said R <^6> , R <^8> , R <^10> , R <^12> is respectively independently an alkyl group which can also take the C1-C20 linear or cyclic repeating structure, It is more preferable that it is a C1-C20 linear alkyl group, It is especially preferable that it is a C1-C10 linear alkyl group, and it is still more preferable that it is a methyl group.

At least one of R ⁵ , R ⁷ , R ⁹ and R ¹¹ is a polyethylene oxy group (hereinafter referred to as EO), a polypropylene oxy group (hereinafter referred to as PO), a polyethylene oxy group substituted with a polypropylene oxy group, an alkyl group (Or may be modified with an epoxy group or a glycidyl group), a glycidyl group, an aralkyl group, or an epoxy group, preferably a polyethylene oxy group and an unsubstituted alkyl group substituted with a polypropylene oxy group (in this case, the alkyl group has 1 to 20 carbon atoms). It is preferable to be an individual, and it is more preferable that it is 1-10), an alicyclic epoxy group substituted alkyl group (It is preferable that this alkyl group in this case is C1-C30, and it is more preferable that it is 1-20.), Glycidyl group substitution. Particularly preferred is at least one selected from an alkyl group (the alkyl group in this case preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms) and an aralkyl group (preferably 8 to 20 carbon atoms). All. That is, as the polymer represented by the general formula (2), polyethylene oxide modification, polypropylene oxide modification, glycidyl modification, alkyl modification (or glycidyl modification), and aralkyl modified polymer are particularly preferable. The said R <^5> , R <^7> , R <^9> and R <^11> may be same or different.

The preferable combination of said R <^5> , R <^7> , R <^9> and R <^11> is demonstrated. First, when R <^5> and R <^9> is group in which at least one of R <^7> and R <^11> is other than a methyl group, the preferable range of R <^5> and R <^9> is the same as the preferable range of said R <^6> , R <^8> , R <^10> and R <^12> . On the other hand, when both R ⁷ and R ¹¹ is a methyl group, R ⁵ and R ⁹ may be modified with polyethylene oxy group, polypropylene oxy group, polyethylene oxy group substituted with polypropylene oxy group, alkyl group (or epoxy group, glycidyl group) Good), glycidyl group, aralkyl group and epoxy group, preferably at least one selected from polyethylene oxy group, unsubstituted alkyl group, alicyclic epoxy group substituted alkyl group, glycidyl group substituted alkyl group and aralkyl group substituted with polypropylene oxy group. desirable.

Subsequently, in the case of R ⁷ and R ¹¹ , at least one of R ⁵ and R ⁹ is a group other than the methyl group, the preferred range of R ⁷ and R ¹¹ is the same as the preferred range of R ⁶ , R ⁸ , R ¹⁰ and R ¹² . On the other hand, when both R ⁵ and R ⁹ is a methyl group, R ⁷ and R ¹¹ is a polyethylene oxy group, polypropylene oxy group, polyethylene oxy group substituted with a polypropylene oxy group, alkyl group (or epoxy group, glycidyl group modified even if Good), glycidyl group, aralkyl group and epoxy group, preferably at least one selected from polyethylene oxy group, unsubstituted alkyl group, alicyclic epoxy group substituted alkyl group, glycidyl group substituted alkyl group and aralkyl group substituted with polypropylene oxy group desirable.

When R <^7> , R <^11> is denatured, said m and n represent the mass percentage which shows the polymerization ratio of a dimethylsiloxane structural unit and a modified siloxane structural unit.

It is preferable that it is 10-90 mass%, and, as for said m, it is more preferable that it is 20-80 mass%.

Moreover, it is preferable that it is 10-90 mass%, and, as for n, it is more preferable that it is 20-80 mass%.

Although the number of units of the repeating unit of the dimethylsiloxane structure is not particularly limited, when the number of repeating units (molecular weight) is increased, the surface locality is improved, and when the number of repeating units is smaller, compatibility with the composition is improved. For example, the number of repeating units may be 1-20, but the number of units is usually determined in consideration of the molecular weight, the polarity of the substituent, and the polarity of the composition. Particularly, since component B is used as an additive in the present invention, it is ubiquitous on the surface with a small amount of addition (low boundary micelle concentration and surface tension lowering ability) and the viscosity of the composition under the premise that it is compatible with the photosensitive resin composition of the present invention. It is preferable to select to suppress a rise (small molecular weight).

It is preferable that the HLB value (Hydrophile-Lipophile Balance, hydrophilic lipophilic balance) of the said component B is 1-15, It is more preferable that it is 1-10, It is especially preferable that it is 1-7.

It is preferable that the weight average molecular weights of the polymer represented by the said General formula (2) are 1000-50,000, It is more preferable that it is 1000-40,000, It is especially preferable that it is 1000-35,000.

The polymer represented by the general formula (2) can be obtained synthetically or commercially. For example, Dow Corning Toray Co., Ltd., Shin-Etsu Chemical Co., Ltd. Polymers, such as these, can be used as component B.

It is preferable that the photosensitive resin composition of this invention contains the polymer represented by the said General formula (2) in 0.001 to 1.00 mass%, and it is more preferable to contain in 0.005 to 0.5 mass%.

(Component C)

Component C is a resin having at least a structural unit having a structural unit having an acid-decomposable group which is decomposed by an acid to generate a carboxyl group or a phenolic hydroxyl group, and a functional group capable of reacting with a carboxyl group or a phenolic hydroxyl group to form a covalent bond.

The component C may have each of said structural units individually by 1 type, or may have 2 or more types. In addition, the component C may have structural units other than each said structural unit.

It is preferable that component C is resin which is alkali-insoluble and becomes alkali-soluble when an acid-decomposable group decomposes. Here, an "acid-decomposable group" means the functional group which can decompose in presence of an acid. In addition, "alkali-soluble" is 0.4 mass% tetramethyl at 23 degreeC, when dip solution of the coating film (3 micrometers in thickness) formed by applying the solution of a compound (resin) on the board | substrate, and heating it at 90 degreeC for 2 minutes. The dissolution rate in the aqueous ammonium hydroxide solution is 0.01 μm / sec or more. On the other hand, "alkali insoluble" means that the said dissolution rate is less than 0.01 µm / second.

<C- (1): structural unit having an acid-decomposable group which is decomposed by an acid to generate a carboxyl group or a phenolic hydroxyl group>

The structural unit which has an acid-decomposable group (henceforth an "acid-decomposable group") which decomposes | dissolves with the acid contained in component C and produces | generates a carboxyl group or a phenolic hydroxyl group is a formula which produces | generates a carboxyl group by decomposing (dissociating) with an acid. Containing a structural unit having a structure represented by formula (Ia) or formula (IIa), or a structural unit having a structure represented by formula (Ib) or formula (IIb) that is decomposed by acid to form phenolic hydroxyl groups desirable.

First, the structural unit which has a structure represented by Formula (Ia) and Formula (Ib) is demonstrated.

In formulas (Ia) and (Ib), R ²¹ each independently represents an alkyl group or a cycloalkyl group.

The alkyl group in R ²¹ may be linear or branched.

As preferable carbon number of the alkyl group in R <^21> , it is preferable that it is 1-20, It is more preferable that it is 1-10, It is still more preferable that it is 1-7.

As preferable carbon number of the cycloalkyl group in R <^21> , it is preferable that it is 3-20, It is more preferable that it is 3-10, It is still more preferable that it is 5-7.

In addition, when these carbon number has a substituent, carbon number of a substituent is also included.

The alkyl group for R ²¹ is, for example, a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, n-pentyl group, neopentyl group, n -Hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, etc. are mentioned.

As a cycloalkyl group in R <^21> , a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, isobornyl group etc. are mentioned, for example.

In addition, the alkyl group and cycloalkyl group in R ²¹ may have a substituent.

As a substituent in the said alkyl group and cycloalkyl group, a C1-C10 alkyl group (methyl group, an ethyl group, a propyl group, a butyl group etc.), a C3-C10 cycloalkyl group, a C6-C10 aryl group, a halogen atom (fluorine atom) , A chlorine atom, a bromine atom, an iodine atom), a cyano group, a nitro group, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, and the like, and these substituents may be further substituted with the above substituents.

Moreover, as an alkyl group or a cycloalkyl group in R <^21> , a C1-C10 alkyl group, a C3-C10 cycloalkyl group, or a C7-C11 aralkyl group is preferable, A C1-C6 alkyl group, C3-C6 group Cycloalkyl group or benzyl group is more preferable, It is more preferable that it is an ethyl group or a cyclohexyl group, It is especially preferable that it is an ethyl group.

In formula (Ia) and formula (Ib), R ²² each independently represents an alkyl group.

The alkyl group in R ²² may be linear or branched.

As preferable carbon number of the alkyl group in R <^22> , it is preferable that it is 1-20, It is more preferable that it is 1-10, It is still more preferable that it is 1-7.

In addition, when these carbon number has a substituent, carbon number of a substituent is also included.

Moreover, as an alkyl group in R <^22> , a C1-C6 alkyl group is preferable and a methyl group is especially preferable.

R ²¹ and R ²² may form a ring, and as a preferred example thereof, a ring is preferably formed by a saturated hydrocarbon chain, and a 5-membered ring structure, that is, tetrahydrofuranyl ester structure or 6-membered ring structure, that is, tetrahydropyranyl ester The structure can be mentioned. Moreover, these ring structures may have a substituent and as a substituent, a C1-C10 alkyl group (methyl group, an ethyl group, a propyl group, a butyl group etc.), a C3-C10 cycloalkyl group, a C6-C10 aryl group, a halogen Atoms (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a nitro group, a hydroxyl group, a C1-C10 alkoxy group etc. can be illustrated. These substituents may further be substituted by the said substituent.

In formula (Ib), Ar ¹ represents a divalent aromatic group and has OCH (OR ²¹ ) (R ²² ) on the aromatic ring.

It does not restrict | limit especially as a bivalent aromatic group in Ar <^1> , A phenylene group, a substituted phenylene group, a naphthylene group, a substituted naphthylene group, etc. can be illustrated, It is preferable that it is a phenylene group or a substituted phenylene group, It is preferable that it is phenylene It is more preferable that it is group, and it is still more preferable that it is a 1, 4- phenylene group.

In addition, the divalent aromatic group in Ar ¹ may have a substituent on an aromatic ring, and as a substituent, a C1-C10 alkyl group (methyl group, an ethyl group, a propyl group, a butyl group etc.), a C3-C10 cycloalkyl group, A C6-C10 aryl group, a halogen atom (fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a nitro group, a hydroxyl group, a C1-C10 alkoxy group etc. can be illustrated, These substituents are mentioned above. You may further substitute by a substituent.

The carboxylic acid monomer capable of forming a structural unit having a structure represented by the formula (Ia) by protecting the carboxyl group can be used as long as it can be a structural unit having an acid-decomposable group by protecting the carboxyl group. For example, acrylic acid Monocarboxylic acids such as methacrylic acid, crotonic acid and α-methyl-p-carboxystyrene; And dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid. Moreover, as a structural unit which has an acid-decomposable group, the monomeric unit derived from the carboxylic acid in which these carboxy groups were protected is mentioned as a preferable thing.

The monomer having a phenolic hydroxyl group capable of forming a structural unit having a structure represented by the formula (Ib) by protecting the phenolic hydroxyl group can be used as long as it can be a structural unit having an acid-decomposable group by protecting the phenolic hydroxyl group. For example, hydroxy styrene, such as p-hydroxy styrene and (alpha) -methyl- p-hydroxy styrene, the compound of Unexamined-Japanese-Patent No. 2008-40183, the compound of Unexamined-Japanese-Patent No. The 4-hydroxybenzoic acid derivatives described in paragraphs [0007] to [0010] of Publication No. 2888454, addition reaction products of 4-hydroxybenzoic acid and methacrylic acid glycidyl, and of 4-hydroxybenzoic acid and glycidyl acrylate Addition reactant etc. are mentioned as a preferable thing. Among these, α-methyl-p-hydroxystyrene, the compounds described in paragraphs [0011] to [0016] of JP-A-2008-40183, and paragraphs [0007] to [0010] of [0007] The 4-hydroxybenzoic acid derivatives described, addition reactants of 4-hydroxybenzoic acid and methacrylic acid glycidyl, and addition reactants of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable.

Among the structural units having an acid-decomposable group having a structure represented by formula (Ia) or formula (Ib), a structural unit represented by the following formula (III) is more preferable as a structural unit having an acid-decomposable group.

In formula (III), R ²⁵ represents an alkyl group or a cycloalkyl group, and the preferred form of R ²⁵ is the same as the preferred form of R ²¹ in formulas (Ia) and (Ib).

In addition, in formula (III), R <^26> represents a hydrogen atom or a methyl group.

As a preferable specific example of the radically polymerizable monomer used in order to form the structural unit represented by Formula (III), For example, 1-ethoxyethyl methacrylate, 1-ethoxyethyl acrylate, 1-methoxyethyl meth Acrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl methacrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl methacrylate, 1-isobutoxyethyl acrylate, 1 -(2-ethylhexyloxy) ethyl methacrylate, 1- (2-ethylhexyloxy) ethyl acrylate, 1-n-propoxyethyl methacrylate, 1-n-propoxyethyl acrylate, 1 -Cyclohexyloxyethyl methacrylate, 1-cyclohexyloxyethyl acrylate, 1- (2-cyclohexylethoxy) ethyl methacrylate, 1- (2-cyclohexylethoxy) ethyl acrylate, 1-benzyl Oxyethyl methacrylate, 1-benzyloxyethyl acrylate, and the like. Preferable examples are ethoxy ethyl acrylate, ethoxyethyl methacrylate and 1 to 1. These structural units can have 1 type individually or in combination of 2 or more types.

The radically polymerizable monomer used in order to form the structural unit which has an acid-decomposable group of the structure represented by Formula (Ia) or Formula (Ib) may use a commercially available thing, and can synthesize | combine what was synthesized by a well-known method. For example, as shown below, it can be synthesized by reacting (meth) acrylic acid with a vinyl ether compound in the presence of an acid catalyst.

Here, R ²⁵ and R ²⁶ correspond to R ²⁵ and R ²⁶ in Formula (III), respectively.

In addition, the structural unit which has an acid-decomposable group can be formed by superposing | polymerizing a carboxyl group or phenolic hydroxyl group containing monomer to be protected with the monomer mentioned later, or its precursor, and then reacting a carboxyl group or phenolic hydroxyl group with a vinyl ether compound. In addition, the specific example of the preferable monomeric unit formed in this way is the same as the monomeric unit derived from the preferable specific example of the said radically polymerizable monomer.

Among the structural units having an acid-decomposable group having a structure represented by formula (Ia) or formula (Ib), the structural unit of the following formula (IV) is also preferable as the structural unit having an acid-decomposable group.

(In formula (IV), R ⁵¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenylene group, and R ^{52 to} R ⁵⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Indicates)

Moreover, the structural unit represented by following formula (IV-1) (IV-4) is also preferable. Moreover, as a structural unit which has an acid-decomposable group, the structural unit represented by following formula (IV-1) or (IV-2) is especially preferable, and the structural unit represented by following formula (IV-1) is more preferable.

(In formula (IV-1)-(IV-4), R <^27> -R <^30> respectively independently represents a hydrogen atom or a methyl group.)

Next, the structural unit which has a structure represented by Formula (IIa) and Formula (IIb) is demonstrated.

In formulas (IIa) and (IIb), R ²³ represents a tertiary alkyl group, R ²⁴ represents a tertiary alkyl group or tert-butoxycarbonyl group, Ar ² represents a divalent aromatic group, and the dashed portion is The coupling point with another structure is shown.

As a tertiary alkyl group in R <^23> and R <^24> , a C4-C20 thing is preferable, A C4-C14 thing is more preferable, A C4-C8 thing is still more preferable.

Moreover, it is preferable that R <^23> in Formula (IIa) is a C4-C12 tertiary alkyl group, It is more preferable that it is a C4-C8 tertiary alkyl group, It is still more preferable that it is a t-butyl group.

Moreover, it is preferable that R <^24> in Formula (IIb) is a C4-C12 tertiary alkyl group and tert-butoxycarbonyl group, It is more preferable that it is a C4-C12 tertiary alkyl group, t-butyl It is more preferable that it is a group, and 2-tetrahydropyranyl group is especially preferable.

In formula (IIb), Ar ² represents a divalent aromatic group and has O (R ²⁴ ) on the aromatic ring.

The preferable form of Ar ² in Formula (IIb) is the same as that of Ar ¹ in Formula (Ib).

The tertiary alkyl group in R ²³ , the tertiary alkyl group in R ⁴ or the tert-butoxycarbonyl group, and the divalent aromatic group in Ar ² may have a substituent, and as a substituent, an alkyl group having 1 to 10 carbon atoms ( Methyl, ethyl, propyl, butyl, etc.), a C3-C10 cycloalkyl group, a C6-C10 aryl group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, A hydroxy group, a C1-C10 alkoxy group, etc. can be illustrated. These substituents may further be substituted by the said substituent.

As a tertiary alkyl group in R <^23> and R <^24> , it is more preferable that it is at least 1 sort (s) chosen from the group which consists of group represented by Formula (V) shown below.

In formula, R <^29> , R <^30> and R <^31> represent a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C6-C12 aryl group, or a C1-C12 aralkyl group each independently, and R Any two of ²⁹ , R ³⁰ and R ^{31 may} be bonded to each other to form a ring together with the carbon atoms to which they are bonded.

The alkyl group having 1 to 12 carbon atoms of R ²⁹ , R ³⁰ and R ³¹ in formula (V) may be linear or branched, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n- Butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, hexyl group (2,3-dimethyl-2-butyl group), n-heptane A methyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, etc. are mentioned.

As a C3-C12 cycloalkyl group, a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group etc. are mentioned, for example.

As a C6-C12 aryl group, a phenyl group, tolyl group, xylyl group, cumenyl group, 1-naphthyl group etc. are mentioned, for example.

As a C7-12 aralkyl group, a benzyl group, the (alpha)-methyl benzyl group, a phenethyl group, a naphthyl methyl group, etc. are mentioned, for example.

In addition, R ²⁹ , R ³⁰ and R ³¹ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. Examples of the ring structure in the case where R ⁹ and R ¹⁰ , R ⁹ and R ^11, or R ¹⁰ and R ¹¹ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, An adamantyl group, tetrahydropyranyl group, and the like.

As a carboxylic acid monomer which can form the monomeric unit which has a structure represented by said Formula (IIa) by protecting a carboxyl group, if it can become a structural unit which has an acid-decomposable group by protecting a carboxyl group, For example, In the description of (Ia), the carboxylic acid monomers described above are preferably listed.

The monomer having a phenolic hydroxyl group capable of forming a monomer unit having a structure represented by the formula (IIb) by protecting the phenolic hydroxyl group can be used as long as it can be a structural unit having an acid-decomposable group by protecting the phenolic hydroxyl group. For example, the monomer which has the phenolic hydroxyl group mentioned above in description of Formula (Ib) is mentioned preferably.

Of the structural units having the structures represented by these formulas (IIa) and (IIb), particularly preferred as structural units having an acid-decomposable group are structural units represented by the following formula (VI).

In formula (VI), R ³¹ represents a tertiary alkyl group, and R ³² represents a hydrogen atom or a methyl group.

In addition, in Formula (VI), the preferable aspect of R <^31> is the same as that of R <^23> in said Formula (IIa).

As a preferable specific example of the radically polymerizable monomer used in order to form the structural unit represented by Formula (VI), For example, tert- butyl methacrylate, tert- butyl acrylate, 2-methyl- 2-methacrylate methacrylate And methyl, 2-methyl-2-adamantyl acrylate, 1-methylcyclohexyl methacrylate, 1-methylcyclohexyl acrylate, and the like, and tert-butyl methacrylate and tert-butyl acrylate are particularly preferred. These structural units can be used individually by 1 type or in combination of 2 or more types.

As a preferable specific example of the structural unit which has an acid-decomposable group, the following monomeric unit can be illustrated.

Among all the monomer units constituting the component C, the content of the monomer unit forming the structural unit having an acid-decomposable group is preferably from 5 to 60 mol%, more preferably from 10 to 50 mol%, particularly preferably from 10 to 40 mol%. desirable. If it is said ratio, the photosensitive resin composition with high sensitivity or a wide exposure latitude will be obtained.

<C- (2): structural unit having a functional group capable of reacting with a carboxyl group or a phenolic hydroxyl group to form a covalent bond>

Examples of the functional group capable of reacting with a carboxyl group or a phenolic hydroxyl group to form a covalent bond include an oxiranyl group, an oxetanyl group, an acid anhydride group, an acid halide group, an isocyanate group, a group represented by the following formula (A), and (meth) acryl Royl groups are listed. Especially, group represented by an oxiranyl group, an oxetanyl group, an acid anhydride group, an acid halide group, an isocyanate group, and following formula (A) is preferable, and the group represented by an oxiranyl group, an oxetanyl group, or a formula (A) is preferable. More preferably, an oxiranyl group and an oxetanyl group are more preferable.

(In formula, R <^2> represents a C1-C9 alkyl group.)

It is preferable to synthesize | combine the component B using the radically polymerizable monomer containing such a functional group.

As a structural unit which has the said oxiranyl group and / or oxetanyl group, it is preferable that it is a structural unit which has an alicyclic epoxy group and / or oxetanyl group, and it is more preferable that it is a structural unit which has an oxetanyl group.

The alicyclic epoxy group is a group in which an aliphatic ring and an epoxy ring form a condensed ring, and specifically, for example, a 3,4-epoxycyclohexyl group, a 2,3-epoxycyclohexyl group, a 2,3-epoxycyclopentyl group And the like are preferably listed.

The group having an oxetanyl group is not particularly limited as long as it has an oxetane ring, but a (3-ethyloxetan-3-yl) methyl group can be preferably exemplified.

The structural unit which has an oxiranyl group and / or an oxetanyl group should just have at least one oxiranyl group or an oxetanyl group in one structural unit, and one or more oxiranyl group and one or more oxetanyl group, two Although it may have the above-mentioned oxiranyl group or two or more oxetanyl groups, although it does not restrict | limit especially, It is preferable to have an oxiranyl group and / or an oxetanyl group in total, and an oxiranyl group and / or an oxetanyl group It is more preferable to have one or two in total, and it is still more preferable to have one oxiranyl group or oxetanyl group.

As a specific example of the radically polymerizable monomer used for forming the structural unit which has an oxiranyl group, For example, glycidyl acrylate, glycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the glycine (alpha)-n-propyl acrylate Cydyl, α-n-butyl acrylate glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7- Epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, paragraphs of Japanese Patent No. 4168443 The compound containing the alicyclic epoxy skeleton as described in [0031]-[0035], etc. are mentioned.

As an example of the radically polymerizable monomer used in order to form the structural unit which has an oxetanyl group, it is (meth) which has the oxetanyl group of Unexamined-Japanese-Patent No. 2001-330953, for example. Acrylic esters etc. are mentioned.

As an example of the radically polymerizable monomer used for forming the structural unit which has an oxiranyl group and / or an oxetanyl group, it is preferable that they are a monomer containing a methacrylic ester structure, and a monomer containing an acrylic ester structure.

Among these monomers, more preferably, a compound containing an alicyclic epoxy skeleton described in Japanese Patent No. 4168443, paragraphs [0034] to [0035] and Japanese Patent Application Laid-Open No. 2001-330953, paragraphs [0011] to [0016] ] Is a (meth) acrylic acid ester having an oxetanyl group, and particularly preferred is a (meth) acrylic acid ester having an oxetanyl group described in paragraphs [0011] to [0016] of JP 2001-330953 A. Among these, preferred are 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, acrylic acid (3-ethyloxetan-3-yl) methyl, and methacrylic acid (3-ethyloxetane- 3-yl) methyl, most preferred are acrylic acid (3-ethyloxetan-3-yl) methyl and methacrylic acid (3-ethyloxetan-3-yl) methyl. These structural units can be used individually by 1 type or in combination of 2 or more types.

As a preferable specific example of the structural unit which has a functional group which can react with a carboxyl group or phenolic hydroxyl group, and can form a covalent bond, the following structural unit and the repeating unit represented by General formula (1) can be illustrated.

Repeating unit represented by the following general formula (1)

(In formula, R <^1> represents a hydrogen atom or a methyl group, and R <^2> represents a C1-C9 alkyl group.)

In General formula (1), R <^1> represents a hydrogen atom or a methyl group, and a hydrogen atom is preferable. R <^2> represents a C1-C9 alkyl group, a C1-C7 alkyl group is preferable, and a C2-C6 alkyl group is more preferable. The alkyl group may be either a linear or branched alkyl group.

The content rate of the monomer unit which forms the structural unit which has a functional group which can react with a carboxyl group or a phenolic hydroxyl group and form a covalent bond among all the monomer units which comprise component C has preferable 10-80 mol%, and 15-70 More preferably, mol% is 20-65 mol% is especially preferable. By containing in said ratio, the physical property of a cured film becomes favorable.

Among these structural units, a structural unit having an oxetanyl group is particularly preferable in view of excellent storage stability of the photosensitive composition.

<C- (3): other structural unit>

The component C may have other structural units other than the said C- (1) structural unit or C- (2) structural unit in the range which does not prevent the effect of this invention. As the other structural unit, a structural unit derived from at least one compound selected from the group consisting of a structural unit having a carboxyl group and / or phenolic hydroxyl group, a styrene derivative, a maleimide derivative, a (meth) acrylic acid and a (meth) acrylate compound containing a hydroxyl group Preferably exemplified. Especially, in this invention, it is more preferable that the said component C has a structural unit derived from at least 1 compound chosen from the group which consists of a styrene derivative, a maleimide derivative, a (meth) acrylic acid, and a hydroxyl-containing (meth) acrylate compound.

[Structural Unit Having Carboxylic Group and / or Phenolic Hydroxyl Group]

Component C may contain, as other structural units, structural units having carboxyl groups and / or phenolic hydroxyl groups in a range in which component C is not alkali-soluble. Carboxyl groups also include carboxylic anhydride residues. As a radically polymerizable monomer used in order to form the structural unit which has a carboxy group, For example, Monocarboxylic acids, such as (meth) acrylic acid and crotonic acid; Dicarboxylic acids, such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid, are preferable. Moreover, as a radically polymerizable monomer used for forming the structural unit which has a carboxylic anhydride residue, maleic anhydride, itaconic anhydride, etc. are preferable, for example. As a radically polymerizable monomer which forms the structural unit which has a phenolic hydroxyl group, For example, hydroxystyrenes, such as p-hydroxy styrene and (alpha) -methyl- p-hydroxy styrene, of Unexamined-Japanese-Patent No. 2008-40183 Preferred are the compounds described in paragraphs [0011] to [0016]. Among these, (meth) acrylic acid and hydroxy styrenes are more preferable. These structural units can be used individually by 1 type or in combination of 2 or more types.

As a preferable specific example, the following structural unit can be illustrated. In addition, R represents a hydrogen atom or a methyl group.

Since excellent sensitivity and developability can be obtained, the content rate of the monomer unit which forms the structural unit which has a carboxyl group and / or phenolic hydroxyl group among all the monomer units which comprise the said component B is 0-20 mol%, 5 is preferable. 15 mol% is more preferable.

Moreover, as a radically polymerizable monomer which forms another structural unit, the compound of Unexamined-Japanese-Patent No. 2004-264623 can be mentioned, for example.

Among these, (meth) acrylic acid ester containing alicyclic structures, such as dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and cyclohexyl acrylate, is preferable from an electrical property improvement viewpoint.

[Structural unit derived from at least one compound selected from the group consisting of styrene derivative, maleimide derivative, (meth) acrylic acid and hydroxyl group-containing (meth) acrylate compound]

It is preferable that component C has a structural unit derived from at least 1 compound chosen from the group which consists of a styrene derivative, a maleimide derivative, (meth) acrylic acid, and a hydroxyl-containing (meth) acrylate compound as another structural unit.

As the styrene derivative, styrene, chloromethyl styrene and acetoxy styrene are preferable.

As maleimide derivatives, N-butyl maleimide and N-cyclohexyl maleimide are preferable.

As hydroxyl-containing (meth) acrylate compound, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Is preferred.

0-50 mol% is preferable, as for the content rate of the monomer unit which forms another structural unit among the all monomer units which comprise the component C, 0-45 mol% is more preferable, 5-40 mol% is especially preferable. By containing in the said ratio, the physical property of a cured film becomes favorable.

<C- (4): Characteristics of Component C Resin>

It is preferable that it is 1,000-100,000, and, as for the weight average molecular weight of component C, it is more preferable that it is 2,000-50,000.

Hereinafter, although the thing preferable as component C is illustrated, this invention is not limited to these.

Moreover, it is preferable that the weight average molecular weights of the component C illustrated below are 2,000-50,000.

Methacrylic acid 1-ethoxyethyl / methacrylate tert-butyl / methacrylate glycidyl copolymer;

Methacrylic acid tetrahydro-2H-furan-2-yl / methacrylate tert-butyl / methacrylate glycidyl / methacrylic acid copolymer;

Methacrylic acid 1-ethoxyethyl / methacrylate tetrahydro-2H-pyran-2-yl / methacrylate glycidyl / methacrylic acid copolymer;

Methacrylic acid 1-ethoxyethyl / methacrylate tetrahydro-2H-pyran-2-yl / methacrylic acid 3,4-epoxycyclohexylmethyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) Ester copolymers;

Methacrylic acid 1-ethoxyethyl / methacrylate tetrahydro-2H-pyran-2-yl / methacrylic acid 3,4-epoxycyclohexylmethyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) Ester / methacrylic acid 2-hydroxyethyl copolymer methacrylic acid 1-ethoxyethyl / methacrylate 2-methyl-2-adamantyl / methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester copolymer;

Methacrylic acid 1-ethoxyethyl / methacrylic acid 1-methyl-1-cyclohexyl / methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxy Propyl) ester copolymers;

Methacrylic acid 1-ethoxyethyl / methacrylic acid tetrahydro-2H-pyran-2-yl / methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacrylo) Yloxypropyl) ester copolymer;

Methacrylic acid 1-ethoxyethyl / methacrylic acid tetrahydro-2H-pyran-2-yl / methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacrylo) Yloxypropyl) ester / methacrylic acid 2-hydroxyethyl copolymer;

Methacrylic acid 1-ethoxyethyl / N-cyclohexylmaleimide / methacrylic acid glycidyl / methacrylic acid copolymer;

Methacrylic acid 1-ethoxyethyl / methacrylic acid / methacrylic acid (3-ethyloxetan-3-yl) methyl / methacrylic acid-2-hydroxyethyl copolymer;

Methacrylic acid 1-ethoxyethyl / methacrylic acid / methacrylic acid glycidyl / methacrylic acid-2-hydroxyethyl copolymer.

Component C can be used individually by 1 type or in combination of 2 or more types.

When using together two or more types, at least 1 type is preferably the form which is resin containing resin containing the structural unit represented by General formula (1) (henceforth "(C ') resin"). It is preferable that the structural unit represented by General formula (1) is contained in 1 to 60 mol% ratio of resin containing the structural unit represented by General formula (1), and it is more contained in 10 to 40 mol% ratio more desirable.

In addition, when including two or more types of resin, it is preferable that 10-50 weight% of (component C) is (C ') resin.

As (C ') resin, resin of the following forms is illustrated preferably.

(Form 1)

(C ') The aspect in which resin containing the structural unit represented by General formula (1) contains an acidic radical further.

(Form 2)

(C ') Resin contains a crosslinkable group (preferably any one or more of an oxiranyl group, an oxetanyl group, an acid anhydride group, an acid halide group, an isocyanate group, and a (meth) acrylate group).

(Form 3)

(C ') resin further contains an acidic radical and a crosslinkable group (preferably an oxiranyl group, an oxetanyl group, an acid anhydride group, an acid halide group, an isocyanate group, (meth) acrylate group), and a crosslinking group Form.

(Form 4)

(C ') resin is an acid labile group, a crosslinkable group (preferably any one or more of an oxiranyl group, an oxetanyl group, an acid anhydride group, an acid halide group, an isocyanate group, a (meth) acrylate group), a crosslinking group, and Form containing further acid.

(Form 5)

The aspect in any one of the said forms 1-4 whose (C ') resin contains another structural unit further.

It is preferable that it is 20-99 mass% with respect to the total solid of the photosensitive resin composition, and, as for the total content of the component C in the photosensitive resin composition of this invention, it is more preferable that it is 40-97 mass%, and it is 60-95 mass% More preferred. When content is this range, when it develops, pattern formation property will become favorable. In addition, solid content of the photosensitive resin composition shows the quantity except volatile components, such as a solvent.

Moreover, in the photosensitive resin composition of this invention, you may use together resin other than the component C in the range which does not prevent the effect of this invention. However, it is preferable that resin content other than component C is smaller than content of component A from a developable viewpoint.

(Component D) Photoacid Generator

The photosensitive resin composition of this invention contains the (component D) photoacid generator.

As the component D, a known photoacid generator can be used, but it is preferable to use a photoacid generator.

The photoacid generator used in the present invention is preferably a compound which generates an acid in response to an active light having a wavelength of 300 nm or more, more preferably a wavelength of 300 to 450 nm, but the chemical structure is not limited. For example, even if it is a photo-acid generator which does not directly react to actinic light of wavelength 300nm or more, if it is a compound which produces | generates an acid in response to actinic light of wavelength 300nm or more by using together with a sensitizer, it can use preferably in combination with a sensitizer.

As the photoacid generator used in the present invention, a photoacid generator in which pKa generates an acid of 4 or less is preferable, and a photoacid generator in which pKa generates an acid of 3 or less is more preferable.

Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imidesulfonate compounds and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from a viewpoint of insulation or a sensitivity.

These photoacid generators can be used individually by 1 type or in combination of 2 or more types.

As an oxime sulfonate compound, ie, a compound which has an oxime sulfonate residue, the compound which has an oxime sulfonate residue of a following formula (B1) can be illustrated preferably.

In formula (B1), R ⁴¹ represents an alkyl group, an alkoxy group, an aryl group, or a halogen atom.

As an alkyl group of R <^41> , a C1-C10 linear or branched alkyl group is preferable. The alkyl group of R ⁴¹ is a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, C6-C11 aryl group, C1-C10 alkoxy group or cycloalkyl group (7,7- It may contain a crosslinked alicyclic group, such as a dimethyl-2-oxonorbornyl group, Preferably it may be substituted by the bicycloalkyl group etc.).

As an alkoxy group of R <^41> , a C1-C4 linear or branched alkoxy group is preferable, and a methoxy group or an ethoxy group is preferable. The alkoxy group may be substituted in the same manner as the alkyl group.

As an aryl group of R <^41> , a C6-C11 aryl group is preferable and a phenyl group or a naphthyl group is more preferable. The aryl group of R ⁴¹ may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group or a halogen atom.

As for the compound containing the oxime sulfonate residue represented by said Formula (B1), it is more preferable that it is an oxime sulfonate compound represented by following formula (B2).

(In formula (B2), R ⁴² is the same as R ⁴¹ in formula (B1), X represents an alkyl group, an alkoxy group or a halogen atom, m1 represents an integer of 0 to 3, and m1 is 2 or 3). When multiple plural Xs may be the same or different)

The alkyl group for X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom is preferably a chlorine atom or a fluorine atom.

m1 is preferably 0 or 1.

Formula (B2) in, and m1 is 1, X is a methyl group, the substitution position of X is the ortho position, R ⁴² is C 1? 10 straight chain alkyl, 7,7-dimethyl-2-oxo-norbornyl group Or a compound that is a p-toluyl group.

As a specific example of the said oxime sulfonate compound, (i)-(i) is mentioned, can be used individually by 1 type, or can use two or more types together. Compound (i)-(iii) can be obtained as a commercial item. It can also be used in combination with other kinds of photoacid generators.

It is more preferable that the compound containing the oxime sulfonate residue represented by said formula (B1) is an oxime sulfonate compound represented by a following formula (B3).

In formula (B3), R ⁴³ represents a halogen atom, a hydroxyl group, an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, a cyano group or a nitro group, and n1 represents an integer of 0 to 5. X 1 is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, or substituted with W A naphthyl group which may be substituted or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a carbon atom having 1 to 5 carbon atoms A halogenated alkyl group or a halogenated alkoxy group having 1 to 5 carbon atoms.

R ⁴³ in the formula (B3) is methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl or perfluoro Rho-n-butyl group, p-tolyl group, 4-chlorophenyl group, or pentafluorophenyl group is preferable, and it is especially preferable that they are a methyl group, an ethyl group, n-propyl group, n-butyl group, or p-tolyl group.

As the halogen atom represented by X ¹ , a fluorine atom, a chlorine atom or a bromine atom is preferable.

As the alkyl group having 1 to 4 carbon atoms represented by X ¹ , a methyl group or an ethyl group is preferable.

As the alkoxy group having 1 to 4 carbon atoms represented by X ¹ , a methoxy group or an ethoxy group is preferable.

As n1, the integer of 0-2 is preferable, and 0 or 1 is especially preferable.

As a preferable aspect of the compound contained in the photo-acid generator represented by Formula (B3), R <^43> represents a methyl group, an ethyl group, n-propyl group, n-butyl group, or 4-tolyl group, and X <^1> represents a hydrogen atom or a methoxy group N1 is in the form of 0 or 1.

Hereinafter, although the especially preferable example of the compound contained in the photo-acid generator represented by Formula (II) is shown, this invention is not limited to these.

α- (methylsulfonyloxyimino) benzyl cyanide (R ⁴³ = methyl group, X ¹ = hydrogen atom)

α- (ethylsulfonyloxyimino) benzyl cyanide (R ⁴³ = ethyl group, X ¹ = hydrogen atom)

α- (n-propylsulfonyloxyimino) benzyl cyanide (R ⁴³ = n-propyl group, X ¹ = hydrogen atom)

α- (n-butylsulfonyloxyimino) benzyl cyanide (R ⁴³ = n-butyl group, X ¹ = hydrogen atom)

α- (4-toluenesulfonyloxyimino) benzyl cyanide (R ⁴³ = 4-tolyl group, X ¹ = hydrogen atom)

α-[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁴³ = methyl group, X ¹ = methoxy group)

α-[(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁴³ = ethyl group, X ¹ = methoxy group)

α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = n-propyl group, X ¹ = methoxy group)

α-[(n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁴³ = n-butyl group, X ¹ = methoxy group)

α-[(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁴³ = 4-tolyl group, X ¹ = methoxy group)

It is preferable that it is a compound represented by a formula (OS-1) as a compound containing the oxime sulfonate residue represented by said formula (B1).

In formula (OS-1), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or a heteroaryl group. . R ¹⁰² represents an alkyl group or an aryl group.

X ¹⁰¹ represents —O—, —S—, —NH—, —NR ¹⁰⁵ —, —CH ₂ —, —CR ¹⁰⁶ H— or —CR ¹⁰⁵ R ¹⁰⁷ —, and R ^{105 to} R ¹⁰⁷ represent an alkyl group or an aryl group Indicates.

R ^{121 to} R ¹²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group or an aryl group. Two of R ^{121 to} R ¹²⁴ may be bonded to each other to form a ring.

R ^{121? 124} as the R is a hydrogen atom, a halogen atom and alkyl group are preferred, and also R ^121? It is also preferred to list form at least two of R ¹ to form ²⁴ an aryl group bonded to each other. Especially, the form whose R <^121> -R <^124> is all hydrogen atoms is preferable from a viewpoint of a sensitivity.

All of the above functional groups may further have a substituent.

It is more preferable that the compound represented by said formula (OS-1) is a compound represented by a following formula (OS-2).

In said formula (OS-2), R <^101> , R <^102> , R <^121> -R <^124> are the same as that of a formula (OS-1), respectively, and its preferable example is also the same.

Of these, formula (OS-1) and the expression (OS-2) of the R ¹⁰¹ is a cyano group or an aryl group, and the resulting form More preferably, the expression (OS-2) represented by R ¹⁰¹ is a cyano group, a phenyl group or that in in The form which is a naphthyl group is the most preferable.

In addition, in the said oxime sulfonate compound, any one may be sufficient respectively, or a mixture may be sufficient with respect to the three-dimensional structure (E, Z etc.) of an oxime and a benzothiazole ring.

Although the specific example (example compound b-1-b-34) of the compound represented by the formula (OS-1) used preferably for this invention below is shown, this invention is not limited to these. In addition, Me represents a methyl group, Et represents an ethyl group, Bn represents a benzyl group, Ts represents a tosyl group, and Ph represents a phenyl group.

Among the above-mentioned compounds, b-9, b-16, b-31, and b-33 are preferable from the viewpoint of both sensitivity and stability.

As a compound containing the oxime sulfonate residue represented by said Formula (B1), it is preferable that it is an oxime sulfonate compound represented by Formula (OS-3), Formula (OS-4), or Formula (OS-5). .

(In formula (OS-3)-In formula (OS-5), R ²⁰¹ , R ²⁰⁴ and R ²⁰⁷ each independently represent an alkyl group, an aryl group or a heteroaryl group, and R ²⁰² , R ²⁰⁵ and R ²⁰⁸ are each independently. A hydrogen atom, an alkyl group, an aryl group or a halogen atom, R ²⁰³ , R ²⁰⁶ and R ²⁰⁹ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, and each represents an X ²⁰¹ ? X ²⁰³ each independently represents O or S, n2? N4 each independently represents 1 or 2, and m2? M4 each independently represents an integer of 0-6.)

In the formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group in R ²⁰¹ , R ²⁰⁴ and R ²⁰⁷ may have a substituent.

In said formula (OS-3) (OS-5), it is preferable that it is a C1-C30 alkyl group which may have a substituent as an alkyl group in R <^201> , R <^204> and R <^207> .

^Examples of the alkyl group in R ²⁰¹ , R ²⁰⁴ and R ²⁰⁷ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group and n-hex Real group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, phenoxyethyl group, methylthioethyl group, phenylthioethyl group, e A oxycarbonylethyl group, a phenoxycarbonylethyl group, and a dimethylaminocarbonylethyl group are mentioned.

Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-de The preferred group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, and benzyl group are preferable.

^Examples of the substituent that the alkyl group in R ²⁰¹ , R ²⁰⁴ and R ²⁰⁷ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. .

Moreover, as said aryl group in R <^201> , R <^204> and R <^207> in the said Formula (OS-3) (OS-5) ^-the C6-C30 aryl group which may have a substituent is preferable.

^Examples of the aryl group for R ²⁰¹ , R ²⁰⁴ and R ²⁰⁷ include a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group, p-phenoxyphenyl group and p-methyl A thiophenyl group, p-phenylthiophenyl group, p-ethoxycarbonylphenyl group, p-phenoxycarbonylphenyl group, and p-dimethylaminocarbonylphenyl group are mentioned.

Among these, a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group are preferable.

^Examples of the substituent which the aryl group in R ²⁰¹ , R ²⁰⁴ and R ²⁰⁷ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, A sulfonic acid group, an aminosulfonyl group, and the alkoxysulfonyl group are mentioned.

In addition, as said heteroaryl group in R <^201> , R <^204> and R <^207> in the said Formula (OS-3) (OS-5), the heteroaryl group of 4-30 total carbons which may have a substituent is preferable.

In the formula (OS-3) to (OS-5), at least one ring may be a heteroaromatic ring in the heteroaryl group in R ²⁰¹ , R ^204, and R ²⁰⁷ , for example, even if the heteroaromatic ring and the benzene ring are condensed. good.

The heteroaryl group in R ²⁰¹ , R ²⁰⁴ and R ²⁰⁷ may have a substituent, and may be a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, or benzoimida. The group remove | excluding one hydrogen atom from the ring selected from the group which consists of a sol ring is mentioned.

Substituents which may have a heteroaryl group for R ²⁰¹ , R ²⁰⁴ and R ²⁰⁷ include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group And sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group.

In the formulas (OS-3) to (OS-5), R ²⁰² , R ²⁰⁵ and R ²⁰⁸ are each preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group.

In the formulas (OS-3) to (OS-5), one or two each of R ²⁰² , R ^205, and R ²⁰⁸ present in two or more compounds in the compound is preferably an alkyl group, an aryl group, or a halogen atom, and 1 It is more preferable that a dog is an alkyl group, an aryl group, or a halogen atom, and it is especially preferable that 1 is an alkyl group and the remainder is a hydrogen atom.

In the formulas (OS-3) to (OS-5), the alkyl group or the aryl group in R ²⁰² , R ²⁰⁵ and R ²⁰⁸ may have a substituent.

As a substituent which the alkyl group or the aryl group in R <^202> , R <^205> and R <^208> may have, the same group as the substituent which the alkyl group or the aryl group in said R <^201> , R <^204> and R <^207> may have can be illustrated.

As an alkyl group in R <^202> , R <^205> and R <^208> , it is preferable that it is a C1-C12 alkyl group which may have a substituent, and it is more preferable that it is a C1-C6 alkyl group which may have a substituent.

Specific examples of the alkyl group in R ²⁰² , R ²⁰⁵ and R ²⁰⁸ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, Allyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, perfluorohexyl group, chloromethyl group, bromomethyl group, methoxymethyl group, benzyl group, phenoxy Ethyl group, methylthioethyl group, phenylthioethyl group, ethoxycarbonylethyl group, phenoxycarbonylethyl group, and dimethylaminocarbonylethyl group are mentioned.

Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group, chloromethyl group, bromomethyl group, methoxymethyl group , Benzyl group is preferable, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group is more preferable, and methyl group, ethyl group, n- The propyl group, n-butyl group and n-hexyl group are more preferable, and a methyl group is especially preferable.

As an aryl group in R <^202> , R <^205> and R <^208> , it is preferable that they are a C6-C30 aryl group which may have a substituent.

Specific examples of the aryl group for R ²⁰² , R ²⁰⁵ and R ²⁰⁸ include a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group, p-phenoxyphenyl group and p-methylthio A phenyl group, p-phenylthiophenyl group, p-ethoxycarbonylphenyl group, p-phenoxycarbonylphenyl group, and p-dimethylaminocarbonylphenyl group are mentioned.

Among these, a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group are preferable.

^Examples of the halogen atom in R ²⁰² , R ²⁰⁵ and R ²⁰⁸ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Among these, a chlorine atom and a bromine atom are preferable.

In the formulas (OS-3) to (OS-5), each of X ^{201 to} X ²⁰³ independently represents O or S, and is preferably O.

In formula (OS-3)? (OS-5), the ring containing X ^{201 to} X ²⁰³ as a reduction is a 5- or 6-membered ring.

In the formulas (OS-3) to (OS-5), n represents 1 or 2, and when X ^{201 to} X ²⁰³ is O, it is preferable that n2 to n4 are each independently 1, and X ^{201 to} X ^{When 203} is S, it is preferable that n2 to n4 are each independently 2.

In said Formula (OS-3)? (OS-5), R ²⁰³ , R ²⁰⁶ and R ²⁰⁹ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. Especially, it is preferable that R <^203> , R <^206> and R <^209> are an alkyl group or an alkyloxy group each independently.

The alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R ²⁰³ , R ²⁰⁶ and R ²⁰⁹ may have a substituent.

In the formulas (OS-3) to (OS-5), the alkyl group for R ²⁰³ , R ²⁰⁶ and R ²⁰⁹ is preferably an alkyl group having 1 to 30 carbon atoms in total which may have a substituent.

As an alkyl group in R <^203> , R <^206> and R <^209> , a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hex Real group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, phenoxyethyl group, methylthioethyl group, phenylthioethyl group, e A oxycarbonylethyl group, a phenoxycarbonylethyl group, and a dimethylaminocarbonylethyl group are mentioned.

Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-de The preferred group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, and benzyl group are preferable.

^Examples of the substituent which the alkyl group in R ²⁰³ , R ²⁰⁶ and R ²⁰⁹ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group and an aminocarbonyl group. .

As said alkyloxy group in R <^203> , R <^206> and R <^209> in said Formula (OS-3)-(OS-5), it is preferable that it is a C1-C30 alkyloxy group which may have a substituent.

^Examples of the alkyloxy group in R ²⁰³ , R ²⁰⁶ and R ²⁰⁹ include methyloxy group, ethyloxy group, butyloxy group, hexyloxy group, phenoxyethyloxy group, trichloromethyloxy group, ethoxyethyloxy group and methyl Thioethyloxy group, phenylthioethyloxy group, ethoxycarbonylethyloxy group, phenoxycarbonylethyloxy group, and dimethylaminocarbonylethyloxy group are mentioned.

Among these, methyloxy group, ethyloxy group, butyloxy group, hexyloxy group, phenoxyethyloxy group, trichloromethyloxy group or ethoxyethyloxy group is preferable.

^Examples of the substituent that the alkyloxy group in R ²⁰³ , R ²⁰⁶ and R ²⁰⁹ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. do.

In the formulas (OS-3) to (OS-5), the aminosulfonyl group for R ²⁰³ , R ²⁰⁶ and R ²⁰⁹ is methylaminosulfonyl group, dimethylaminosulfonyl group, phenylaminosulfonyl group, methylphenylaminosulfonyl group, Aminosulfonyl groups are listed.

As said alkoxysulfonyl group in R <^203> , R <^206> and R <^209> in said Formula (OS-3)-(OS-5), a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, butyloxysulfonyl Groups are listed.

In addition, in said formula (OS-3) (OS-5), m <2> -m <4> represents the integer of 0-6 each independently, It is preferable that it is an integer of 0-2, It is more preferable that it is 0 or 1, It is especially preferable that it is zero.

Moreover, it is especially preferable that the compound containing the oxime sulfonate residue represented by said Formula (B1) is an oxime sulfonate compound represented by either of following formula (OS-6)? (OS-11).

In formula (OS-6) to (OS-11), R ^{301 to} R ³⁰⁶ each independently represent an alkyl group, an aryl group, or a heteroaryl group, R ³⁰⁷ represents a hydrogen atom or a bromine atom, and R ^{308 to} R ³¹⁰ , R ³¹³ , R ³¹⁶ and R ³¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, and R ³¹¹ And R ³¹⁴ each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ³¹² , R ³¹⁵ , R ³¹⁷ and R ³¹⁹ each independently represent a hydrogen atom or a methyl group)

R ^{301 to} R ³⁰⁶ in Formulas (OS-6) to (OS-11) are the same as R ²⁰¹ , R ²⁰⁴ and R ^{207 in} Formulas (OS-3) to (OS-5), and are preferable. The form is the same.

R ³⁰⁷ in Formula (OS-6) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

R ^{308 to} R ³¹⁰ , R ³¹³ , R ³¹⁶ and R ³¹⁸ in formulas (OS-6) to (OS-11) each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, and a bro It represents a mother methyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group, It is preferable that it is a C1-C8 alkyl group, a halogen atom, or a phenyl group, It is more preferable that it is a C1-C8 alkyl group, It is a C1-C6 It is more preferable that it is an alkyl group, and it is especially preferable that it is a methyl group.

R <^311> and R <^314> in a formula (OS-8) and a formula (OS-9) respectively independently represent a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, and it is preferable that they are a hydrogen atom.

In formulas (OS-8) to (OS-11), R ³¹² , R ³¹⁵ , R ³¹⁷ and R ³¹⁹ each independently represent a hydrogen atom or a methyl group, and are preferably hydrogen atoms.

In addition, in the said oxime sulfonate compound, any one or a mixture may be sufficient about the stereostructure (E, Z) of an oxime.

Although the following exemplary compound is mentioned as a specific example of the oxime sulfonate compound represented by said formula (OS-3)-a formula (OS-5), This invention is not limited to these.

In the photosensitive resin composition of this invention, it is preferable to contain 0.1-10 weight part with respect to 100 weight part of (component C) copolymers, and, as for the (component D) photoacid generator, it is more preferable that 0.5-10 weight part is contained. .

(Component E) Solvent

It is preferable that the photosensitive resin composition of this invention contains the (component E) solvent.

It is preferable that the photosensitive resin composition of this invention is further prepared as a solution which melt | dissolved the component A-component D which is an essential component, and the arbitrary components mentioned later in the (component E) solvent.

As a solvent used for the photosensitive resin composition of this invention, a well-known solvent can be used and ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol Dialkyl ethers, propylene glycol monoalkyl ether acetates, butylene glycol monoalkyl ethers, butylene glycol monoalkyl ether acetates, butylene glycol dialkyl ethers, butylene glycol dialkyl ether acetates, diethylene glycol Dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones, etc. Can be illustrated. As a solvent used for the photosensitive resin composition of this invention, the solvent as described in Paragraph [0074] of Unexamined-Japanese-Patent No. 2009-258722 is mentioned, for example.

These solvents can be used individually by 1 type or in mixture of 2 or more types.

It is preferable to use together single 1 type or 2 types, and, as for the solvent which can be used for this invention, it is more preferable to use 2 types together, and a propylene glycol monoalkyl ether acetate or dialkyl ether, diacetates, and diethylene It is more preferable to use glycol dialkyl ethers or esters together with butylene glycol alkyl ether acetates.

Moreover, as component E, it is preferable that they are a boiling point of 130 degreeC or more, a solvent below 160 degreeC, a solvent with a boiling point of 160 degreeC or more, or a mixture thereof, a solvent with a boiling point of 130 degreeC or more and less than 160 degreeC, a solvent with a boiling point of 160 degreeC or more and 200 degrees C or less, or these It is more preferable that it is a mixture of, and it is still more preferable that it is a mixture of the boiling point of 130 degreeC or more and the solvent below 160 degreeC, and the solvent of boiling point 160 degreeC or more and 200 degrees C or less.

As a solvent with a boiling point of 130 degreeC or more and less than 160 degreeC, propylene glycol monomethyl ether acetate (boiling point 146 degreeC), propylene glycol monoethyl ether acetate (boiling point 158 degreeC), propylene glycol methyl- n-butyl ether (boiling point 155 degreeC), propylene glycol Methyl-n-propyl ether (boiling point of 131 degreeC) can be illustrated.

As a solvent of boiling point 160 degreeC or more, 3-ethoxy propionate ethyl (boiling point 170 degreeC), diethylene glycol methyl ethyl ether (boiling point 176 degreeC), propylene glycol monomethyl ether propionate (boiling point 160 degreeC), dipropylene glycol methyl ether acetate (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C ), Diethylene glycol monoethyl ether acetate (boiling point 220 ° C.), dipropylene glycol dimethyl ether (boiling point 175 ° C.), and 1,3-butylene glycol diacetate (boiling point 232 ° C.) can be exemplified.

It is preferable that content of the (component E) solvent in the photosensitive resin composition of this invention is 50-3,000 mass parts with respect to 100 mass parts of said components C, It is more preferable that it is 100-2,000 mass parts, It is 150-1,500 mass parts More preferred.

<Other Ingredients>

In the photosensitive resin composition of this invention, (component F) sensitizer demonstrated below as an arbitrary component as needed, (component G) antioxidant, (component H) crosslinking agent, (component I) adhesion improving agent, (component J) Known additives such as basic compounds, (component K) plasticizers, (component L) thermal radical generators and thermal acid generators, ultraviolet absorbers, thickeners, and organic or inorganic precipitation inhibitors can be added.

(Component F) sensitizer

The positive photosensitive resin composition of this invention can contain a (component F) sensitizer.

By containing a sensitizer, it is effective for the improvement of exposure sensitivity, and it is especially effective when an exposure light source is g and h line mixed line.

As the sensitizer, anthracene derivatives, acridon derivatives, thioxanthone derivatives, coumarin derivatives, base styryl derivatives and ditylbenzene derivatives are preferable.

Anthracene derivatives include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9,10-dibromoanthracene, 2-ethylanthracene and 9,10-dimethoxyanthracene are preferred.

As the acridon derivative, acridon, N-butyl-2-chloroacridone, N-methylacridone, 2-methoxyacridone, and N-ethyl-2-methoxyacridone are preferable.

As a thioxanthone derivative, thioxanthone, diethyl thioxanthone, 1-chloro-4- propoxy thioxanthone, and 2-chloro thioxanthone are preferable.

As coumarin derivatives, coumarin-1, coumarin-6H, coumarin-110, and coumarin-102 are preferable.

Examples of the base styryl derivative include 2- (4-dimethylaminostyryl) benzoxazole, 2- (4-dimethylaminostyryl) benzothiazole and 2- (4-dimethylaminostyryl) naphthothiazole.

Examples of the ditylbenzene derivatives include ditylbenzene, di (4-methoxystyryl) benzene, and di (3,4,5-trimethoxystyryl) benzene.

Among these, anthracene derivatives are preferable, and a 9,10- dialkoxy andrasene (1-6 carbon atoms of an alkoxy group) is more preferable.

The following is mentioned as a specific example of a sensitizer. In the following, Me represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group.

It is preferable that it is 0.1-10 mass parts with respect to 100 mass parts of component C, and, as for content of the (component F) sensitizer in the positive photosensitive resin composition of this invention, it is more preferable that it is 0.5-10 mass parts. (Component F) If content of a sensitizer is 0.1 mass part or more, desired sensitivity will be easy to be obtained, and if it is 10 mass parts or less, transparency of a coating film will be easy to be ensured.

(Component G) Antioxidant

The photosensitive resin composition of this invention may contain the (component G) antioxidant. (G) As antioxidant, a well-known antioxidant can be contained. By adding the (G) antioxidant, there is an advantage that the coloring of the cured film can be prevented, the reduction in the film thickness due to decomposition can be reduced, and the heat transparency is excellent.

Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites, thiosulfates, and hydroxylamines. Derivatives; and the like. Among these, a phenolic antioxidant is especially preferable from a viewpoint of coloring of a cured film and a film thickness reduction. These may be used individually by 1 type, and may mix and use 2 or more types.

As a commercial item of a phenolic antioxidant, adecastabu AO-60 and adecastabu AO-80 (above, ADEKA® Corporation make and Ilganox 1098 (made by Ciba Japan Corporation)) are mentioned, for example.

(Component G) It is preferable that content of antioxidant is 0.1-6 mass% with respect to the total solid of the photosensitive resin composition, It is more preferable that it is 0.2-5 mass%, It is especially preferable that it is 0.5-4 mass%. By setting it as this range, sufficient transparency of the formed film is obtained and the sensitivity at the time of pattern formation also becomes favorable.

Moreover, you may add the various ultraviolet absorbers, metal inactivating agents, etc. which were described in "The expansion of a polymer additive (Daily Industry News)" as additives other than antioxidant to the photosensitive resin composition of this invention.

(Component H) Crosslinking Agent

It is preferable that the photosensitive resin composition of this invention contains the (component H) crosslinking agent.

As a crosslinking agent, the compound which has at least 1 ethylenically unsaturated double bond among the compound which has 2 or more oxiranyl group or oxetanyl group, and the alkoxy methyl group containing crosslinking agent in the molecule | numerator demonstrated below can be added, for example. By adding a crosslinking agent, a cured film can be made into a stronger film.

<Compounds having two or more oxiranyl groups or oxetanyl groups in the molecule>

Specific examples of the compound having two or more oxiranyl groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolak type epoxy resins, cresol novolak type epoxy resins, and aliphatic epoxy resins.

These can be obtained as a commercial item. For example, bisphenol-A epoxy resins include JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, manufactured by Japan Epoxy Resins Co., Ltd.), and the like. These can be used individually by 1 type or in combination of 2 or more types.

Preferred among these are bisphenol A type epoxy resins, bisphenol F type epoxy resins, and phenol novolac type epoxy resins. In particular, a bisphenol-A epoxy resin is preferable.

As an example of a compound which has two or more oxetanyl groups in a molecule | numerator, arone oxatane OXT-121, OXT-221, OX-SQ, PNOX (above, Toagosei Co., Ltd. product) can be used.

In addition, the compound containing an oxetanyl group can be used individually or in mixture with the compound containing an oxiranyl group.

When the total amount of component C is 100 mass parts, 1-50 mass parts is preferable, and, as for the addition amount of the compound which has two or more oxiranyl group or oxetanyl group in a molecule | numerator, 3-30 mass parts is more preferable.

<Alkoxymethyl group-containing crosslinking agent>

As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, alkoxymethylated urea and the like are preferable. These are obtained by converting methylol groups of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril or methylolated urea into alkoxymethyl groups, respectively. The kind of the alkoxymethyl group is not particularly limited, and for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, butoxymethyl group and the like can be mentioned. From the viewpoint of the amount of outgas generated, a methoxymethyl group is particularly preferable. .

Among these, as an alkoxy methyl group containing crosslinking agent, an alkoxy methylation melamine, the alkoxy methylation benzoguanamine, and the alkoxy methylation glycoluril are preferable, and an alkoxy methylation glycoluril is especially preferable from a transparency viewpoint.

These alkoxymethyl group containing crosslinking agents are available as a commercial item, for example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170 , 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Corporation), Nakarak MX-750, -032, -706, -708, -40, -31, -270, -280, -290, Nikarak MS-11 , Nikarak MW-30HM, -100LM, -390 (above, manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.

It is preferable that it is 0.05-50 mass parts with respect to 100 mass parts of component C, and, as for the addition amount of the alkoxy methyl group containing crosslinking agent in the case of using an alkoxy methyl group containing crosslinking agent for the photosensitive resin composition of this invention, it is more preferable that it is 0.5-10 mass parts. By adding in this range, preferable alkali solubility at the time of image development, and the outstanding solvent resistance of a film | membrane after hardening are obtained.

<Compounds having at least one ethylenically unsaturated double bond>

As a compound which has at least 1 ethylenically unsaturated double bond, (meth) acrylate compounds, such as monofunctional (meth) acrylate, bifunctional (meth) acrylate, and trifunctional or more (meth) acrylate, can be used preferably. .

As monofunctional (meth) acrylate, 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isoboronyl (meth) acrylate, 3-methoxybutyl (meth) acryl Late, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, and the like.

As a bifunctional (meth) acrylate, for example, ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol fluorene diacrylate, bisphenoxyethanol fluorene diacrylate, etc. are mentioned.

As (meth) acrylate more than trifunctional, for example, trimetholpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra ( Meta) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like.

The compound which has at least 1 ethylenically unsaturated double bond among these can be used individually by 1 type or in combination of 2 or more types.

It is preferable that it is 50 mass parts or less with respect to 100 mass parts of said components C, and, as for the usage ratio of the compound which has at least 1 ethylenically unsaturated double bond in the photosensitive resin composition of this invention, it is more preferable that it is 30 mass parts or less. By containing the compound which has at least 1 ethylenically unsaturated double bond in such a ratio, the heat resistance, surface hardness, etc. of the insulating film obtained from the photosensitive resin composition of this invention can be improved. When adding the compound which has at least 1 ethylenically unsaturated double bond, it is preferable to add (component L) thermal radical generating agent.

(Component I) Adhesion Corrector

The photosensitive resin composition of this invention may contain the (component I) adhesion improving agent.

The adhesion improving agent which can be used for the photosensitive resin composition of this invention is a compound which improves adhesiveness of the inorganic substance described, for example, silicon compounds, such as a silicon, a silicon oxide, silicon nitride, and metal, such as gold, copper, aluminum, and an insulating film. Specifically, a silane coupling agent, a thiol type compound, etc. are mentioned. As an adhesion improving agent used for this invention, a silane coupling agent aims at the modification of an interface, It does not restrict | limit especially A well-known thing can be used.

As a preferable silane coupling agent, (gamma) -aminopropyl trimethoxysilane, (gamma) -aminopropyl triethoxysilane, (gamma)-glycidoxy propyltrialkoxy silane, (gamma)-glycidoxy propyl alkyl dialkoxysilane, (gamma)-meta Krilloxypropyltrialkoxysilane, γ-methacryloxypropylalkyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane And vinyltrialkoxysilanes.

Among these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, and γ-glycidoxypropyltrialkoxysilane is more preferable.

These can be used individually by 1 type or in combination of 2 or more types. They are effective for improving adhesion with the substrate and also for adjusting the taper angle with the substrate.

0.1-20 mass parts is preferable with respect to 100 mass parts of (component C) resin, and, as for content of the (component I) adhesion improving agent in the photosensitive resin composition of this invention, 0.5-10 mass parts is more preferable.

(Component J) Basic Compound

The photosensitive resin composition of this invention may contain the (component J) basic compound.

As a basic compound, although it can use as a chemically amplified resist, it can select arbitrarily among these, and can use it. For example, aliphatic amine, aromatic amine, heterocyclic amine, quaternary ammonium hydroxide, quaternary ammonium salt of carboxylic acid, etc. are mentioned.

As a specific example of a basic compound, the compound of Paragraph [0052]-[0056] of Unexamined-Japanese-Patent No. 2009-98616 can be illustrated.

Although the basic compound which can be used for this invention may be used individually by 1 type, or may use 2 or more types together, It is preferable to use 2 or more types together, It is more preferable to use 2 types together, It uses two types of heterocyclic amines together More preferably.

It is preferable that it is 0.001-1 mass part with respect to 100 mass parts of (component C) resin, and, as for content of (component J) in the photosensitive resin composition of this invention, it is more preferable that it is 0.005-0.2 mass part.

(Component K) Plasticizer

The photosensitive resin composition of this invention may contain the (component K) plasticizer.

Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerine phthalate, dibutyl stannate, dioctyl adipic acid, triacetyl glycerine, and the like.

It is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of (component C) resin, and, as for the addition amount of the (component K) plasticizer in the photosensitive resin composition of this invention, it is more preferable that it is 1-10 mass parts.

(Component L) Thermal Radical Generator

The photosensitive resin composition of this invention may also contain the (component L) thermal radical generator, and when it contains an ethylenically unsaturated compound like the compound which has at least 1 ethylenically unsaturated double bond in the above, (component L) thermal radical It is preferable to contain a generator.

As the thermal radical generator in the present invention, a known thermal radical generator can be used.

Thermal radical generators are compounds which generate radicals by thermal energy to initiate or accelerate the polymerization reaction of the polymerizable compound. The cured film obtained by adding a thermal radical generating agent becomes tough more, and heat resistance and solvent resistance may improve.

Preferred thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketooxime ester compounds, borate compounds, adinium compounds, metallocene compounds, active ester compounds and carbon halogen bonds. The compound which has a compound, an azo compound, a bibenzyl compound, etc. are mentioned.

A thermal radical generating agent may be used individually by 1 type, and can also use 2 or more types together.

The addition amount of the (component L) thermal radical generator in the photosensitive resin composition of the present invention is preferably from 0.01 to 50 parts by mass, and preferably from 0.1 to 20 parts by mass, when the (component C) resin is 100 parts by mass from the viewpoint of improving film properties. It is more preferable, and it is most preferable that it is 0.5-10 mass parts.

[Production method of hardened film]

Next, the manufacturing method of the cured film of this invention is demonstrated.

The manufacturing method of the cured film of this invention is characterized by including the process of the following (1)-(5).

(1) an application step of applying the positive photosensitive resin composition of the present invention on a substrate;

(2) a solvent removal step of removing the solvent from the applied positive photosensitive resin composition;

(3) an exposure step of exposing with actinic light;

(4) a developing step of developing with an aqueous developer;

(5) Post-baking process to thermoset.

Each process is demonstrated in order below.

In the application process of (1), it is preferable to apply the positive photosensitive resin composition of this invention on a board | substrate, and to set it as the wet film containing a solvent.

In the solvent removal process of (2), it is preferable to form a dry coating film on a board | substrate by removing a solvent from the said film | membrane applied by reduced pressure (vaccum) and / or heating.

In the exposure process of (3), it is preferable to irradiate the obtained coating film with actinic light of wavelength 300nm or more and 450nm or less. In this step, the photoacid generator (component D) is decomposed to generate acid. By the catalysis of the generated acid, the acid-decomposable group contained in the (component C) resin is hydrolyzed to produce carboxyl groups and / or phenolic hydroxyl groups.

In the region where the acid catalyst is produced, post-exposure heat treatment: Post Exposure Bake (hereinafter referred to as "PEB") can be performed as necessary to accelerate the hydrolysis reaction. PEB can promote the generation of carboxyl groups from acid-decomposable groups.

In the present invention, the acid-decomposable group in the component C has a low activation energy for decomposition by acid, is easily decomposed by an acid derived from an acid generator by exposure, and is developed by developing without necessarily PEB in order to generate a carboxyl group. It is also possible to form a positive image.

In addition, by performing PEB at a relatively low temperature, hydrolysis of the acid-decomposable group can be promoted without causing a crosslinking reaction. It is preferable that the temperature at the time of PEB is 30 degreeC or more and 130 degrees C or less, 40 degreeC or more and 110 degrees C or less are more preferable, 50 degreeC or more and 80 degrees C or less are especially preferable.

In the developing process of (4), it is preferable to develop the polymer which has advantageous carboxyl group using alkaline developing solution. A positive image can be formed by removing the exposed portion area.

In the post-baking step (5), the resulting positive image is heated to decompose an acid-decomposable group in component B to generate a carboxyl group, and a cured film can be formed by crosslinking with an oxiranyl group and / or oxetanyl group. It is preferable to heat this heating at high temperature 150 degreeC or more, It is more preferable to heat at 180-250 degreeC, It is especially preferable to heat at 200-250 degreeC. Although heating time can be set suitably by heating temperature etc., it is preferable to set it in the range of 10 to 90 minutes.

It is preferable to add a step of totally irradiating actinic light, preferably ultraviolet rays, to the developing pattern before the postbaking process, since the crosslinking reaction can be promoted by an acid generated by actinic light irradiation.

Next, the formation method of the cured film using the photosensitive resin composition of this invention is demonstrated concretely.

<Preparation method of the photosensitive resin composition>

The essential components of component A-component E are mixed by a predetermined ratio or by any method, and it melt | dissolves and prepares the photosensitive resin composition. For example, after making component A-component D into the solution which melt | dissolved in the (component E) solvent previously, respectively, these can also be mixed in a predetermined ratio and the resin composition can be prepared. The composition solution prepared as described above may be used for use after being filtered using a filter having a pore size of 0.2 μm.

<(1) Application process and (2) Solvent removal process>

A desired dry film can be formed by applying the photosensitive resin composition to a predetermined substrate and removing the solvent by reduced pressure and / or heating (prebaking). As said board | substrate, the glass plate etc. which provided the black matrix layer, the color filter layer, and provided the transparent conductive circuit layer etc. can be illustrated, for example in manufacture of a liquid crystal display element. Although it does not restrict | limit especially as a method of applying a photosensitive resin composition to a board | substrate, Especially, in this invention, it is preferable to apply a sightseeing resin composition to a board | substrate. The coating method to a board | substrate is not specifically limited, For example, methods, such as a slit coating method, a spray method, a roll coating method, and a spin coating method, can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for large substrates. Here, a large board | substrate means the board | substrate of each side being 1 m or more in size.

In addition, the heating conditions of (2) solvent removal process are the ranges in which the acid-decomposable group in resin of component C in an unexposed part decomposes, and does not make resin of component C soluble in alkaline developing solution, and also according to the kind and compounding ratio of each component Although different, Preferably it is about 30 to 120 second at 80-130 degreeC.

<(3) Exposure Step>

In an exposure process, actinic light is irradiated to the board | substrate with a coating film through the mask which has a predetermined pattern. The actinic ray is not particularly limited as long as it can be exposed, but an actinic ray having a wavelength of 300 nm or more and 450 nm or less can be preferably used. After an exposure process, heat processing (PEB) is performed as needed.

A low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a laser generator, etc. can be used for exposure by actinic light.

When mercury lamps are used, actinic rays having wavelengths such as g-ray (436 nm), i-ray (365 nm), h-ray (405 nm) and the like can be preferably used. Mercury lamps are preferred in view of their suitability for large area exposure compared to lasers.

When using a laser, 343 nm and 355 nm can be used for a solid (YAG) laser, 351 nm (XeF) can be used for an excimer laser, and 375 nm and 405 nm can be used for a semiconductor laser. Among these, 355 nm and 405 nm are more preferable from a viewpoint of stability, price, etc. A laser can be irradiated to a coating film once or in multiple times.

The energy density per pulse of laser is preferably 0.1 mJ / cm 2 or more and 10,000 mJ / cm 2 or less. 0.3 mJ / cm <2> or more is more preferable in order to fully harden a coating film, 0.5 mJ / cm <2> or more is most preferable, 1,000 mJ / cm <2> or less is more preferable in order not to decompose a coating film by an ablation phenomenon, and 100 mJ / Most preferably cm 2 or less.

The pulse width is preferably 0.1 nsec or more and 30,000 nsec or less. 0.5 nsec or more is more preferable in order not to decompose a color film by an ablation phenomenon, 1 nsec or more is most preferable, 1,000 nsec or less is more preferable, and 50 nsec or less is most preferable in order to improve the fitting degree at the time of scanning exposure. Do.

Moreover, 1-50,000 Hz is preferable and, as for the frequency of a laser, 10-1,000 Hz is more preferable. If the frequency of the laser is less than 1 Hz, the exposure processing time is long. If the laser frequency is more than 50,000 Hz, the degree of fitting at the time of scanning exposure decreases.

In order to shorten an exposure process time, 10 Hz or more is more preferable, 100 Hz or more is the most preferable, In order to improve the fitting degree at the time of scan exposure, 10,000 Hz or less is more preferable, 1,000 Hz or less is the most preferable.

Compared with a mercury lamp, a laser is preferable in that it is easy to tighten a focus, and the cost of the mask of pattern formation in an exposure process is unnecessary, and it can cost-down.

Although it does not restrict | limit especially as an exposure apparatus which can be used for this invention, As what is marketed, Callisto (made by V Technology Co., Ltd.), AEGIS (made by V Technology Co., Ltd.) or DF2200G (Dainippon Screen Mfg. Co., Ltd.) and the like. Moreover, the apparatus of that excepting the above can also be used preferably.

Moreover, irradiation light can also be adjusted through spectroscopic filters, such as a long wavelength cutoff filter, a short wavelength cutoff filter, and a bandpass filter, as needed.

<(4) Developing Step>

In a developing process, it is preferable to remove an exposure part area | region and to form an image pattern using basic developing solution (alkaline developing solution). As a basic compound, For example, alkali metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide; Alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; Ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline hydroxide; Aqueous solutions, such as sodium silicate and sodium metasilicate, can be used. Moreover, the aqueous solution which added an appropriate amount of water-soluble organic solvents and surfactants, such as methanol and ethanol, to the aqueous solution of the said alkalis can also be used as a developing solution.

It is preferable that pH of a developing solution is 10.0-14.0.

The developing time is preferably 30 to 180 seconds, and the developing method may be any of a liquid immersion method and a dip method. After development, flowing water can be washed for 30 to 90 seconds to form a desired pattern.

<(5) Postbaking process (crosslinking process)>

With respect to the pattern corresponding to the unexposed region obtained by the development, using a heating apparatus such as a hot plate or an oven, and at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, on a hot plate, it is 5 to 60. If it is an oven for 30 to 90 minutes, it will decompose the acid-decomposable group in component A by heat-processing, generate | occur | produces a carboxyl group and / or phenolic hydroxyl group, and will react with the said functional group in component A, and it is excellent in heat resistance, hardness, etc. A protective film or an interlayer insulating film can be formed. In addition, when performing heat processing, transparency can also be improved by performing in nitrogen atmosphere.

In addition, prior to the heat treatment, the acid is removed from the (component D) photoacid generator present in the unexposed portion by post-baking (re-exposure / post-baking) after re-exposure to the patterned substrate by actinic light. It is preferable to generate | occur | produce and function as a catalyst which accelerates a crosslinking process.

That is, it is preferable that the formation method of the cured film of this invention includes the re-exposure process which re-exposes by actinic light between a developing process and a postbaking process.

Although the exposure in a re-exposure process may be performed by the same means as the said exposure process, in the said re-exposure process, it is preferable to perform whole surface exposure to the side in which the film | membrane was formed by the photosensitive resin composition of this invention of a board | substrate. As a preferable exposure amount of a re-exposure process, it is 100-1,000mJ / cm <2>.

[Curing film]

The cured film of this invention is a cured film obtained by hardening | curing the photosensitive resin composition of this invention.

The cured film of this invention can be used suitably as an interlayer insulation film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.

By the photosensitive resin composition of this invention, the interlayer insulation film which is excellent in insulation and has high transparency also when baked at high temperature is obtained. Since the interlayer insulation film which uses the photosensitive resin composition of this invention has high transparency and excellent cured film physical property, it is useful for the use of an organic electroluminescence display or a liquid crystal display device.

[Organic EL Display, Liquid Crystal Display]

The organic electroluminescence display and liquid crystal display of this invention are equipped with the cured film of this invention, It is characterized by the above-mentioned.

The organic EL display device or liquid crystal display device of the present invention is not particularly limited except having a protective film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention, and various known organic EL display devices and liquid crystals having various structures. And a display device.

In addition, the photosensitive resin composition of this invention and the cured film of this invention can be used for various uses, without being limited to the said uses. For example, in addition to a protective film and an interlayer insulation film, it can use suitably for the microlens etc. which are provided on the color filter in the spacer for keeping the thickness of a liquid crystal layer constant in a liquid crystal display device, and a solid-state image sensor.

1 shows a configuration conceptual diagram of an example of an organic EL display device. In the bottom emission type organic EL display device, a typical sectional view of the substrate is shown, and the planarization film 4 is provided.

It may form a bottom-gate type TFT (1), and comprising a state covering the TFT (1) to the Si ₃ N ₄ insulation film 3 is formed on the glass substrate 6. After the contact hole (not shown) is formed in the insulating film 3, a wiring 2 (1.0 mu m in height) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the TFT 1 with the organic EL element formed between the TFTs 1 or in a later step.

In addition, in order to planarize the unevenness caused by the formation of the wiring 2, the planarization layer 4 is formed on the insulating film 3 with the unevenness of the wiring 2 embedded.

On the planarization film 4, the bottom emission type organic electroluminescent element is formed. That is, on the planarization film 4, the 1st electrode 5 which consists of ITO is connected to the wiring 2 through the contact hole 7, and is formed. In addition, the 1st electrode 5 is corresponded to the anode of organic electroluminescent element.

The insulating film 8 of the shape which covers the periphery of the 1st electrode 5 is formed, and providing this insulating film 8 prevents the short between the 1st electrode 5 and the 2nd electrode formed by a subsequent process. can do.

Although not shown in FIG. 1, a hole transporting layer, an organic light emitting layer, and an electron transporting layer are sequentially deposited and provided through a desired pattern mask, and then a second electrode made of Al is formed on the entire surface above the substrate, and then sealed. It is sealed by bonding using a glass plate for glass and an ultraviolet curable epoxy resin, and an organic matrix organic EL display device of the active matrix type in which the TFT 1 for driving this is connected to each organic EL element is obtained.

2 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10. This color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on its back side, and the liquid crystal panel corresponds to all pixels arranged between two glass substrates 14 and 15 to which a polarizing film can be attached. The elements of the TFT 16 are arranged. In each element formed on the glass substrate, the ITO transparent electrode 19 which forms a pixel electrode through the contact hole 18 formed in the cured film 17 is wired. On the ITO transparent electrode 19, the RGB color filter 22 which has arrange | positioned the layer of the liquid crystal 20 and a black matrix is provided.

(Example)

An Example is given to the following and this invention is demonstrated to it further more concretely. The materials, the amounts used, the ratios, the treatment contents, the treatment sequences, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the embodiment shown below.

Synthesis of Polymer C-1

0.5 parts by mass of phenothiazine was added to 144.2 parts by mass of ethyl vinyl ether (2 molar equivalents), and 86.1 parts by mass of methacrylic acid (1 molar equivalent) was added dropwise while cooling the reaction system to 10 ° C. or lower at room temperature (25 ° C.). It stirred for 4 hours. After adding 5.0 parts by mass of p-toluenesulfonic acid pyridinium, the mixture was stirred at room temperature for 2 hours and allowed to stand at room temperature overnight. 5 parts by mass of sodium bicarbonate and 5 parts by mass of sodium sulfate were added to the reaction solution, the mixture was stirred at room temperature for 1 hour, the insolubles were concentrated under reduced pressure at 40 ° C. or lower, and the yellow oily substance was distilled under reduced pressure to give a boiling point (bp,). 134.0 mass parts of methacrylic acid 1-ethoxyethyl of 43-45 degreeC / 7mmHg fraction were obtained as a colorless oil.

Obtained methacrylic acid 1-ethoxyethyl (79.1 mass parts (0.5 mol equivalent)), glycidyl methacrylate (GMA) (71.1 mass parts (0.5 mol equivalent)), and propylene glycol monomethyl ether acetate (PGMEA) ( 125 mass parts) was heated at 70 degreeC under nitrogen stream. While stirring the mixed solution, a mixed solution of the radical polymerization initiator V-65 (2,2'-azobis (2,4-dimethylvaleronitrile), manufactured by Wako Pure Chemical Industries, Ltd.) and PGMEA was added to achieve the target molecular weight. The required amount was dripped over 2.5 hours. After completion of the dropping, a PGMEA solution (solid content concentration: 40% by mass) of polymer C-1 was obtained by reacting at 70 ° C for 4 hours. The weight average molecular weight measured by the gel permeation chromatography (GPC) of the obtained polymer C-1 was 12,000.

<Synthesis of Polymers C-2 to C-20>

Polymer C-2 to C-20 were synthesized in the same manner as in the synthesis of polymer C-1, except that each monomer used and its amount of use were changed to those shown in the following table. In addition, each copolymerization ratio of Table 2 is described in molar ratio.

In addition, the copolymerization ratio of Table 2 is molar ratio, and the symbol of Table 2 is as follows.

MAEVE: -1-ethoxyethyl methacrylate

MACHVE: Methacrylic acid-1-cyclohexyloxyethyl

MATHPE: Methacrylic Acid Tetrahydro-2H-pyran-2-yl

MATHF: Methacrylic Acid Tetrahydrofuran-2-yl

t-BMA: tert-butyl methacrylate

GMA: Glycidyl Methacrylate

OXE-30: methacrylic acid (3-ethyloxetan-3-yl) methyl (manufactured by Osaka Organic Chemical Industry Ltd.)

MAA: methacrylic acid

HEMA: 2-hydroxyethyl methacrylate

St: Styrene

PHSEVE: 4- (1-ethoxyethyloxy) styrene

PHStBOC: 4- (t-butoxycarbonyloxy) styrene

CHMI: N-cyclohexyl maleimide

In addition, MACHVE and MATHPE were synthesize | combined by changing the vinyl ether of MAEVE synthesis method into cyclohexyl vinyl ether and dihydropyran, respectively.

PHSEVE was synthesized by changing methacrylic acid in the MAEVE synthesis method to 4-hydroxystyrene.

PHStBOC was obtained by reacting 4-hydroxystyrene with t-butoxycarboxylic anhydride under basic conditions, followed by extraction, followed by purification by silica gel chromatography.

<Synthesis of MATHF (tetrahydrofuran-2-yl methacrylate)>

Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C. and camphor sulfonic acid (4.6 g, 0.02 mol) was added. 2,3-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was dripped at this solution. After stirring for 1 hour, saturated aqueous sodium hydrogen carbonate solution (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, the insolubles were filtered and concentrated under reduced pressure to 40 DEG C or lower, and the yellow oily residue was collected. Distillation under reduced pressure was carried out to obtain 125 g of tetrahydrofuran-2-yl methacrylate (MATHF) having a boiling point (bp) of 54 to 56 ° C / 3.5 mmHg fraction as a colorless oil (yield 80%).

(Synthesis of Polymer C ')

In a three-necked flask, diethylene glycol ethyl methyl ether (manufactured by TOHO Chemical Industry Co., Ltd., Hisorb EDM, 45 g) was placed in a three-necked flask, and heated to 90 ° C under a nitrogen atmosphere. To the solution, methyl methacrylate (MMA, manufactured by Wako Pure Chemical Industries, Ltd., 3.27 g), 2-tetrahydrofuranyl methacrylate (MATHF, Synthetic, 22.17 g), and hydroxyethyl methacryl were used as the monomer component. Rate (HEMA, manufactured by Wako Pure Chemical Industries, Ltd., 6.57 g), 3-ethyl-3-oxetanylmethyl methacrylate (OXE-30, manufactured by Osaka Organic Chemical Industry Ltd., 20.26 g) and n-part Toxymethyl acrylate (NBMA, manufactured by Tokyo Chemical Industry Co., Ltd., 9.43 g), and dimethyl-2,2'-azobis (2-methylpropionate) (V-601, Wako Pure Chemical) as a polymerization initiator 8 mol% of 7.36 g of Monomer, manufactured by Industries, Ltd. was dissolved, and added dropwise over 2 hours. It stirred for 2 hours after completion | finish of dripping. V-601 (1.84 g, 2 mol% based on the monomer) was further added to the solution, followed by further stirring for 2 hours to complete the reaction. This obtained binder C'-1. The weight average molecular weight was 12000.

C'-2 to C'-4 were synthesize | combined similarly except changing a monomer type etc. as shown to the following table | surface.

The unit of the monomer component of the said table | surface is shown by mol%. The initiator is shown as mol% when the monomer component is 100 mol%. Solid content concentration is shown by monomer weight / (monomer weight + solvent weight) x 100 (unit: weight%). In addition, the reaction temperature in the case of using V-601 as an initiator was 90 degreeC, and the reaction temperature in the case of using V-65 was 70 degreeC (also about the following table | surface).

In the above table, PHS represents p-hydroxystyrene (synthetic), MAEVE represents 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), and GMA represents glycidyl methacrylate (Wako). Pure Chemical Industries, Ltd.), IBMA represents i-butoxymethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), St represents styrene (Wako Pure Chemical Industries, Ltd.), and V -65 represents 2,2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.).

<Component A used in the Example>

The component A (A-1-12) used by the Example and the component A (A-13) used by the comparative example are shown below. In addition, these were produced by the well-known synthetic | combination method and polymerization method.

<Component B Used in the Example>

The component B (B-1-B-26) used by the Example and the component B (B-27) used by the comparative example are shown below.

In the table, E0 represents a divalent linking group derived from a polyethyleneoxy group, PO represents a divalent linking group derived from a polypropyleneoxy group, and a and b represent a ratio of EO and PO so that each component B satisfies HLB. , R represents a hydrogen atom or an alkyl group of C = 1-8.

[Examples and Comparative Examples]

(1) Preparation of Photosensitive Resin Composition Solution

After mixing each component shown in the following table to make a uniform solution, it filtered using the polytetrafluoroethylene filter which has a pore size of 0.2 micrometer, and prepared the photosensitive resin composition solution of an Example and a comparative example, respectively.

Photoacid generator

PAG-1: Oxime sulfonate compound shown below, IRGCURE PAG103 (made by Ciba Specialty Chemicals)

PAG-2: PAI-1001 (manufactured by Midori Kagaku Co., Ltd.)

PAG-3: PAI-101 (by Midori Kagaku Co., Ltd.)

PAG-4 PAG-6: a compound having the structure

Solvent E1: Diethylene Glycol Methyl Ethyl Ether

Solvent E2: Propylene Glycol Monomethyl Ether Acetate

In addition, in a table | surface, "solid content" shows the value (unit: mass%) of (remaining quantity / composition amount) * 100 at the time of evaporating and drying a composition.

<Evaluation of coating property>

Each photosensitive resin composition solution adjusted in each of Examples and Comparative Examples was coated with a slit die on a 1,500 mm × 1,800 mm Cr deposited glass substrate (glass was produced by EAGLE2000, Corning Incorporated) by a coating speed of 100 mm / sec and a coating gap of 100 μm. The coating film was applied under a coating flow rate of 0.5 ml / s so as to have a dry film thickness of 4 μm (wet thickness of 20 μm), and vacuum-dried in a reduced pressure drying chamber so as to achieve a vacuum degree of 0.4 Torr. This dried substrate was dried on a hot plate at 90 ° C. × 120 seconds, and then observed in the dark using a Na lamp, a white light, and a green lamp, and evaluated the coating stripe, reduced pressure drying pin marks, and dry unevenness based on the following criteria.

[Coated stripe]

(Circle): There is no coating stripe.

(Triangle | delta): There is a little stripe in the peripheral end.

X: There is a stripe on the front side.

[Dry non-uniformity]

(Circle): A dry nonuniformity (interference pattern) is not observed at all.

(Triangle | delta): Although observed a little, it is in an allowable range.

X: The dry nonuniformity (interference pattern) exceeding a permissible range is observed.

[Pressurized Dry Pin Mark]

Contact marks of the pins supporting the substrate in the reduced pressure drying chamber were determined based on the following criteria.

(Circle): No vacuum drying pin mark is observed at all.

(Triangle | delta): Although observed a little, it is in an allowable range.

X: The vacuum drying pin trace exceeding a permissible range is observed.

<Pixel Defect Evaluation Generated at Application>

The board | substrate was counted by the pixel defect number resulting from the board | substrate on AOI (color filter defect inspection apparatus by TAKANO Co., Ltd.).

(Circle): It is ten or less in the board | substrate whole surface.

(Triangle | delta): 11-25 pieces in front of a board | substrate.

X: 26 or more pieces are in front of a board | substrate.

<Plan evaluation after postbaking>

The board | substrate with which the said image development was completed was fully exposed at 300mJ / cm <2> (roughness 20mW / cm <2>), and post-baking was performed by 230 degreeC * 1 hour in a convection oven, and the surface state was observed with the optical microscope.

(Circle): There is no unevenness by surface flatness.

(Triangle | delta): Although there exist some unevenness | corrugation, it is in an allowable range.

X: Separation of components is observed, and there are severe irregularities on the entire surface.

<Liquid crystal contamination evaluation (liquid crystal specific resistance)>

Each photosensitive resin composition solution adjusted in each of Examples and Comparative Examples was spin-coated onto a 100 mm × 100 mm glass substrate (EAGLE2000, manufactured by Corning Incorporated) so as to have a dry film thickness of 4 μm (wet thickness 20 μm), and in a reduced pressure drying chamber. It vacuum-dried so that it might reach 0.4 Torr. After drying this dry board | substrate at 90 degreeC * 120 second on a hotplate, it fully exposed at 300mJ / cm <2>, and post-baking was performed at 230 degreeC * 1 hour in a convection oven. After peeling the finished coating film from the substrate, it is mixed with a liquid crystal (Merck & Co., Inc., MLC-6608) and heated at 120 ° C for 5 hours, and then an ultra-micrometer (ADC Corporation, digital ultra-high resistance / micrometer) Liquid crystal specific resistance was measured using the ammeter 8340A). The evaluation result was determined as follows.

(Circle): A resistivity is equivalent to the liquid crystal in which nothing mixed.

(Triangle | delta): Although a specific resistance falls slightly compared with the liquid crystal which mixed nothing, it is in an allowable range.

X: Compared with the liquid crystal in which the specific resistance has not mixed anything, it falls significantly.

In general, it was excellent in that the liquid crystal specific resistance exhibited a high value in terms of low pollution degree to the liquid crystal and reliability of the panel.

<Particle>

The particle amount (unit: piece / ml) after 1 week of refrigeration at 4 degreeC and the particle | grains just after manufacture was measured, respectively by the following method.

A laser was irradiated to the resist liquid passing through the transparent flow path, and the number of particles having a size of 0.3 µm or more was counted by measuring the amount of scattered light by the particles (light scattering method).

The liquid particle counter (KS-42A) made from LION Corporation was used for the measurement.

The result of having performed the above evaluation was recorded in the following table | surface.

From the above table, it was found that the composition of the present invention is a positive photosensitive resin composition which is excellent in applicability, can prevent precipitation during cold storage, has little development unevenness and pixel defects, and obtains a cured film excellent in planarity.

(Example 101)

<Production of Organic EL Display Device>

An organic EL display device using a thin film transistor (TFT) was produced by the following method (see Fig. 1).

A glass substrate 6, the insulating film 3 made of Si ₃ N ₄ forming a TFT (1) of the bottom gate type on, and in a state covering the TFT (1) was formed. Subsequently, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (1.0 μm in height) connected to the TFT 1 through this contact hole is formed on the insulating film 3. did. This wiring 2 is for connecting the TFT 1 with the organic EL element formed between the TFTs 1 or in a later step.

In addition, in order to planarize the unevenness caused by the formation of the wiring 2, the planarization layer 4 was formed on the insulating film 3 with the unevenness of the wiring 2 embedded. Formation of the planarization film 4 on the insulating film 3 is carried out by slit coating the photosensitive resin composition of Example 3 on a substrate and prebaking (90 占 폚 x 2 minutes) on a hot plate, and then using a high pressure mercury lamp from a mask. After irradiating i line | wire (365 nm) 30mJ / cm <2> (roughness 20mW / cm <2>), it developed in alkaline aqueous solution, the pattern was formed, and heat-processed at 230 degreeC for 60 minutes. When apply | coating the said photosensitive resin composition, applicability | paintability was favorable and generation | occurrence | production of a wrinkle and a crack was not recognized by the cured film obtained after exposure, image development, and baking. Moreover, the film thickness of the planarization film 4 which produced 500 nm of average level | step differences of the wiring 2 was 2,000 nm.

Next, the bottom emission type organic electroluminescent element was formed on the obtained planarization film 4. First, the 1st electrode 5 which consists of ITO on the planarization film 4 was connected to the wiring 2 through the contact hole 7, and was formed. Then, the resist was apply | coated and prebaked, and it exposed and developed through the mask of a desired pattern. The pattern process was performed by the wet etchant which used ITO etchant as a mask for this resist pattern. Then, the said resist pattern was stripped using the resist stripping liquid (mixed liquid of monoethanolamine and dimethyl sulfoxide (DMSO)). The 1st electrode 5 obtained in this way is corresponded to the anode of organic electroluminescent element.

Next, the insulating film 8 of the shape which covers the periphery of the 1st electrode 5 was formed. It formed by the method similar to the above using the photosensitive resin composition of Example 3 for the insulating film 8. By providing this insulating film 8, the short between the 1st electrode 5 and the 2nd electrode formed in a subsequent process can be prevented.

Further, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited and installed in a vacuum deposition apparatus through a desired pattern mask. Next, the 2nd electrode which consists of Al was formed in the whole surface above a board | substrate. The obtained said board | substrate was taken out from the vapor deposition machine, and it sealed by sticking using the sealing glass plate and an ultraviolet curable epoxy resin.

As described above, an active matrix organic EL display device in which a TFT 1 for driving this is connected to each organic EL element is obtained. It was found that it was an organic EL display device that exhibited good display characteristics and was highly reliable where voltage was applied through the drive circuit.

(Example 102)

Evaluation similar to Example 101 was changed to the ultrahigh pressure mercury lamp, and it implemented using the UV-LED light source exposure machine. As a result, the same result as in Example 101 was obtained.

(Example 103)

Example 103 was the same as the evaluation of sensitivity performed on the photosensitive resin composition of Example 101 except that the substrate was changed from the glass substrate 6 (Corning 1737, 0.7 mm thick (manufactured by Corning Incorporated)) to a 6 inch silicon wafer. Sensitivity was evaluated. As a result, the same result as in Example 101 was obtained.

(Example 104)

In Example 104, an exposure machine is used. Sensitivity was evaluated similarly to the evaluation of the sensitivity performed about the photosensitive resin composition of Example 101 except having changed to FX-803M (gh-Line stepper) by Nikon Corporation by the PLA-501F exposure machine. As a result, the same result as in Example 101 was obtained.

(Example 105)

In Example 105, the photosensitive resin composition of Example 101 was used and an exposure machine was used. Sensitivity was evaluated similarly to the evaluation of the sensitivity which performed about the photosensitive resin composition of Example 2 except having changed into the 355 nm laser exposure machine in the produced PLA-501F exposure machine, and performed 355 nm laser exposure. As a result, the same result as in Example 101 was obtained.

In addition, as a 355 nm laser exposure machine, V Technology Co., Ltd. Using "EGIS" of production (wavelength 355nm, pulse width 6nsec), exposure amount is Ophir Optronics Ltd. It measured using "PE10B-V2" of production.

As mentioned above, it was found that the photosensitive resin composition of an Example shows the outstanding sensitivity irrespective of a board | substrate and an exposure machine.

Claims (14)

(Component A) The copolymer which contains the structural unit A and structural unit B represented by following General formula (1), and whose weight average molecular weight is 1,000-10,000,
(Component B) The polymer whose weight average molecular weight represented by following General formula (2) is 1,000-50,000,
(Component C) a resin having a structural unit having an acid-decomposable group decomposed by an acid to generate a carboxyl group or phenolic hydroxyl group, and a functional group capable of reacting with a carboxyl group or phenolic hydroxyl group to form a covalent bond,
(Component D) a photoacid generator, and
(Component E) contains a solvent,
A positive photosensitive resin composition, wherein the content of the component A is 0.001 to 1.00 mass%, and the content of the component B is 0.001 to 1.00 mass%.

[In General Formula (1), R <^1> and R <^3> represents a hydrogen atom or a methyl group each independently, R <^2> represents a C1-C4 linear alkylene group, R <^4> represents a hydrogen atom or an alkyl group, L is An alkylene group having 3 to 6 carbon atoms is represented, p and q are mass percentages indicating the polymerization ratio of structural unit A and structural unit B, p represents 10 to 80 mass%, q represents 20 to 90 mass%, r represents an integer of 1 to 18, and n represents an integer of 1 to 10]

[In general formula (2), R <^5> -R <^12> is respectively independently an amino group, a hydroxyl group, a carboxyl group, a glycidyl group, a thiol group, the alkyl group and alkylene group which can also take the repeating structure of a C1-C20 linear or cyclic structure. , Aralkyl group and alkoxy group, m and n represent the mass percentage which represents the polymerization ratio of the dimethylsiloxane structural unit and the modified siloxane structural unit.] The method of claim 1,
At least one of said R <^5> , R <^7> , R <^9> and R <^11> in the said General formula (2) is a polyethyleneoxy group substituted by the polypropyleneoxy group, an unsubstituted alkyl group, an alicyclic epoxy group substituted alkyl group, and a glycidyl group substituted alkyl group And at least one selected from an aralkyl group. The method of claim 1,
Said L in the said General formula (1) is a branched alkylene group represented by following General formula (3), The positive photosensitive resin composition characterized by the above-mentioned.

[In General Formula (3), R ¹³ represents an alkyl group having 1 to 4 carbon atoms.] The method of claim 3, wherein
The positive photosensitive resin composition, wherein R ¹³ in General Formula (3) is an ethyl group. The method of claim 1,
Said component C further has a structural unit derived from at least 1 compound chosen from the group which consists of a styrene derivative, a maleimide derivative, a (meth) acrylic acid, and a hydroxyl-containing (meth) acrylate compound. The positive type photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
A positive photosensitive resin composition, wherein the acid-decomposable group of component C is a group represented by the following general formula (Ia), general formula (Ib), general formula (IIa), or general formula (IIb).

[In general formula (Ia), general formula (Ib), general formula (IIa), and general formula (IIb), R <^21> represents an alkyl group or a cycloalkyl group each independently, R <^22> represents an alkyl group each independently, and R ²¹ and R ²² may form a ring, R ²³ represents a tertiary alkyl group, R ²⁴ represents a tertiary alkyl group or tert-butoxycarbonyl group, and Ar ¹ and Ar ² each independently represent a divalent aromatic group And dashed line indicates a bonding point with another structure] The method of claim 1,
Positive type photosensitive resin composition characterized by including at least one of an oxiranyl group and an oxetanyl group as a functional group of the said component C. The method of claim 7, wherein
Said functional group is an oxetanyl group, The positive type photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
The said component D is an oxime sulfonate compound, The positive photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
The said component E is a solvent with a boiling point of 130 degreeC or more and less than 160 degreeC, a solvent with a boiling point of 160 degreeC or more, or a mixture thereof. (1) an application step of applying the positive photosensitive resin composition according to any one of claims 1 to 10 on a substrate;
(2) a solvent removal step of removing the solvent from the applied positive photosensitive resin composition;
(3) an exposure step of exposing with actinic light;
(4) a developing step of developing with an aqueous developer; And
(5) The manufacturing method of the cured film characterized by including the post-baking process of thermosetting. It was manufactured by the manufacturing method of the cured film of Claim 11, The cured film characterized by the above-mentioned. The method of claim 12,
It is an interlayer insulation film, The cured film characterized by the above-mentioned. The cured film of Claim 12 is provided, The organic electroluminescence display or liquid crystal display device characterized by the above-mentioned.

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