KR20130024812A - Photosensitive resin composition, cured film, method for forming cured film, organic el display device, and liquid crystal display device - Google Patents

Abstract

PURPOSE: A photosensitive resin composition, a cured film, and a method for forming the cured film are provided to ensure excellent storage stability, dry etching resistance, and surface strength. CONSTITUTION: A photosensitive resin composition contains a copolymer, a photoacid generator, and a solvent. The pKa value of generated acid in the photoacid generator is 4 or less. The copolymer has a unit(a5) containing a crosslinking group.

Description

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

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

More specifically, the positive type photosensitive resin composition suitable for formation of the planarization film | membrane of electronic components, such as a liquid crystal display device, an organic electroluminescence display, an integrated circuit element, a solid-state image sensor, a protective film, and an interlayer insulation film, and its use It is related with the formation method of a cured film.

Background Art Conventionally, in electronic components such as liquid crystal display elements, integrated circuit elements, solid-state imaging elements, organic ELs, and the like, generally, a flattening film for imparting flatness on the surface of the electronic component, a protective film or insulating property for preventing deterioration or damage of the electronic component. The photosensitive resin composition is used when forming the interlayer insulation film for holding | maintenance. For example, a TFT type liquid crystal display element is provided with a polarizing plate on a glass substrate, forms a transparent conductive circuit layer such as indium tin oxide (ITO) and a thin film transistor (TFT), and is coated with an interlayer insulating film to form a back plate. On the other hand, a polarizing plate is provided on a glass substrate, and the pattern of a black matrix layer and a color filter layer is formed as needed, and also a transparent conductive circuit layer and an interlayer insulation film are formed one by one as a top plate, and this back plate and a top plate It is produced by enclosing the liquid crystal between the two plates to face each other via a spacer.

As a highly sensitive photosensitive resin composition for an interlayer insulating film, for example, Patent No. 4315013 discloses (A) (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) epoxy group-containing unsaturated compound, (B) 1, A photosensitive resin composition containing a 2-quinone diazide compound is proposed, and Patent Publication No. 4207604 discloses (A) (a1) a norbornene compound having an acetal structure or a ketal structure or an acetal or ketal structure. (Meth) acrylic acid ester compound, (a2) A structural unit selected from a specific crosslinking group, (a3) High molecular weight polystyrene conversion weight average molecular weight formed by copolymerizing other olefinic unsaturated compound (2000) or (B) irradiation The radiation sensitive resin composition for interlayer insulation film formation containing the compound which generate | occur | produces an acid below pKa is proposed by this.

Moreover, as a conventional liquid crystal display device, the thing of patent No. 3362008 is known. Moreover, as a conventional photosensitive resin composition, the thing of Unexamined-Japanese-Patent No. 2009-151099 is known.

An object of the first embodiment of the present invention is to provide a photosensitive resin composition capable of forming an interlayer insulating film having high volume resistivity and dielectric breakdown voltage and high electrical stability, and a method of forming a cured film using the photosensitive resin composition, and the forming method. It provides the cured film formed by this, and the organic electroluminescence display and liquid crystal display device containing the said cured film.

The objective of the 2nd Embodiment of this invention is providing the photosensitive resin composition which is excellent in storage stability, and can form the cured film excellent in dry etching resistance and surface hardness.

Another object of the second embodiment of the present invention is to provide a method for forming a cured film using the photosensitive resin composition, a cured film formed by the forming method, and an organic EL display device and a liquid crystal display device containing the cured film. To provide.

One of the said subjects of this invention was solved by the means as described in the following <1>, <10>, <12>, <14>, or <15>. It describes below with <2>-<9>, <11>, and <13> which is preferable embodiment.

<1> (component A) The structural unit represented by formula (a1), the structural unit represented by formula (a2), the structural unit represented by formula (a3), and / or the structural unit represented by formula (a4) A photosensitive resin composition characterized by containing a copolymer having, a photoacid generator having a pKa of (acid component B) generated acid of 4 or less, and a (component C) solvent,

(In formula, R <^1> represents a hydrogen atom or a methyl group, R <^2> represents a C1-C6 alkyl group, R <^3> represents a C1-C6 alkyl group or a C4-C7 cycloalkyl group, and R <^2> and R ³ may bond and form a ring, R <^4> represents a hydrogen atom or a methyl group, R <^5> represents a hydrogen atom or a methyl group, R <^6> represents a hydrogen atom or a methyl group, X is a single bond, C1-C4 An alkylene group or an alkyleneoxy group having 2 to 4 carbon atoms, and A represents a carbon 5-membered ring having one saturated carbon 5-membered ring or an unsaturated double bond)

The photosensitive resin composition as described in said <1> in which <2> component A further has another structural unit (a5) containing a crosslinkable group other than the structural unit represented by said formula (a2),

<3> Photosensitive resin composition as described in said <1> or <2> whose said structural unit (a5) is a structural unit represented by a following formula (a5-1) or (a5-2),

(Wherein R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents a hydrogen atom or a methyl group)

The photosensitive resin composition in any one of said <1>-<3> in which <4> component A further has a structural unit represented by a following formula (a6),

(Wherein R ⁹ represents a hydrogen atom or a methyl group)

<5> wherein R ³ is, an ethyl group or a cyclohexyl group, a photosensitive resin composition according to any one of the above <1> to <4>,

<6> Photosensitive resin composition in any one of said <1>-<5> whose component B is an oxime sulfonate compound which has at least 1 of the oxime sulfonate residue represented by a following formula (B-0),

(Wherein, the broken line portion indicates the bonding position with other structures)

<7> To <6>, in which the oxime sulfonate compound having at least one of the oxime sulfonate residues represented by Formula (B-0) is an oxime sulfonate compound represented by the following Formula (B-1). Described photosensitive resin composition,

(Wherein, R ^B4 represents a hydrogen atom or a methyl group, R ^B5 represents an alkyl group having 1 to 8 carbon atoms, p-toluyl group, phenyl group, camphoryl group, trifluoromethyl group or nonafluorobutyl group)

<8> The said <6> whose oxime sulfonate compound which has at least 1 of the oxime sulfonate residue represented by said Formula (B-0) is an oxime sulfonate compound represented by following formula (B-2). Described photosensitive resin composition,

(Wherein, R ^B1 represents an alkyl group, an alkoxy group or a halogen atom, and R ^B2 represents an alkyl group or an aryl group)

The photosensitive resin composition in any one of said <1>-<8> which further contains a <9> photosensitizer,

<10> (1) The application | coating process of apply | coating the photosensitive resin composition in any one of said <1>-<9> on a board | substrate, (2) The solvent removal process which removes a solvent from the apply | coated photosensitive resin composition, (3 ) An exposure step of exposing the photosensitive resin composition from which the solvent is removed by actinic light, (4) a developing step of developing the exposed photosensitive resin composition with an aqueous developer, and (5) thermosetting the developed photosensitive resin composition. A method of forming a cured film including a postbaking step,

The formation method of the cured film as described in said <10> including the process of carrying out the whole surface exposure of the developed photosensitive resin composition after the <11> said image development process and before the said post-baking process,

<12> Cured film formed by the method as described in said <10> or <11>,

The cured film as described in said <12> which is a <13> interlayer insulation film,

<14> Organic electroluminescence display provided with the cured film as described in said <12> or <13>,

<15> The liquid crystal display device provided with the cured film as described in said <12> or <13>.

The other of the said subject of this invention was solved by the means as described in the following <16>, <21>, <23>, <25>, or <26>. It describes below with <17>-<20>, <22>, and <24> which is preferable embodiment.

<16> (component A ") The structural unit which has a structural unit (a1") which has an acid group protected by the acid-decomposable group, and a structural unit (a2 ") which has an epoxy group and / or an oxetanyl group, and is represented by following formula (1) A copolymer having no unit, (Component B ") photoacid generator, (Component C") The polymer which has a structural unit represented by following formula (1), and (Component D ") solvent are contained, It is characterized by the above-mentioned. Photosensitive resin composition,

(In formula, R <^1> represents a hydrogen atom or a methyl group, R <^2> represents a C1-C6 alkyl group, a C1-C6 alkoxy group, a hydroxyl group, or a 2, 3- epoxy propoxymethyl group, n is 1-5. Represents an integer)

The photosensitive resin composition as described in said <16> which is a <17> chemically amplified positive type photosensitive resin composition,

The photosensitive resin composition as described in said <16> or <17> whose structural unit represented by <18> said formula (1) is a structural unit represented by following formula (1-1),

(Wherein R ¹ represents a hydrogen atom or a methyl group)

<19> Photosensitive resin composition in any one of said <16>-<18> whose said structural unit (a1 ") is a structural unit represented by Formula (A2),

(In formula (A2), R <^1> and R <^2> represents a hydrogen atom, an alkyl group, or an aryl group each independently, At least one of R <^1> and R <^2> is an alkyl group or an aryl group, and R <^3> may have a substituent An alkyl group, a cycloalkyl group, or an aryl group, and R ¹ Or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group)

The photosensitive resin composition in any one of said <16>-<19> whose <20> component B "is a compound which has an oxime sulfonate residue,

<21> (1) The application | coating process of apply | coating the photosensitive resin composition in any one of said <16>-<20> on a board | substrate, (2) The drying process which removes a solvent from the apply | coated photosensitive resin composition, (3) An exposure step of exposing the photosensitive resin composition from which the solvent has been removed by actinic light, (4) a developing step of developing the exposed photosensitive resin composition with an aqueous developer, and (5) a post for thermosetting the developed photosensitive resin composition. A method of forming a cured film including a baking step,

The formation method of the cured film as described in said <21> including the process of carrying out the whole surface exposure of the developed photosensitive resin composition after the <22> said image development process and before the said post-baking process,

<23> Cured film formed by the method as described in said <21> or <22>,

The cured film as described in said <23> which is a <24> interlayer insulation film,

<25> Organic electroluminescence display provided with the cured film as described in said <23> or <24>,

<26> The liquid crystal display device provided with the cured film as described in said <23> or <24>.

According to the 1st aspect of this invention, the photosensitive resin composition which can form an interlayer insulation film with high volume resistivity and dielectric breakdown voltage, and high electrical stability, the formation method of the cured film using the said photosensitive resin composition, and the hardening formed by the said formation method. An organic EL display device and a liquid crystal display device containing the film and the cured film could be provided.

According to the 2nd Embodiment of this invention, the photosensitive resin composition which was excellent in storage stability and which can form the cured film excellent in dry etching resistance and surface hardness was able to be provided.

Moreover, according to the 2nd Embodiment of this invention, the organic EL display device and liquid crystal display device containing the cured film formed by the formation method of the cured film using the said photosensitive resin composition, the said formation method, and the said cured film can be provided. Could.

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.

Below, the photosensitive resin composition in the 1st and 2nd embodiment of this invention is explained in full detail, respectively.

The photosensitive resin composition (henceforth only called "resin composition") in 1st aspect of this invention is a structural unit represented by (component A) Formula (a1), and a structural unit represented by Formula (a2) And a copolymer having a structural unit represented by formula (a3) and / or a structural unit represented by formula (a4), a photoacid generator having a pKa of (component B) generated acid of 4 or less, and a (component C) solvent It is characterized by containing.

Since the positive photosensitive resin composition of this invention has high volume resistivity and dielectric breakdown voltage of the cured film obtained, an interlayer insulation film with high electrical stability can be formed.

(In formula, R <^1> represents a hydrogen atom or a methyl group, R <^2> represents a C1-C6 alkyl group, R <^3> represents a C1-C6 alkyl group or a C4-C7 cycloalkyl group, and R <^2> and R ³ may bond and form a ring, R <^4> represents a hydrogen atom or a methyl group, R <^5> represents a hydrogen atom or a methyl group, R <^6> represents a hydrogen atom or a methyl group, X is a single bond, C1-C4 An alkylene group or an alkyleneoxy group having 2 to 4 carbon atoms, and A represents a carbon 5-membered ring having one saturated carbon 5-membered ring or an unsaturated double bond)

In recent years, in TFT type liquid crystal display elements, in the trend of large screen, high brightness, high definition, high speed response, thinning, etc., as an interlayer insulation film formation composition used therein, the outstanding electrical characteristic is calculated | required more than before. It is becoming.

As a result of examination by the present inventors, in display devices, such as an organic electroluminescence display and a liquid crystal display device, when the volume resistivity and dielectric breakdown voltage of an interlayer insulation film are small, electrical stability is low and it adversely affects the reliability of a display apparatus. I found out.

In the photosensitive resin composition for the interlayer insulating film described in the above-mentioned Patent Nos. 4315013 and 44207604, since the volume resistivity and the dielectric breakdown voltage are low, the reliability of the display device is not satisfied. It was found that improvement was needed.

In view of the above, the present inventors and the like have conducted detailed studies, and found that the photosensitive resin composition according to the first embodiment of the present invention can form an interlayer insulating film having high volume resistivity and dielectric breakdown voltage and high electrical stability. Paid.

The photosensitive resin composition in 2nd aspect of this invention has a structural unit (a1 ") which has an acidic group protected by the (component A") acid-decomposable group, and a structural unit (a2 ") which has an epoxy group or an oxetanyl group. , A copolymer having no structural unit represented by the following formula (1), a (component B ") photoacid generator, a (component C") polymer having a structural unit represented by the following formula (1), and (component D ″) a solvent.

(In formula, R <^1> represents a hydrogen atom or a methyl group, R <^2> represents a C1-C6 alkyl group, a C1-C6 alkoxy group, a hydroxyl group, or a 2, 3- epoxy propoxymethyl group each independently, and n Represents an integer of 1 to 5)

In recent years, in TFT type liquid crystal display elements, in the trend of large screen, high brightness, high definition, high speed response, thinning, etc., as an interlayer insulation film formation composition used therein, the outstanding electrical characteristic is calculated | required more than before. It is becoming.

For example, depending on the manufacturing process of an electronic component, the cured film formed from the photosensitive resin composition may be exposed to dry etching, and sufficient resistance to dry etching is needed (refer patent document 3362008). Although the composition of Unexamined-Japanese-Patent No. 2009-151099 is mentioned as a composition excellent in dry etching resistance, storage stability was not enough.

Moreover, since various functional layers may overlap on the upper layer of an interlayer insulation film, surface hardness is calculated | required. The photosensitive resin composition which satisfy | fills these various requirements is not known conventionally.

In view of the above, the present inventors and the like conducted a detailed study and found that the photosensitive resin composition according to the second embodiment of the present invention is excellent in storage stability and capable of forming a cured film excellent in dry etching resistance and surface hardness. .

In addition, in this specification, when there is no notice in particular that "photosensitive resin composition of this invention", the photosensitive resin composition in 1st embodiment of this invention, and the photosensitive property in 2nd embodiment of this invention Both sides of the resin composition are shown.

It is preferable that the photosensitive resin composition of this invention is a positive photosensitive resin composition.

Moreover, it is more preferable that the 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. The 1,2-quinonediazide compound in which the pKa of the generated acid exceeds 4 generates a carboxyl group by a sequential photochemical reaction, but the quantum yield is necessarily 1 or less.

On the other hand, the photoacid generator 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. The quantum yield exceeds 1 and becomes a large value such as a power of 10, for example, and high sensitivity is obtained as a result of so-called chemical amplification.

Hereinafter, each component shown by these (component A) etc. is also called "component A", etc., respectively.

In addition, in description of group (atom group) in this specification, the description which is not describing substitution and unsubstitution includes what has a substituent with the thing which does not have a substituent. For example, an "alkyl group" contains not only the alkyl group (unsubstituted alkyl group) which does not have a substituent but the alkyl group (substituted alkyl group) which has a substituent. Here, the permissible substituent is inert and does not change the chemical function of the compound containing the specific group, and examples of the permissible substituent include a halogen atom, an alkoxy group and a hydroxyl group.

In addition, in this invention, "(meth) acrylic acid ester" means an acrylic acid ester and / or methacrylic acid ester. The same applies to "(meth) acrylic acid" and the like.

In addition, in this invention, description of "the lower limit-an upper limit" which shows a numerical range shows "above the lower limit and below the upper limit" unless there is particular notice. That is, it means the numerical range including a lower limit and an upper limit which are disadvantages.

Hereinafter, each component of the photosensitive resin composition in 1st aspect of this invention, and each component of the photosensitive resin composition in 2nd aspect of this invention are demonstrated in order.

(Component A) Air having a structural unit represented by formula (a1), a structural unit represented by formula (a2), a structural unit represented by formula (a3) and / or a structural unit represented by formula (a4) coalescence

The photosensitive resin composition in 1st aspect of this invention is a structural unit represented by (component A) Formula (a1), the structural unit represented by Formula (a2), and the structural unit represented by Formula (a3) And / or a copolymer having a structural unit represented by formula (a4).

Component A is either the structural unit represented by formula (a3) or the structural unit represented by formula (a4), or both of the structural unit represented by formula (a3) and the structural unit represented by formula (a4). Has Especially, it is preferable that component A has both a structural unit represented by a formula (a3), and a structural unit represented by a formula (a4).

Component A may have the structural unit represented by Formula (a1) individually by 1 type, or may have 2 or more types. The same applies to the structural units represented by the formulas (a2) to (a4).

In addition, the component A may have structural units other than the structural unit represented by Formula (a1)-a formula (a4).

Moreover, "the structural unit represented by Formula (a1)" etc. are also called "structural unit (a1)", etc.

Component A is an alkali insoluble or poorly soluble, and is preferably a -COOCH (R ²⁾ OR ^3, etc. This is the alkali-soluble resin when the decomposition of the structural unit (a1) having in the molecule.

The component A is not excluded from the introduction of an acid group as long as the whole thereof is kept insoluble in alkali. As an example of the case where an acidic group is introduce | transduced into component A, the case which has a structural unit (a7-5) etc. which are mentioned later are mentioned, for example.

<Structural unit represented by formula (a1)>

Component A has at least a structural unit represented by formula (a1).

(In formula, R <^1> represents a hydrogen atom or a methyl group, R <^2> represents a C1-C6 alkyl group, R <^3> represents a C1-C6 alkyl group or a C4-C7 cycloalkyl group, and R <^2> and R ³ may combine to form a ring)

The partial structure of -COOCH (R ² ) OR ^{3 in} the structural unit represented by the formula (a1) is decomposed by an acid, for example, by an acid generated from component B by exposure to active light. , -COOH (carboxy group). By newly forming a carboxyl group, alkali solubility increases, an exposure part becomes soluble, and image development can be performed. Moreover, also in an unexposed part, the said partial structure decomposes | disassembles and produces | generates a carboxyl group by the heat processing in the post-baking process mentioned later. The produced | generated carboxyl group can form bridge | crosslinking by reacting with the epoxy group etc. of the structural unit represented by Formula (a2).

R ¹ in the formula (a1) is preferably a methyl group from the viewpoint of the uniformity of the polymerization rate of each monomer during polymerization.

In addition, even if R <^2> and R <^3> in the said Formula (a1) combine and form the ring, it is not necessary to form the ring.

Hereinafter, it demonstrates dividing into the case where R <^2> and R <^3> do not form a ring, and the case which forms a ring.

When R ² and R ³ do not form a ring-

The alkyl group in R ² may be linear or branched.

As carbon number of R <^2> , it is preferable that it is 1-4, It is more preferable that it is 1 or 2, It is more preferable that it is 1.

The alkyl group in R ³ may be linear or branched.

As carbon number of the alkyl group in R <^3> , it is preferable that it is 1-4, It is more preferable that it is 1-3, It is more preferable that it is 1 or 2.

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

Moreover, when these carbon number has a substituent, the carbon number of a substituent is also contained.

The alkyl group in R ³ 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 <^3> , 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.

The alkyl group in R ² , and the alkyl group and cycloalkyl group in R ³ 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 hydroxyl group, a C1-C10 alkoxy group, etc. can be illustrated, These substituents may further be substituted by the said substituent.

Moreover, as an alkyl group or a cycloalkyl group in R <^3> , a C1-C10 alkyl group, a C3-C10 cycloalkyl group, or a C1-C11 aralkyl group is preferable, and a C1-C6 alkyl group is preferable. The cycloalkyl group having 3 to 6 carbon atoms or the benzyl group is more preferable, it is more preferable that it is an ethyl group or a cyclohexyl group, and it is particularly preferable that it is an ethyl group.

Among these structures, particularly preferred as structural units having an acid-decomposable group are structural units represented by formula (a1-1).

(In formula, R <^1> represents a hydrogen atom or a methyl group, R <^3> represents a C1-C6 alkyl group or a C4-C7 cycloalkyl group.)

Expression of the R ¹ and R ³ according to (a1-1) is an R ¹ and R ³ each consent in the formula (a1), a preferred embodiment is also the same respectively.

As a preferable specific example of the radically polymerizable monomer used in order to form the structural unit represented by a formula (a1-1), 1-ethoxy ethyl methacrylate, 1-ethoxy ethyl acrylate, 1-methacrylate, for example. Methoxyethyl methacrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl methacrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl methacrylate, 1-isobutoxyethylacrylic Rate, 1- (2-ethylhexyloxy) ethyl methacrylate, 1- (2-ethylhexyloxy) ethyl acrylate, 1-n-propoxyethyl methacrylate, 1-n-propoxyethylacrylic Rate, 1-cyclohexyloxyethyl methacrylate, 1-cyclohexyloxyethyl acrylate, 1- (2-cyclohexylethoxy) ethyl methacrylate, 1- (2-cyclohexylethoxy) ethyl acrylate, 1-benzyloxyethyl methacrylate, 1-benzyloxyethyl acrylate, etc. are mentioned, Hi preferable examples are a-ethoxyethyl acrylate-ethoxyethyl methacrylate and 1 to 1. These structural units can have 1 type individually or in combination of 2 or more types.

When R ² and R ³ form a ring-

R ² and R ³ may form a ring.

As an example of the group which formed the ring with R <^2> and R <^3> , a 2-tetrahydropyranyl group and a 2-tetrahydrofuranyl group are preferable.

That is, it is preferable that R <^2> and R <^3> combine and form a C3 or 4 alkylene group, and it is especially preferable to form a C3 alkylene group.

As a preferable specific example of the radically polymerizable monomer used in order to form these structural units, For example, tetrahydro-2H-pyran-2-yl methacrylate, tetrahydro-2H-pyran-2-yl acrylate, meta Krylic acid tetrahydrofuran-2-yl, acrylic acid tetrahydrofuran-2-yl, etc. are mentioned.

As a radically polymerizable monomer used in order to form the structural unit represented by a formula (a1), a commercially available thing may be used and what was synthesize | combined by a well-known method can also be used. For example, it can synthesize | combine by making (meth) acrylic acid react with a vinyl ether compound in presence of an acidic catalyst, as shown below.

(In formula, R <^1> and R <^3> correspond to R <^1> and R <^3> in Formula (a1-1), respectively.)

In addition, the structural unit represented by a formula (a1) can be formed by copolymerizing the (meth) acrylate compound protected by the said corresponding acid-decomposable group with the other monomer mentioned later, for example. Moreover, after superposing | polymerizing (meth) acrylic acid with the other monomer mentioned later and its precursor, it can also form by making a carboxyl group react with a vinyl ether compound. Moreover, 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.

5-60 mol% is preferable, as for content of the monomer unit which forms the structural unit represented by Formula (a1), among all the monomer units which comprise component A, 10-55 mol% is more preferable, 15-50 Mole% is particularly preferred. By making it contain in the said ratio, the cured film with high sensitivity and high volume resistivity can be obtained.

<Structural unit represented by formula (a2)>

Component A has at least a structural unit represented by Formula (a2). By having the structural unit represented by Formula (a2), the cured film with high volume resistivity and dielectric breakdown voltage can be obtained.

The epoxy group of the structural unit represented by a formula (a2) can react with the carboxy group in a system by the heat processing in the post-baking process mentioned later, or epoxy groups can react and form bridge | crosslinking.

(Wherein R ⁴ represents a hydrogen atom or a methyl group)

R ⁴ in the formula (a2) is preferably a hydrogen atom from the viewpoint of the uniformity of the polymerization rate of each monomer at the time of polymerization.

In the formula (a2), the bonding position of the glycidyloxymethyl group on the benzene ring is not particularly limited, and may be the o position or the m position with respect to the benzene ring to which the carbon atom to which R ⁴ is bonded is bonded. Although it may be a p position, it is preferable from a viewpoint of obtaining a cured film with high volume resistivity and dielectric breakdown voltage.

As a structural unit represented by said formula (a2), the structural unit represented by a following formula (a2-1) can be illustrated preferably.

(Wherein R ⁴ represents a hydrogen atom or a methyl group)

R ⁴ in formula (a2-1) is synonymous with R ⁴ in formula (a2), and preferred embodiments thereof are also the same.

As a monomer which forms the structural unit represented by said formula (a2), the compound represented by a following formula (a2 ') can be illustrated preferably.

(Wherein R ⁴ represents a hydrogen atom or a methyl group)

Expression of the R ⁴ in the (a2 ') is, and R ⁴ and consent of the formula (a2), as a preferred aspect.

Even if the structural unit represented by a formula (a2) superposes | polymerizes and forms the compound represented by said formula (a2 '), for example, after polymerizing a hydroxymethyl styrene compound, a glycidyl group is introduce | transduced by a polymer reaction. Although it may be sufficient, it is preferable to superpose | polymerize and form the compound represented by said formula (a2 '). When the compound represented by the said Formula (a2 ') is superposed | polymerized and formed, the structural unit represented by Formula (a2) in component A is also a monomer unit represented by Formula (a2).

1-60 mol% is preferable, as for content of the monomer unit which forms the structural unit represented by Formula (a2), among all the monomer units which comprise component A, 2-50 mol% is more preferable, 5-40 More preferably, mol% is 10-20 mol% is especially preferable. By containing in the said ratio, the cured film with high volume resistivity and dielectric breakdown voltage can be obtained.

<Structural unit represented by formula (a3)>

Component A has a structural unit represented by a formula (a3) and / or a structural unit represented by a formula (a4).

(Wherein R ⁵ represents a hydrogen atom or a methyl group)

It is preferable that R <^5> in said formula (a3) is a hydrogen atom from a viewpoint of the uniformity of the superposition | polymerization rate of each monomer at the time of superposition | polymerization.

As a monomer which forms the structural unit represented by said formula (a3), the compound represented by a following formula (a3 ') can be illustrated preferably.

R <^5> in Formula (a3 ') is synonymous with R <^5> in said Formula (a3), and its preferable aspect is also the same.

It is preferable that the structural unit represented by a formula (a3) superposes | polymerizes and forms the compound represented by said formula (a3 '). When the compound represented by the said Formula (a3 ') is superposed | polymerized and formed, the structural unit represented by Formula (a3) in component A is also a monomer unit represented by Formula (a3).

<Structural unit represented by formula (a4)>

Component A has a structural unit represented by a formula (a3) and / or a structural unit represented by a formula (a4).

(Wherein R ⁶ represents a hydrogen atom or a methyl group, X represents a single bond, an alkylene group of 1 to 4 carbon atoms or an alkyleneoxy group of 2 to 4 carbon atoms, and A represents a saturated carbon 5-membered ring or an unsaturated double bond) Carbon five-membered ring having)

R ⁶ in the formula (a4) is preferably a methyl group from the viewpoint of the uniformity of the polymerization rate of each monomer during polymerization.

It is preferable that X in said Formula (a4) is a single bond, a methylene group, a propyleneoxy group, or an ethyleneoxy group, and it is more preferable that it is a single bond, a methylene group, or an ethyleneoxy group.

In the formula (a4), the ring structure A may or may not be present.

As an alicyclic structure group comprised by the norbornene ring and ring structure A in the said Formula (a4), it is especially preferable that it is a tricyclo [5.2.1.0 ^2,6 ] decane-8-yl group.

As a monomer which forms the structural unit represented by a formula (a4), the (meth) acrylate compound which has an alicyclic structure can be illustrated preferably, and the compound represented by a following formula (a4 ') can be illustrated more preferably. have.

(Wherein R ⁶ represents a hydrogen atom or a methyl group, X represents a single bond, an alkylene group of 1 to 4 carbon atoms or an alkyleneoxy group of 2 to 4 carbon atoms, and A represents a saturated carbon 5-membered ring or an unsaturated double bond) Carbon five-membered ring having)

Formula R ^6, X and A in the (a4 ') is, and R ^6, X and A and agreement in the formula (a4), as a preferred aspect.

Specific examples of the compound represented by formula (a4 ') include tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate and tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxy Ethyl (meth) acrylate etc. are mentioned.

Especially, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate is the most preferable.

1-70 mol% is preferable, and, as for the total content of the monomer unit which forms the structural unit represented by Formula (a3), and the structural unit represented by Formula (a3) among all the monomeric units which comprise component A, 60 mol% is more preferable, 5-50 mol% is more preferable, 15-35 mol% is especially preferable. By containing in the said ratio, the cured film with high volume resistivity and dielectric breakdown voltage can be obtained.

When component A has a structural unit represented by Formula (a3), content of the monomeric unit which forms the structural unit represented by Formula (a3) among all the monomer units which comprise component A is 1-60 mol%. It is preferable, 2-50 mol% is more preferable, 10-50 mol% is further more preferable, 15-25 mol% is especially preferable.

In addition, when component A has a structural unit represented by Formula (a4), content of the monomeric unit which forms the structural unit represented by Formula (a4) among all the monomer units which comprise component A is 1-50 mol. % Is preferable, 2-40 mol% is more preferable, 5-25 mol% is more preferable, 10-15 mol% is especially preferable.

<Structural unit having a crosslinking group (structural unit (a5))>

It is preferable that component A further has a structural unit (also called "structural unit (a5)") which has another crosslinkable group different from the structural unit represented by said formula (a2) from a physical property of a cured film. .

As a crosslinkable group, it is preferable that it is a functional group which can react with a carboxy group and can form a covalent bond. Specifically, an epoxy group, an oxetanyl group, an acid anhydride group, an acid halide group, and an isocyanate group are mentioned preferably, It is preferable to synthesize | combine the component A using the radically polymerizable monomer containing this functional group. Among the crosslinkable groups, an epoxy group and / or an oxetanyl group is preferable.

As a structural unit which has the said epoxy 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 Etc. are mentioned preferably.

As a group which has an oxetanyl group, if it has an oxetane ring, there is no restriction | limiting in particular, The (3-ethyloxetan-3-yl) methyl group can be illustrated preferably.

The structural unit (monomer unit) which has an epoxy group and / or an oxetanyl group should just have at least 1 epoxy group or an oxetanyl group in one structural unit (monomer unit), and at least 1 epoxy group and 1 or more oxetanyl group It may have 2 or more epoxy groups, or 2 or more oxetanyl groups, and although it does not specifically limit, It is preferable to have 1-3 epoxy groups and / or oxetanyl groups in total, Epoxy group and / or oxetanyl group It is more preferable to have one or two in total, and it is more preferable to have one epoxy group or oxetanyl group.

As a specific example of the radically polymerizable monomer used in order to form the structural unit which has an epoxy group, it is the glycidyl acrylate, the glycidyl methacrylate, the (alpha)-ethyl acrylate glycidyl, the (alpha)-n-propyl acrylate, for example. 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, (alpha)-ethylacrylic-acid 6,7-epoxyheptyl, the compound containing the alicyclic epoxy skeleton of Paragraph 0031-0035 of patent 4168443, etc. are mentioned.

As an example of the radically polymerizable monomer used in order to form the structural unit which has an oxetanyl group, (meth) acrylic acid ester etc. which have the oxetanyl group of Paragraph 0011 of Unexamined-Japanese-Patent No. 2001-330953-0016, etc. are mentioned, for example. Can be mentioned.

As an example of the radically polymerizable monomer used in order to form the structural unit which has an epoxy group and / or an oxetanyl group, it is preferable that they are a monomer containing a methacrylic acid ester structure, and a monomer containing an acrylate ester structure.

Among these monomers, more preferably, the compound containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of 4168443 and the oxetanyl group described in paragraphs 0011 to 0016 of JP 2001-330953 A ( It is meta) acrylic acid ester, and it is (meth) acrylic acid ester which has an oxetanyl group of Paragraph 0011 of Unexamined-Japanese-Patent No. 2001-330953-0016. Among these, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, acrylic acid (3-ethyloxetan-3-yl) methyl, and methacrylic acid (3-ethyloxetane 3-yl) methyl is preferred, and acrylic acid (3-ethyloxetan-3-yl) methyl and methacrylic acid (3-ethyloxetan-3-yl) methyl are most preferred. These monomers can be used individually by 1 type or in combination of 2 or more types.

As a structural unit which has a crosslinkable group, the structural unit represented by a following formula (a5-1) or a formula (a5-2) can be illustrated preferably.

(Wherein R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents a hydrogen atom or a methyl group)

R ^{7 in} the formula (a5-1) and R ⁸ in the formula (a5-2) are preferably a methyl group from the viewpoint of the uniformity of the polymerization rate of each monomer during polymerization.

When component A has a structural unit which has a crosslinkable group, 0.5-50 mol% is preferable and, as for the content rate of the monomer unit which forms the structural unit which has a crosslinkable group among all the monomer units which comprise component A, 1-40 Mol% is more preferable, and 5-30 mol% is especially preferable. By containing in the said ratio, the physical property of a cured film becomes favorable.

<Structural unit represented by formula (a6)>

It is preferable that component A further has a structural unit represented by a following formula (a6) from a developable viewpoint.

(Wherein R ⁹ represents a hydrogen atom or a methyl group)

R ⁹ in the formula (a6) is preferably a methyl group from the viewpoint of the uniformity of the polymerization rate of each monomer during polymerization.

When component A has a structural unit represented by Formula (a6), the content rate of the monomer unit which forms the structural unit represented by Formula (a6) among all the monomer units which comprise component A is 0.5-40 mol%. It is preferable, 1-20 mol% is more preferable, and 5-10 mol% is especially preferable. By containing in the said ratio, the physical property of a cured film becomes favorable.

<Other structural unit (a7)>

Component A may contain structural units other than the said structural unit (a1)-(a6) (henceforth an appropriate "structural unit (a7)") in the range which does not prevent the effect of this invention. .

Although it does not specifically limit as a radically polymerizable monomer used in order to form a structural unit (a7), For example, Paragraph 0021 of Unexamined-Japanese-Patent No. 2004-264623-the compound of 0024 are mentioned (However, Structural units (a1) to (a6) are excluded).

Preferred aspects of the preferred structural unit (a7) and the radically polymerizable monomer used for forming the structural unit (a7) will be specifically described.

[Structural unit (a7-1) having a carboxylic acid alkyl ester residue]]

It is preferable that component A has a structural unit (a7-1) which has a carboxylic acid alkyl ester residue from a transparency viewpoint.

As a structural unit (a7-1) which has a carboxylic acid alkyl ester residue, it is preferable that it is a structural unit represented by a following formula (a7-1).

(In formula, R <^10> represents a hydrogen atom or a methyl group, and R <^11> represents a C1-C12 alkyl group.)

R ¹⁰ in the formula (a7-1) is preferably a methyl group from the viewpoint of the uniformity of the polymerization rate of each monomer at the time of polymerization.

It is preferable that R <^11> in said Formula (a7-1) is a C1-C8 alkyl group, It is more preferable that it is a C1-C4 alkyl group, It is especially preferable that it is a methyl group. In addition, the alkyl group in said R <^11> may be linear or may have a branch. Moreover, as R <^11> , it is preferable that they are a methyl group or 2-ethylhexyl group.

As a monomer which forms the structural unit (a7-1) which has the said carboxylic acid alkyl ester residue, an alkyl (meth) acrylate compound can be illustrated preferably, and the compound represented by a following formula (a7'-1) is more preferable. This can be illustrated.

Expression of the R ¹⁰ and R ¹¹ in (a7'-1), and R ¹⁰ and R ¹¹ and each agreement in the formula (a7-1), the same is also a preferred embodiment.

[Structural Unit (a7-2) Having Maleimide Residue]]

It is preferable that component A has a structural unit (a7-2) which has a maleimide residue from a thermosetting viewpoint.

As a structural unit (a7-2) which has a maleimide residue, it is preferable that it is a structural unit represented by a following formula (a7-2).

(In formula, R <^12> represents group represented by an alkyl group, a cycloalkyl group, an aryl group, or following formula (S).)

(In formula, x represents the integer of 2-10, and a dashed part shows the bonding position of the nitrogen atom in Formula (a7-2).)

It is preferable that R <^12> in said Formula (a7-2) is group represented by a C1-C12 alkyl group, a C5-C12 cycloalkyl group, a C6-C12 aryl group, or the said Formula (S), It is more preferable that it is a group represented by a benzyl group, a cyclohexyl group, a phenyl group, or the said Formula (S).

It is preferable that it is 2-8, and, as for x in said Formula (S), it is more preferable that it is 2-7.

As a monomer which forms the structural unit (a7-2) which has the said maleimide residue, the compound represented by a following formula (a7'-2) can be illustrated preferably.

R ¹² in the formula in (a7'-2) is, and R ¹² and agreed in the formula (a7-2), the same is also a preferred embodiment.

Specific examples of the compound represented by formula (a7'-2) include phenylmaleimide, cyclohexyl maleimide, benzyl maleimide, N-succinimidyl-3-maleimide benzoate and N-succinimidyl-4-male Midbutylate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide and the like. Especially, N-cyclohexyl maleimide and N-phenylmaleimide are especially preferable.

[Structural Unit (a7-3) Having a Hydroxy Group]]

It is preferable that component A has a structural unit (a7-3) which has a hydroxyl group from a developable viewpoint.

As a structural unit (a7-3) which has a hydroxyl group, it is preferable that it is a structural unit represented by a following formula (a7-3).

(In formula, R <^13> represents a hydrogen atom or a methyl group, y represents the integer of 2-11.)

R ¹³ in the formula (a7-3) is preferably a methyl group from the viewpoint of the uniformity of the polymerization rate of each monomer at the time of polymerization.

It is preferable that it is an integer of 2-8, y in said Formula (a7-3), It is more preferable that it is an integer of 2-4, It is especially preferable that it is 2.

As a monomer which forms the structural unit (a7-3) which has the said hydroxyl group, the compound represented by a following formula (a7'-3) can be illustrated more preferable.

Formula R ¹³ and y in the (a7'-3) is, and R ¹³ and y and each agreement in the formula (a7-3), the same is also a preferred embodiment.

[Structural unit (a7-4) having a polyether structure]

It is preferable that component A has a structural unit (a7-4) which has a polyether structure from a developable viewpoint.

As a structural unit (a7-4) which has a polyether structure, it is preferable that it is a structural unit represented by a following formula (a7-4-1) or a formula (a7-4-2).

(In formula, R <^14> represents a hydrogen atom or a methyl group, R <^15> represents a hydrogen atom, a C1-C12 alkyl group, or a phenyl group, X represents a single bond or a bivalent coupling group, m and n are each independently, Represents an integer from 0 to 50, except that m and n do not become 0 together)

The formula (a7-4-1), and R ¹⁴ in the formula (a7-4-2) is, in terms of the uniformity of the polymerization rate of the monomers at the time of polymerization, a methyl group is preferred.

It is preferable that R <^15> in said Formula (a7-4-1) and said Formula (a7-4-2) is a C1-C8 alkyl group or a phenyl group, It is more preferable that it is a C1-C4 alkyl group, It is more preferable that it is a methyl group. In addition, the alkyl group in said R <^15> may be linear or may have a branch.

In the formulas (a7-4-1) and (a7-4-2), X is preferably a single bond or a divalent linking group having 1 to 50 carbon atoms, and is preferably a single bond or alkyl having 1 to 20 carbon atoms. It is more preferable that it is a benzene group, and it is still more preferable that it is a single bond.

It is preferable that m and n in said Formula (a7-4-1) and said Formula (a7-4-2) are each independently an integer of 0-40, and it is more preferable that it is an integer of 0-20.

Also, -C in the formula (a7-4-1) and the formula (a7-4-2) ₃ H ₆ O- _{is, -CH (CH 3) CH 2} O- or -CH ₂ CH (CH ₃ ) O- is preferred.

As a monomer which forms the structural unit (a7-4) which has the said polyether structure, the compound represented by a following formula (a7'-4-1) or a formula (a7'-4-2) can be illustrated more preferable. have.

R <^14> , R <^15> , X, m, and n in Formula (a7'-4-1) and Formula (a7'-4-2) are said Formula (a7'-4-1) and Formula (a7 ') It is synonymous with R <^14> , R <^15> , X, m, and n in -4-2), and a preferable aspect is also the same.

[Structural unit (a7-5) having a carboxyl group]]

It is preferable that component A has a structural unit (a7-5) which has a carboxy group.

As a monomer which forms the structural unit (a7-5) which has the said carboxyl group, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc. are mentioned, for example.

Among these, (meth) acrylic acid is preferable and methacrylic acid is especially preferable.

Moreover, as a structural unit (a7-5) which has a carboxy group, it is preferable that it is a structural unit represented by a following formula (a7-5-1) or a formula (a7-5-2), and is a following formula (a7-5-1) It is especially preferable that it is a structural unit represented by).

These structural units (a7) may have 1 type independently in component A, or may have 2 or more types.

In all the monomer units which comprise component A, 0-50 mol% is preferable, as for the content rate of the monomer unit which forms a structural unit (a7), 0-20 mol% is more preferable, 0-10 mol% is more desirable.

Moreover, it is preferable that it is 2,000-100,000, as for the polystyrene conversion weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) of component A, 3,000-50,000 are more preferable, 4,000-30,000 are especially preferable.

The photosensitive resin composition in 1st aspect of this invention can contain component A individually by 1 type or in combination of 2 or more types.

It is preferable that it is 20-99 weight% with respect to the total solid of the photosensitive resin composition, and, as for content of the component A in the photosensitive resin composition in 1st Embodiment of this invention, it is more preferable that it is 40-97 weight%. And it is more preferable that it is 60 to 95 weight%. If content of component A is this range, the pattern formation property at the time of image development will become favorable. In addition, solid content of the photosensitive resin composition represents the quantity except volatile components, such as a solvent.

Moreover, the photosensitive resin composition in 1st Embodiment of this invention may use together resin other than component A in the range which does not prevent the effect of this invention. However, it is preferable that content of resin other than component A is smaller than content of component A from a developable viewpoint.

(Component B) A photoacid generator having a pKa of 4 or less

The photosensitive resin composition in 1st aspect of this invention contains the photoacid generator (it is only called "photoacid generator") whose pKa of (component B) generating acid is 4 or less.

As a photo-acid generator used by this invention, although the compound which responds to actinic light of wavelength 300nm or more, Preferably wavelength 300-450nm, and produces | generates an acid is preferable, It is not limited to the chemical structure. Moreover, also about the photo-acid generator which does not directly react to actinic light of wavelength 300nm or more, if it is a compound which responds to actinic light of wavelength 300nm or more by using together with a sensitizer and produces | generates an acid, it will be used conveniently in combination with a sensitizer. Can be.

As a photoacid generator whose acid decomposition constant (pKa) of the generated acid used by this invention is 4 or less, the photoacid generator whose pKa of the generated acid is 3 or less is preferable.

Moreover, about pKa, a value can be calculated | required by a well-known measuring method, a well-known calculation method, and / or a literature value.

Examples of photoacid generators having a pKa of the generated acid of 4 or less include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imidesulfonate compounds, and oximes. Sulfonate compounds; and the like. Among these, it is preferable to use an oxime sulfonate compound from an insulating viewpoint. These photoacid generators can be used individually by 1 type or in combination of 2 or more types.

As these specific examples, the following can be illustrated.

As trichloromethyl-s-triazines, 2- (3-chlorophenyl) bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) bis (4,6-trichloro Rhomethyl) -s-triazine, 2- (4-methylthiophenyl) bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) bis (4 , 6-trichloromethyl) -s-triazine, 2-piperonylbis (4,6-trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] bis (4,6-trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] bis (4,6-trichloromethyl) -s-triazine, 2 -[2- (4-diethylamino-2-methylphenyl) ethenyl] bis (4,6-trichloromethyl) -s-triazine or 2- (4-methoxynaphthyl) bis (4, 6-trichloromethyl) -s-triazine and the like;

As the diaryl iodonium salts, diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, 4-methoxy Phenylphenyl iodonium trifluoroacetate, phenyl-4- (2'-hydroxy-1'-tetradecaoxy) phenyl iodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1 ' -Tetradecaoxy) phenyl iodonium hexafluoro antimonate, or phenyl-4- (2'-hydroxy-l'- tetradecaoxy) phenyl iodonium p-toluenesulfonate;

As the triarylsulfonium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenyl Sulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium trifluoroacetate, and the like;

As quaternary ammonium salts, tetramethylammoniumbutyltris (2,6-difluorophenyl) borate, tetramethylammoniumhexyltris (p-chlorophenyl) borate, tetramethylammoniumhexyltris (3-trifluoromethylphenyl) Borate, benzyldimethylphenylammoniumbutyltris (2,6-difluorophenyl) borate, benzyldimethylphenylammoniumhexyltris (p-chlorophenyl) borate, benzyldimethylphenylammoniumhexyltris (3-trifluoromethylphenyl) borate ;

Examples of diazomethane derivatives include bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane and the like;

As imide sulfonate derivatives, trifluoromethylsulfonyloxybicyclo [2.2.1] -hepto-5-ene-dicarboxyimide, succinimide trifluoromethylsulfonate, phthalimide trifluoromethylsulfo Nate, N-hydroxynaphthalimide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimidepropanesulfonate and the like;

As an oxime sulfonate compound, the compound shown below.

The photosensitive resin composition in the 1st Embodiment of this invention is. (Component B) It is preferable to contain the oxime sulfonate compound which has at least 1 of the oxime sulfonate residue represented by a following formula (B-0) as a photo-acid generator. Moreover, a broken line part shows the bonding position with another chemical structure.

(Wherein, the broken line portion indicates the bonding position with other structures)

As an oxime sulfonate compound represented by said Formula (B-0), it is preferable that it is an oxime sulfonate compound represented by a following formula (B-1).

(Wherein, R ^B4 represents a hydrogen atom or a methyl group, R ^B5 represents an alkyl group having 1 to 8 carbon atoms, p-toluyl group, phenyl group, camphoryl group, trifluoromethyl group or nonafluorobutyl group)

It is preferable that R <^B4> in said Formula (B-1) is a methyl group.

The alkyl group having 1 to 8 carbon atoms and the nonafluorobutyl group in R ^B5 of the formula (B-1) may be linear or may have a branch.

Moreover, it is preferable that it is 1-4, and, as for carbon number of the alkyl group in said ^RB5 , it is more preferable that it is 1-3.

Further, camphoryl (camphoryl) a combination of a sulfur atom group and position in the R ^B5 is not particularly limited, is preferably 10 position. That is, it is preferable that the said camphoryl group is a 10-camphoryl group.

R ^B5 in the formula (B-1) is preferably a methyl group, n-propyl group, n-octyl group, p-toluyl group or camphoryl group, and n-propyl group, n-octyl group or p-tolu It is more preferable that it is a diary or a camphoryl group, and it is still more preferable that it is n-propyl group or p-toluyl group.

Moreover, it is preferable that it is an oxime sulfonate compound represented with a following formula (B-2) as an oxime sulfonate compound represented by said Formula (B-0).

(In the formula, R ^B1 is a hydrogen atom, a methyl group or a methoxy group, R ^B2 represents a butyl group or nonafluoro with an alkyl group, p- Tolu group, a phenyl group, camphor group, a trifluoromethyl group having a carbon number of 1 to 8)

It is preferable that R <^B1> in said Formula (B-2) is a hydrogen atom.

R ^B2 in the formula (B-2) is preferably a methyl group, n-propyl group, n-octyl group or p-toluyl group, camphoryl group or phenyl group, and methyl group, n-propyl group, n-jade It is more preferable that they are a methyl group, p-toluyl group, or a camphoryl group.

Alkyl-butyl group, nonafluorobutyl group having 1 to 8 carbon atoms in the R ^B2 are, even straight-chain, may have a branch.

In addition, the bonding position of the sulfur atom of camphoryl (camphoryl) group in the above R ^B2 is not particularly limited, is preferably 10 position. That is, it is preferable that the said camphoryl group is a 10-camphoryl group.

It is preferable that content of the (component B) photo-acid generator in the photosensitive resin composition in 1st aspect of this invention is 0.1-10 weight part with respect to 100 weight part of components A, and it is 0.2-10 weight part More preferably, it is more preferable that it is 0.5-7 weight part.

(Component C) Solvent

The photosensitive resin composition in 1st aspect of this invention contains the (component C) solvent.

It is preferable that the photosensitive resin composition in 1st aspect of this invention is prepared as the solution which melt | dissolved the component A and the component B which are essential components, and the optional component mentioned later in the (component C) solvent.

As a solvent used for the photosensitive resin composition in 1st aspect of this invention, a well-known solvent can be used and ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, ethylene glycol monoalkyl ether acetate, propylene Glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol di Alkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones, etc. can be illustrated.

Moreover, as a solvent used for the photosensitive resin composition in 1st Embodiment of this invention, the solvent of 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, as for the solvent which can be used for this invention, It is more preferable to use 2 types together, It uses propylene glycol monoalkyl ether acetates and diethylene glycol dialkyl ether together. More preferred.

It is preferable that content of the component C in the photosensitive resin composition in 1st aspect of this invention is 50-3,000 weight part with respect to 100 weight part of component A, It is more preferable that it is 100-2,000 weight part, 150 It is more preferable that it is-1500 parts by weight.

The photosensitive resin composition in 1st Embodiment of this invention may contain other components arbitrary as said component A-component C as an essential component. Optional components include (component D) sensitizer, (component E) basic compound, (component F) crosslinking agent, (component G) adhesion improving agent, (component H) surfactant, (component I) development accelerator, (component J) Antioxidant, (component K) plasticizer, (component L) thermal radical generator, (component M) thermal acid generator, (component N) acid increasing agent, and the like. The additive which can be used in the present invention is not limited to these, and various additives known in the art can be used.

(Component D) sensitizer

It is preferable that the photosensitive resin composition in 1st aspect of this invention contains the (component D) sensitizer in order to accelerate the decomposition | disassembly and to improve a sensitivity in combination with the component B mentioned above.

As a sensitizer, the photosensitizer which absorbs actinic light or a radiation and becomes an electron excited state can be illustrated preferably. The sensitizer which has become an electron-excited state comes into contact with photoacid generators such as component B to generate an action such as electron transfer, energy transfer, and heat generation. As a result, the photoacid generator causes chemical change to decompose to produce an acid.

As an example of a preferable sensitizer, the compound which belongs to the following compounds, and has an absorption wavelength in 350 nm-450 nm range is mentioned.

Polynuclear aromatics (e.g. pyrene, perylene, triphenylene, anthracene), xanthenes (e.g. fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (e.g. , Xanthones, thioxanthones, dimethyl thioxanthones, diethyl thioxanthones, cyanines (e.g., thiacarbocyanine, oxacarbocyanine), melocyanines (e.g., melocyanine , Carbomelocyanine), rhodicyanines, oxonols, thiazines (e.g. thionine, methylene blue, toluidine blue), acridines (e.g. acridine orange, chloroflavin, Acriflavin), acridones (e.g. acridon, 10-butyl-2-chloroacridone), anthraquinones (e.g. anthraquinones), squaryliums (e.g. Arlium), styryls, base styryls, and coumarins (eg, 7-diethylamino-4-methylcoumarin). Among these sensitizers, a sensitizer which absorbs actinic rays or radiation to be in an electron excited state and has an electron transfer action to a photoacid generator is preferable, and polynuclear aromatics, acridones, coumarins and base styryls are particularly preferable. And anthracene is the most preferable.

A sensitizer may use a commercially available thing and may be synthesize | combined by a well-known synthetic method.

As for the addition amount of a sensitizer, 20-300 weight part is preferable with respect to 100 weight part of component B from a viewpoint of compatibility of a sensitivity and transparency, and 30-200 weight part is especially preferable.

(Component E) Basic Compound

It is preferable that the photosensitive resin composition in 1st Embodiment of this invention contains a (component E) basic compound.

(Component E) It can be used selecting arbitrarily as a basic compound from what is used by chemically amplified register. For example, aliphatic amine, aromatic amine, heterocyclic amine, quaternary ammonium hydroxide, and quaternary ammonium salt of carboxylic acid are mentioned.

Examples of the aliphatic amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, and diethanolamine. , Triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, etc. are mentioned.

As aromatic amine, aniline, benzylamine, N, N- dimethylaniline, diphenylamine, etc. are mentioned, for example.

As the heterocyclic amine, for example, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8- Oxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N '-[2- (4-morpholine) Ethyl] thio urea, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3.0] -7-undecene, and the like.

As quaternary ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexyl ammonium hydroxide, etc. are mentioned, for example. have.

As quaternary ammonium salt of carboxylic acid, tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate, etc. are mentioned, for example.

The basic compound used for this invention may be used individually by 1 type, or may use 2 or more types together.

Content of the (component E) basic compound in the photosensitive resin composition in 1st aspect of this invention is 0.001-1 weight part with respect to 100 weight part of components A from a viewpoint of compatibility of a PED characteristic and a sensitivity. It is preferable and it is more preferable that it is 0.002-0.5 weight part.

(Component F) Crosslinking Agent

It is preferable that the photosensitive resin composition in 1st Embodiment of this invention contains a (component F) crosslinking agent as needed. (Component F) A cured film can be made a stronger film by adding a crosslinking agent.

(Component F) As a crosslinking agent, the compound which has a 2 or more epoxy group or an oxetanyl group in the molecule | numerator mentioned below, the alkoxy methyl group containing crosslinking agent, or the compound which has at least 1 ethylenically unsaturated double bond can be added, for example. have.

Among these crosslinking agents, particularly preferred are compounds having two or more epoxy groups or oxetanyl groups in the molecule.

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

As a specific example of the compound which has two or more epoxy groups in a molecule | numerator, a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, an aliphatic epoxy resin, etc. are mentioned.

These are available as commercial products. For example, as bisphenol-A epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, Japan epoxy resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (EPICLON1055) As mentioned above, it is made by DIC Corporation etc., As a bisphenol F-type epoxy resin, JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan epoxy resin Co., Ltd.), EPICLON830, EPICLON835 (above, DIC Corporation) ), LCE-21, RE-602S (above, Nihon Kayaku Co., Ltd.), etc., As a phenol novolak-type epoxy resin, it is JER152, JER154, JER157S70, JER157S65 (above, Japan epoxy resin Co., Ltd. product) ), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by DIC Corporation), and the like, and examples of the cresol novolac type epoxy resin include EPICLON N-660 and EPICLON N-665. , EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, made by DIC Corporation), EOCN-1020 (more, made by Nihon Kayaku Co., Ltd.), etc. As an aliphatic epoxy resin, ADEKA RESIN E P-4080S, EP-4085S, EP-4088S (above, made by ADEKA Co., Ltd.), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, Copper PB 4700 (or higher) And Daicel Chemical Industries, Ltd.). In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above, made by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN -501, EPPN-502 (above, made by ADEKA Corporation), etc. are mentioned. These may be used alone or in combination of two or more.

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 a specific example of a compound which has two or more oxetanyl groups in a molecule | numerator, Aaronoxetane 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 epoxy group.

0.1-50 weight part is preferable with respect to 100 weight part of components A, and, as for the addition amount of the compound which has two or more epoxy groups or oxetanyl group in a molecule | numerator to 100 weight part of components A, 0.5-30 weight part is more preferable, 1-10 More preferred parts are by weight.

<Alkoxymethyl group-containing crosslinking agent>

As the alkoxy methyl group-containing crosslinking agent, alkoxy methylated melamine, alkoxy methylated benzoguanamine, alkoxy methylated glycoluril, alkoxy methylated urea and the like are preferable. These are obtained by converting methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylol group of methylolated urea into an alkoxymethyl group, respectively. Although it does not specifically limit about the kind of this alkoxy methyl group, For example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, butoxymethyl group etc. are mentioned, Especially, from a viewpoint of the generation amount of outgas, especially a methoxymethyl group Is preferred.

Among these alkoxymethyl group-containing crosslinking agents, alkoxymethylated melamine, alkoxymethylated benzoguanamine and alkoxymethylated glycoluril are mentioned as preferable crosslinking agents, and alkoxymethylated glycoluril is particularly preferable from the viewpoint of transparency.

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 (more than Mitsui Cyanamid Co., Ltd.), Nikarak MX-750, -032, -706, -708, -40, -31, -270, -280, -290 , Nicarak MS-11, Nicarak MW-30HM, -100LM, -390 (above, manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.

It is preferable that the addition amount of the alkoxy methyl group containing crosslinking agent at the time of using an alkoxy methyl group containing crosslinking agent for the photosensitive resin composition in 1st aspect of this invention is 0.05-50 weight part with respect to 100 weight part of components A, and It is more preferable that it is 10 weight part. By adding in this range, preferable alkali solubility at the time of image development, and the solvent resistance excellent in the 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 suitably. have.

As monofunctional (meth) acrylate, 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isoboroyl (meth) acrylate, 3-methoxybutyl (meth), for example Acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, etc. are mentioned.

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, bisphenoxy ethanol fluorene diacrylate, and the like.

As (meth) acrylate more than trifunctional, for example, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

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

It is preferable that the use ratio of the compound which has at least 1 ethylenically unsaturated double bond in the photosensitive resin composition in 1st aspect of this invention is 50 weight part or less with respect to 100 weight part of component A, and it is 30 weight It is more preferable that it is below. 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 cured film obtained from the photosensitive resin composition can be improved. When adding the compound which has at least 1 ethylenically unsaturated double bond, it is preferable to add the thermal radical generating agent mentioned later.

(Component G) Adhesion improver

It is preferable that the photosensitive resin composition in 1st Embodiment of this invention contains the (component G) adhesion improving agent.

The (component G) adhesion improving agent which can be used for the photosensitive resin composition in 1st aspect of this invention is an inorganic substance used as a board | substrate, for example, silicon compounds, such as a silicon, a silicon oxide, a silicon nitride, gold, copper, It is a compound which improves the adhesiveness of metals, such as aluminum, and an insulating film. Specifically, a silane coupling agent, a thiol type compound, etc. are mentioned. The silane coupling agent as the (component G) adhesion improving agent used in the present invention is for the purpose of modifying the interface, and a known one can be used without particular limitation.

As a preferable silane coupling agent, (gamma) -aminopropyl trimethoxysilane, (gamma) -aminopropyl triethoxysilane, (gamma)-glycidoxy propyl trialkoxysilane, (gamma)-glycidoxy propyl dialkoxysilane, (gamma)-, Methacryloxypropyl trialkoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyl trialkoxysilane, γ-mercaptopropyl trialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane And vinyltrialkoxysilane.

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

Moreover, the following compound can also be employ | adopted preferably.

In the above, Ph is a phenyl group.

The (G) alkoxy silane compound in the photosensitive resin composition of this invention does not specifically limit to these, A well-known thing can be used. In addition, you may use these 1 type individually or in combination of 2 or more types. These materials are effective for improving adhesion to the substrate and also for adjusting the taper angle with the substrate.

0.1-30 weight part is preferable with respect to 100 weight part of component A, and, as for content of the (component G) adhesion improving agent in the photosensitive resin composition in 1st aspect of this invention, 0.5-20 weight part is more preferable. .

(Component H) Surfactant (Fluorine-type surfactant, Silicone type surfactant, etc.)

It is preferable that the photosensitive resin composition in 1st Embodiment of this invention contains (component H) surfactant (fluorine-type surfactant, silicone type surfactant, etc.).

As surfactant, the copolymer (3) containing structural unit A and structural unit B shown below is mentioned as a preferable example. It is preferable that it is 1,000 or more and 10,000 or less, and, as for the weight average molecular weight (Mw) of the said copolymer, it is more preferable that it is 1,500 or more and 5,000 or less. The weight average molecular weight is a value of polystyrene conversion measured by gel permeation chromatography (GPC).

In the copolymer (3), R ²¹ and R ²³ each independently represent a hydrogen atom or a methyl group, R ²² represents a straight chain alkylene group having 1 to 4 carbon atoms, and R ²⁴ represents a hydrogen atom or 1 to 4 carbon atoms. An alkyl group, L represents an alkylene group having 3 to 6 carbon atoms, p and q are weight percentages indicating the polymerization ratio, p represents a numerical value of 10% by weight to 80% by weight, and q is 20% by weight or more The numerical value of 90 weight% or less is shown, r represents the integer of 1 or more and 18 or less, n represents the integer of 1 or more and 10 or less.

It is preferable that L in the structural unit B is an alkylene group represented by following formula (4).

In formula (4), R <^25> represents a C1-C4 alkyl group, From a compatibility and the wettability with respect to a to-be-coated surface, a C1-C3 alkyl group is preferable and a C2-C3 alkyl group is more preferable. Do.

Moreover, it is preferable that the sum (p + q) of p and q is p + q = 100, ie, 100 weight%.

Specific examples of fluorine-based surfactants and silicone-based surfactants include JP 62-36663, JP 61-226746, JP 61-226745, JP 62-170950, JP 63. Surfactants described in each publication, such as -34540, Japanese Patent Laid-Open No. 7-230165, Japanese Patent Laid-Open No. 8-62834, Japanese Patent Laid-Open No. 9-54432, Japanese Patent Laid-Open No. 9-5988, Japanese Patent Laid-Open No. 2001-330953, etc. These may be mentioned, and a commercially available surfactant can also be used. As a commercially available surfactant which can be used, F-top EF301, EF303 (above, Mitsubishi Material Denshi Chemical Co., Ltd.), fluoride FC430, 431 (above, Sumitomo 3M Co., Ltd. product), mega Pack F171, F173, F176, F189, R08 (above, made by DIC Corporation), Supron S-382, SC101, 102, 103, 104, 105, 106 (above, made by Asahi Glass Co., Ltd.), PolyFox Fluorine-type surfactant or silicone type surfactant, such as series (made by OMNOVA company) and KF-6012 (made by Shin-Etsu Chemical Co., Ltd.), can be mentioned. Moreover, polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone type surfactant.

These surfactant can be used individually by 1 type or in mixture of 2 or more types. Moreover, you may use together a fluorochemical surfactant and silicone type surfactant.

It is preferable that the addition amount of (component H) surfactant (fluorine-type surfactant, silicone type surfactant, etc.) in the photosensitive resin composition in 1st aspect of this invention is 10 weight part or less with respect to 100 weight part of components A. It is more preferable that it is 0.01-10 weight part, and it is more preferable that it is 0.01-1 weight part.

(Component I) Development accelerator

It is preferable that the photosensitive resin composition in 1st Embodiment of this invention contains (component I) development accelerator.

(Component I) As the development accelerator, any compound having a development promoting effect can be used, but a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group is preferable, The compound which has a carboxyl group or a phenolic hydroxyl group is more preferable, and the compound which has a phenolic hydroxyl group is especially preferable.

Moreover, 100-2,000 are preferable, as for the molecular weight of (component I) image development promoter, 150-1,500 are more preferable, 150-1,000 are especially preferable.

As an example of the development accelerator, as having an alkyleneoxy group, polyethylene glycol, monomethyl ether of polyethylene glycol, dimethyl ether of polyethylene glycol, polyethylene glycol glyceryl ester, polypropylene glycol glyceryl ester, polypropylene glycol diglyceryl ester , Polybutylene glycol, polyethylene glycol bisphenol A ether, polypropylene glycol bisphenol A ether, alkyl ether of polyoxyethylene, alkyl ester of polyoxyethylene, and compounds described in Japanese Patent Application Laid-Open No. 9-222724. Can be mentioned.

As a thing which has a carboxy group, the compound of Unexamined-Japanese-Patent No. 2000-66406, Unexamined-Japanese-Patent No. 9-6001, Unexamined-Japanese-Patent No. 10-20501, Unexamined-Japanese-Patent No. 11-338150, etc. are mentioned.

As having a phenolic hydroxyl group, JP-A-2005-346024, JP-A-10-133366, JP-A 9-194415, JP-A 9-222724, JP-A 11-171810 The compound of Unexamined-Japanese-Patent No. 2007-121766, Unexamined-Japanese-Patent No. 9-297396, Unexamined-Japanese-Patent No. 2003-43679, etc. are mentioned. Among these, 2-10 phenol compounds are preferable for a benzene ring, and 2-5 phenol compounds are more suitable for a benzene ring. As a particularly preferable thing, the phenolic compound disclosed as a dissolution promoter in Unexamined-Japanese-Patent No. 10-133366 is mentioned.

(Component I) The image development promoter may be used individually by 1 type, and can also use 2 or more types together.

As for the addition amount of the (component I) image development promoter in the photosensitive resin composition in 1st aspect of this invention, 0.1-30 weight part is preferable with respect to 100 weight part of components A from a viewpoint of a sensitivity and a residual film ratio, 0.2-20 weight part is more preferable, and it is especially preferable that it is 0.5-10 weight part.

(Component J) Antioxidant

The photosensitive resin composition in 1st Embodiment of this invention may contain antioxidant (component J).

(Component J) As antioxidant, a well-known antioxidant can be contained. (Component J) By adding antioxidant, there exists an advantage that the coloring of a cured film can be prevented, or the film thickness reduction by decomposition can be reduced, and it is excellent in heat resistance transparency.

Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites, thiosulfates, and hydroxyls. Amine 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, For example, adecastaBAO-15, adecastabe AO-18, adecastabe AO-20, adecastabe AO-23, adecastabe AO-30, adecastab AO-37, Adecastabe AO-40, Adecastabe AO-50, Adecastabe AO-51, Adecastabe AO-60, Adecastabe AO-70, Adecastave AO-80, Adecastave AO -330, Adecastabe AO-412S, Adecastabe AO-503, Adecastabe A-611, Adecastabe A-612, Adecastabe A-613, Adecastabe PEP-4C, Adecastabe PEP- 8, Adecastub PEP-8W, Adecastub PEP-24G, Adecastab PEP-36, Adecastab PEP-36Z, Adecastab HP-10, Adecastab 2112, Adecastab 260, Adecastab 522A, Adecastab1178, Adecastab 1500, Adecastab C, Adecastab 135A, Adecastab 3010, AdecastabTPP, Adecastab CDA-1, Adecastab CDA-6, Adecastab ZS -27, Adeka Tabs ZS-90, Adecastab ZS-91 (above, made by ADEKA), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF, Irganox 1035 , Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irgaphos 168, Irgamod 295 (manufactured by BASF Corporation), and the like. Among them, adecastava AO-60, adecastava AO-80, Irganox 1726, Irganox 1035, and Irganox 1098 can be suitably used.

(Component J) It is preferable that content of antioxidant is 0.1-6 weight% with respect to the total solid of the photosensitive resin composition, It is more preferable that it is 0.2-5 weight%, It is especially preferable that it is 0.5-4 weight%. . 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.

As additives other than antioxidants, various ultraviolet absorbers, metal deactivators, and the like described in "New Development of Polymer Additives (Nikkan Kogyo Co., Ltd.)", etc. are used as the photosensitive resin composition in the first embodiment of the present invention. You may add to.

(Component K) Plasticizer

The photosensitive resin composition in 1st Embodiment of this invention may contain the (component K) plasticizer.

(Component K) Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerine phthalate, dibutyl tartarate, dioctyl adipate, and triacetylglycerine.

It is preferable that it is 0.1-30 weight part with respect to 100 weight part of component A, and, as for content of the (component K) plasticizer in the photosensitive resin composition in 1st aspect of this invention, it is more preferable that it is 1-10 weight part. Do.

(Component L) Thermal radical generator

The photosensitive resin composition in 1st aspect of this invention may contain the (component L) thermal radical generating agent, and contains the ethylenically unsaturated compound like the compound which has the above-mentioned at least 1 ethylenically unsaturated double bond. In that case, it is preferable to contain the (component L) thermal radical generator.

As a thermal radical generating agent in this invention, a well-known thermal radical generating agent can be used.

A thermal radical generating agent is a compound which generate | occur | produces a radical by the energy of heat, and starts or accelerates the polymerization reaction of a polymeric compound. By adding a thermal radical generating agent, the obtained cured film becomes tough more and heat resistance and solvent resistance may improve.

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

(Component L) The thermal radical generating agent may be used individually by 1 type, and can also use 2 or more types together.

As for content of the (component L) thermal radical generating agent in the photosensitive resin composition in 1st aspect of this invention, 0.01-50 weight part is preferable with respect to 100 weight part of components A from a viewpoint of a film physical property improvement. , 0.1-20 weight part is more preferable, and it is most preferable that it is 0.5-10 weight part.

(Component M) Thermal Acid Generator

In this invention, in order to improve the film | membrane physical property in low temperature hardening, you may use the (component M) thermal acid generator.

A thermal acid generator is a compound which an acid generate | occur | produces by heat, Usually, a thermal decomposition point is a compound of the range of 130 degreeC-250 degreeC, Preferably it is 150 degreeC-220 degreeC, For example, a sulfonic acid, a carboxylic acid, a disulfide by heating. It is a compound which produces | generates low nucleophilic acid, such as ponylimide.

As the generated acid, disulfonylimide substituted with sulfonic acid, substituted alkyl carboxylic acid or arylcarboxylic acid of the electron withdrawing group or the same electron withdrawing group with strong pKa of 2 or less is preferable. Examples of the electron withdrawing group include haloalkyl groups such as halogen atoms such as fluorine atoms and trifluoromethyl groups, nitro groups and cyano groups.

Moreover, in this invention, it is also preferable to use the sulfonic acid ester which generate | occur | produces an acid by heat, without generating an acid substantially by irradiation of exposure light.

The fact that an acid does not generate | occur | produce substantially by irradiation of exposure light can be judged that there is no change in a spectrum by IR spectrum and NMR spectrum measurement before and after exposure of a compound.

It is preferable that it is 230-1,000, and, as for the molecular weight of a thermal acid generator, it is more preferable that it is 230-800.

The sulfonic acid ester which can be used by this invention may use a commercial thing, and may use the thing synthesize | combined by a well-known method. The sulfonic acid ester can be synthesized, for example, by reacting sulfonyl chloride or sulfonic anhydride with a corresponding polyhydric alcohol under basic conditions.

0.5-20 weight part is preferable with respect to 100 weight part of components A, and, as for content to the photosensitive resin composition of a thermal acid generator, 1-15 weight part is more preferable.

(Component N) Acid Extender

The photosensitive resin composition in 1st Embodiment of this invention can use a (component N) acid increasing agent for the purpose of a sensitivity improvement.

The acid increasing agent used in this invention is a compound which can generate | occur | produce an acid further by an acid catalyst reaction, and can raise the acid concentration in a reaction system, and is a compound which exists stably in the state in which an acid does not exist. Since one or more acids are increased in one reaction, such compounds accelerate the reaction with the progress of the reaction, but since the generated acid itself induces self-decomposition, the strength of the acid generated here is It is preferable that it is 3 or less as an acid decomposition constant and pKa, and it is especially preferable that it is 2 or less.

As a specific example of an acid increasing agent, Paragraph 0203-0223 of Unexamined-Japanese-Patent No. 10-1508, Paragraph 0016-0055 of Unexamined-Japanese-Patent No. 10-282642, and Japanese Patent Laid-Open No. 9-512498, page 39, 12th line The compound of 2nd line of a 47th page is mentioned.

As an acid increasing agent which can be used in this invention, it decomposes | dissolves with the acid which generate | occur | produced from the acid generator, and pKa, such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzene sulfonic acid, trifluoromethanesulfonic acid, phenylphosphonic acid, etc. The compound which produces | generates the acid of 3 or less is mentioned.

It is preferable to make content of the acid increasing agent into the photosensitive resin composition 10-1,000 weight part with respect to 100 weight part of component B from a viewpoint of the dissolution contrast of an exposure part and an unexposed part, and it is more preferable to set it as 20-500 weight part. desirable.

(Component A ") Air having structural unit (a1") which has an acidic group protected by an acid-decomposable group, and structural unit (a2 ") which has an epoxy group or an oxetanyl group, and does not have a structural unit represented by Formula (1) coalescence

The photosensitive resin composition in 2nd aspect of this invention has a structural unit (a1 ") which has an acidic group protected by the (component A") acid-decomposable group, and a structural unit (a2 ") which has an epoxy group or an oxetanyl group. Moreover, the copolymer which does not have a structural unit represented by said Formula (1) is contained. The structural unit represented by Formula (1) is explained in full detail in component C ".

Moreover, "structural unit (a1") "etc. which have an acidic group protected by an acid-decomposable group" are also called "structural unit (a1") "etc. only.

Component A "may have a structural unit (a1") individually by 1 type, or may have 2 or more types. The same applies to the structural unit (a2 ").

In addition, the component A "may have structural units other than the structural unit represented by a structural unit (a1"), a structural unit (a2 "), and Formula (1).

It is preferable that component A "is alkali insoluble or poorly soluble, and becomes resin which becomes alkali-soluble when the acid-decomposable group which has in a molecule | numerator decomposes.

As long as the component A "is kept insoluble in alkali or poorly soluble in the whole, introduction of an acidic group is not excluded. As an example of the case where an acidic group is introduce | transduced into component A", the structural unit (a3) mentioned later, for example is mentioned. The case which has "-2) etc. is mentioned.

<Structural Unit (a1 ") Having an Acid Group Protected with an Acid Degradable Group>

Component A can be made into the highly sensitive photosensitive resin composition by having the structural unit (a1 ") which has an acidic group protected by the acid-decomposable group.

As an acidic group, a carboxyl group and phenolic hydroxyl group are mentioned preferably.

(1-1) A structural unit in which the carboxyl group has a moiety protected by an acid-decomposable group

(1-1) As the structural unit having a moiety in which the carboxyl group is protected with an acid-decomposable group, the carboxyl groups contained in the structural units described in (1-1-1) and (1-1-2) described later are protected by an acid-decomposable group. It is preferable that it is a structural unit which has a residue.

(1-1-1) Structural unit having a carboxyl group

As a structural unit which has a carboxy group, the structural unit derived from unsaturated carboxylic acid etc. which have at least 1 carboxy group in a molecule | numerator, such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated tricarboxylic acid, is mentioned.

Examples of the unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, and the like. Moreover, as unsaturated dicarboxylic acid, a maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example. The acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid, Specifically, maleic anhydride, itaconic anhydride, a citraconic anhydride etc. are mentioned. In addition, the unsaturated polyhydric carboxylic acid may be mono (2- (meth) acryloyloxyalkyl) ester of polyhydric carboxylic acid, for example, succinic acid mono (2- (meth) acryloyloxyethyl), monophthalic acid (2) -(Meth) acryloyloxyethyl) etc. are mentioned. The unsaturated polyhydric carboxylic acid may be mono (meth) acrylate of the sock end dicarboxy polymer, and examples thereof include? -Carboxypolycaprolactone mono (meth) acrylate. As the unsaturated carboxylic acid, (meth) acrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used. Especially, in order to form the structural unit which has a carboxyl group from a developable viewpoint, it is preferable to use the anhydride etc. of (meth) acrylic acid or unsaturated polyhydric carboxylic acid, and it is more preferable to use (meth) acrylic acid.

The structural unit (1-1-1) which has a carboxy group may be comprised individually by 1 type, and may be comprised by 2 or more types.

(1-1-2) Structural unit which has ethylenically unsaturated group and acid anhydride residue together

It is preferable that the structural unit (1-1-2) which has an ethylenically unsaturated group and an acid anhydride residue together is a structural unit derived from the hydroxyl group which exists in the structural unit which has an ethylenically unsaturated group, and the monomer obtained by making an acid anhydride react. .

As an acid anhydride, a well-known thing can be used, Specifically, Dibasic acid anhydrides, such as maleic anhydride, a succinic anhydride, itaconic anhydride, a phthalic anhydride, tetrahydro phthalic anhydride, a hexahydro phthalic anhydride, a chloric anhydride; And acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride and biphenyltetracarboxylic anhydride. In these, phthalic anhydride, tetrahydro phthalic anhydride, or succinic anhydride is preferable from a developable viewpoint.

The reaction rate with respect to the hydroxyl group of an acid anhydride is from a developable viewpoint, Preferably it is 10-100 mol%, More preferably, it is 30-100 mol%.

(1-1) A structural unit in which the carboxyl group has a moiety protected by an acid-decomposable group

The structural unit having a residue in which the carboxyl group is protected with an acid-decomposable group is preferably a residue in which the carboxyl group contained in the structural unit described in the above (1-1-1) or (1-1-2) is protected by an acid-decomposable group. It is a structural unit having.

As an acid-decomposable group, a well-known thing can be used as an acid-decomposable group in a positive resist for KrF and a positive resist for ArF, and is not specifically limited. As the acid-decomposable group, groups (e.g., acetal functional groups such as tetrahydropyranyl group and ethoxyethyl group) which are relatively easy to decompose by acid, and groups which are relatively difficult to decompose by acid (e.g., t-butyl T-butyl-based functional groups such as ester groups and t-butyl carbonate groups) are known. As the structural unit (1-1), a structural unit having a residue in which the carboxyl group is protected by acetal or a residue in which the carboxyl group is protected by ketal is preferable in view of sensitivity, pattern shape, and formation of contact hole.

Moreover, it is more preferable from a viewpoint of a sensitivity that a carboxy group is a residue protected by the acetal or ketal represented by a formula (A1) among acid-decomposable groups. When the carboxyl group is a residue protected by acetal or ketal represented by the formula (A1), the entirety of the residue has a structure of -C (= O) -O-CR ¹ R ² (OR ³ ).

(In formula (A1), R <^1> and R <^2> represents a hydrogen atom, an alkyl group, or an aryl group each independently, At least one of R <^1> and R <^2> is the said alkyl group or an aryl group, and R <^3> is , An alkyl group, or an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether)

In formula (A1), as said alkyl group in R <^1> , R <^2> and R <^3> , any of linear, branched, or cyclic | annular may be sufficient.

As a linear or branched alkyl group, it is preferable that it is C1-C12, It is more preferable that it is C1-C6, It is more preferable that it is C1-C4. Specifically, a methyl group and an ethyl group can be illustrated preferably.

As a cyclic alkyl group, it is preferable that it is C3-C12, It is more preferable that it is C4-C8, It is more preferable that it is C4-C6. Specifically, a cyclohexyl group can be illustrated preferably.

In Formula (A1), as said aryl group in R <^1> , R <^2> and R <^3> , it is preferable that it is C6-C12, and it is more preferable that it is C6-C10. The said aryl group may have a substituent, and as a substituent, a C1-C6 alkyl group can be illustrated preferably. As an aryl group, a phenyl group, a tolyl group, a xylyl group, a cumenyl group, 1-naphthyl group etc. can be illustrated, for example, A phenyl group is preferable.

In addition, R <^1> , R <^2> and R <^3> in Formula (A1) combine with each other, and can combine with the carbon atom to which they couple | bond together, and can form a ring. Examples of the ring structure when R ¹ and R ² , R ¹ and R ^3, or R ² and R ³ 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.

In formula (A1), one of R ¹ and R ² is preferably a hydrogen atom or a methyl group.

As a radically polymerizable monomer used in order to form the structural unit which has a residue represented by Formula (A1), a commercially available thing may be used, for example, the method of Paragraph 0025-0026 of Unexamined-Japanese-Patent No. 2009-098616, etc. In addition, you may use what synthesize | combined by a well-known method.

As the structural unit (1-1) having a residue in which the carboxyl group is protected with an acid-decomposable group, the structural unit represented by the formula (A2) is more preferable.

(In formula (A2), R <^1> and R <^2> represents a hydrogen atom, an alkyl group, or an aryl group each independently, At least one of R <^1> and R <^2> is an alkyl group or an aryl group, and R <^3> may have a substituent An alkyl group, a cycloalkyl group, or an aryl group, R ¹ or R ² and R ³ may be linked to each other to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group.

Had formula (A2) of, R ¹ ~ R ³ are, the same formula and R ¹ ~ R ³ in (A1), as a preferred range.

In formula (A2), R <^1> and R <^2> has a hydrogen atom or a C1-C3 alkyl group, and a hydrogen atom or a methyl group is preferable. R ³ is preferably a linear, branched or cyclic alkyl group having 6 or less carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and more preferably an ethyl group, a cyclohexyl group, or a benzyl group. As cyclic ether which R <^1> or R <^2> and R <^3> connected, the tetrahydropyranyl group and the tetrahydrofuranyl group are preferable. R ⁴ is preferably a methyl group. X is preferably a single bond or a phenylene group.

As a preferable specific example of structural unit (1-1), the following structural unit can be illustrated. In addition, R represents a hydrogen atom or a methyl group.

As structural unit (1-1), the residue which the carboxy group was protected by the tertiary alkyl group represented by Formula (A3) may be sufficient. Compared with the residue protected by acetal or ketal, although it is inferior in sensitivity, it is preferable at the point which is excellent in storage stability. Further, when the carboxyl group of the protected moiety with a tertiary alkyl group represented by the formula (A3), as a whole of the residue, -C (= O) is a structure of ^{-O-CR 1 R 2 R 3} .

In formula (A3), R ¹ , R ² and R ³ each independently represent an alkyl group or an aryl group, and any two of R ¹ , R ² and R ³ may be bonded to each other to form a ring. Specific examples of the alkyl group and the aryl group in R ¹ to R ³ of the formula (A3) are the same as the specific examples of the alkyl group and the aryl group in the formula (A1).

In a formula (A3), as a preferable example, the combination of R < ¹ > R <^2> = R < ³ > methyl group, R <^1> = R <^2> = methyl group, and the combination of R < ³ > benzyl group can be illustrated.

(1-2) Structural unit in which a phenolic hydroxyl group has the residue protected by the acid-decomposable group

(1-2) As a structural unit which has the residue which the phenolic hydroxyl group protected by the acid-decomposable group, the structural unit which has the residue which protected the structural unit which has the (1-2-1) phenolic hydroxyl group by an acid-decomposable group is preferable. Do.

(1-2-1) Structural unit having phenolic hydroxyl group

As a structural unit which has a phenolic hydroxyl group, the structural unit in hydroxy styrene-type structural unit and novolak-type resin is mentioned. Among the structural units having a phenolic hydroxyl group, the structural unit represented by the formula (A4) is preferable from the viewpoint of transparency and sensitivity.

(In formula (A4), R <^20> represents a hydrogen atom or a methyl group, R <^21> represents a single bond or a bivalent coupling group, R <^22> represents a halogen atom or an alkyl group each independently, and a represents the integer of 1-5. B represents an integer of 0 to 4, and a + b is 5 or less)

As a bivalent coupling group of R <^21> , the ester bond (-COO-) and alkylene group which a carbon atom couple | bonds with a main chain can be illustrated, A linear or branched C1-C6 alkylene group is preferable. In the case of -COO-, since sensitivity can be improved and transparency of a cured film can be improved, it is preferable. Especially, it is preferable that R <^21> is a single bond and ester bond. In addition, the said divalent coupling group may have a substituent, and a halogen atom, a hydroxyl group, an alkoxy group etc. are mentioned as a substituent.

In addition, although a shows the integer of 1-5, it is preferable that a is 1 or 2, and it is more preferable that a is 1 from a viewpoint of the effect of this invention or manufacture point.

In addition, when the bond position of the hydroxyl group in a benzene ring makes the carbon atom couple | bonded with R <^{21> a} reference | standard (one position), it is preferable to couple | bond at four positions.

Although b shows the integer of 0-4, it is preferable that b is 0 from a viewpoint of the effect of this invention and the point which manufacture is easy.

(1-2) Structural unit in which a phenolic hydroxyl group has the residue protected by the acid-decomposable group

It is preferable that the phenolic hydroxyl group of the structural unit which has a phenolic hydroxyl group protected by the acid-decomposable group is a structural unit which has the residue protected by the acid-decomposable group (1-2-1). Do.

As an acid-decomposable group, a well-known thing can be used as mentioned above, It does not specifically limit.

Even if the phenolic hydroxyl group is a residue protected by an acid-decomposable group, the phenolic hydroxyl group is a structural unit having a residue protected by acetal or ketal, and the basic physical properties of the resist, in particular, the sensitivity and pattern shape, the storage stability of the photosensitive resin composition, It is preferable from a viewpoint of formability. Moreover, it is more preferable from a viewpoint of a sensitivity that a phenolic hydroxyl group is a residue protected by the acetal or ketal represented by Formula (A1) among the residues in which a phenolic hydroxyl group was protected by the acid-decomposable group. In this case, as a whole of the residue, the structure is -Ar-O-CR ¹ R ² (OR ³ ). Ar represents an arylene group.

As a preferable example of the acetal ester structure of a phenolic hydroxyl group, the combination of R < ¹ > R < ² > R < ³ > methyl group or R < ¹ > R <^2> = methyl group and R < ³ > benzyl group can be illustrated.

As a specific example of the acetal protecting group and ketal protecting group of a phenolic hydroxyl group, 1-alkoxyalkyl group is mentioned, For example, 1-ethoxyethyl group, 1-methoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxy Ethyl group, 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) Ethyl group, 1-benzyloxyethyl group, etc. are mentioned, Especially, 1-ethoxyethyl group is preferable. These may be used alone or in combination of two or more.

The constitutional unit having a residue in which the carboxyl group is protected with an acid-decomposable group is faster than the structural unit having a residue in which the phenolic hydroxyl group is protected with an acid-decomposable group. Therefore, in the case where it is desired to develop rapidly, a structural unit having a residue in which the carboxyl group is protected with an acid-decomposable group is preferable. On the contrary, when it is desired to slow development, it is preferable to use a structural unit having a moiety in which a phenolic hydroxyl group is protected with an acid-decomposable group.

<Structural unit (a2 ") having an epoxy group or an oxetanyl group>

Component A "contains the structural unit (a2") which has an epoxy group or an oxetanyl group.

The structural unit (a2 ") should just have at least one epoxy group or an oxetanyl group in one structural unit, and it may contain 1 or more epoxy groups, 1 or more oxetanyl groups, 2 or more epoxy groups, or 2 or more oxetas Although it may have a nil group, it is not specifically limited, It is preferable to have 1-3 epoxy groups and / or oxetanyl groups in total, It is more preferable to have 1 or 2 epoxy groups and / or oxetanyl groups in total, Epoxy group or It is more preferable to have one oxetanyl group.

As a structural unit (a2 "), it is preferable that it is a structural unit which has an oxetanyl group from a viewpoint of a sensitivity and storage stability.

In addition, as a combination of the structural unit (a1 ") and the structural unit (a2") in component A, a structural unit (a1 ") is a structural unit which has a carboxy group protected by the acid-decomposable group, and a structural unit (a2") is The combination which is a structural unit which has an oxetanyl group is preferable.

As a group which has an oxetanyl group, if it has an oxetane ring, there is no restriction | limiting in particular, The (3-ethyloxetan-3-yl) methyl group can be illustrated preferably.

As a specific example of the radically polymerizable monomer used in order to form the structural unit which has an epoxy group, it is the glycidyl acrylate, the glycidyl methacrylate, the (alpha)-ethyl acrylate glycidyl, the (alpha)-n-propyl acrylate, for example. 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, paragraph 0031 of Patent No. 4168443 The compound containing the alicyclic epoxy skeleton as described in -0035 is mentioned.

As an example of the radically polymerizable monomer used in order to form the structural unit which has an oxetanyl group, (meth) acrylic acid ester etc. which have the oxetanyl group of Paragraph 0011 of Unexamined-Japanese-Patent No. 2001-330953-0016, etc. are mentioned, for example. Can be mentioned.

As an example of the radically polymerizable monomer used in order to form the structural unit which has an epoxy group and / or an oxetanyl group, it is preferable that they are a monomer containing a methacrylic acid ester structure, and a monomer containing an acrylate ester structure.

Among these monomers, more preferably, the compound containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of 4168443 and the oxetanyl group described in paragraphs 0011 to 0016 of JP 2001-330953 A ( It is meta) acrylic acid ester, and it is (meth) acrylic acid ester which has an oxetanyl group of Paragraph 0011 of Unexamined-Japanese-Patent No. 2001-330953-0016. Among these, preferred are 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, acrylic acid (3-ethyloxetan-3-yl) methyl, and methacrylic acid (3-ethyl Oxetan-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 a structural unit (a2 "), the structural unit represented by following (a2" -1)-(a2 "-6) can be illustrated.

<Other structural units>

Component A "is a structural unit other than the said structural unit (a1") and the said structural unit (a2 ") in the range which does not prevent the effect of this invention (henceforth an enemy" structural unit (a3 ")"). It may contain.

Although it does not specifically limit as a radically polymerizable monomer used in order to form a structural unit (a3 "), For example, Paragraph 0021 of Unexamined-Japanese-Patent No. 2004-264623-the compound of 0024 can be mentioned (however, it mentioned above) Constituent units (a1 ") and constituent units (a2") are excluded).

Preferable aspects as the radical polymerizable monomer used for forming the preferred structural unit (a3 ") and the structural unit (a3") are explained concretely.

[Structural unit (a3 "-1) having a styrene structure]

It is preferable that component A "has at least a structural unit (structural unit (a3" -1)) represented by Formula (a3 "-1).

(Wherein R ³ represents a hydrogen atom or a methyl group)

It is preferable that R <^3> in said Formula (a3 "-1) is a hydrogen atom from a viewpoint of the uniformity of the superposition | polymerization rate of each monomer at the time of superposition | polymerization.

As a monomer which forms the structural unit represented by said formula (a3 "-1), the compound represented by a following formula (a3'-1) can be illustrated preferably.

Expression of the R ³ in (a3'-1) is, and R ³ and agreed in the formula (a3 "-1), as a preferred aspect.

It is preferable that the structural unit represented by a formula (a3 "-1) superposes | polymerizes and forms the compound represented by said formula (a3'-1). The compound represented by said formula (a3'-1) is polymerized When formed, the structural unit represented by formula (a3 "-1) in component A" is also a monomer unit represented by formula (a3 "-1).

[Structural unit (a3 "-2) having a carboxyl group and / or acid anhydride structure)

It is preferable that component A "has a structural unit (a3" -2) which has a carboxyl group and / or an acid anhydride structure, and it is more preferable to have a structural unit (a3 "-2-1) which has a carboxyl group.

As a monomer which forms the structural unit (a3 "-2-1) which has the said carboxyl group, For example, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, vinyl benzoic acid, etc. Can be mentioned.

Among these, (meth) acrylic acid is preferable and methacrylic acid is especially preferable.

Moreover, as a structural unit (a3 "-2-1) which has a carboxy group, it is preferable that it is a structural unit represented by a following formula (a3" -2-1-1) or a formula (a3 "-2-1-2), And a structural unit represented by the following formula (a3 "-2-1-1) are particularly preferable.

In addition, component A "is a structural unit (a3" -2) which has a carboxyl group and / or an acid anhydride structure, It is preferable to have a structural unit (a3 "-2-2) derived from unsaturated carboxylic acid and / or unsaturated carboxylic anhydride. Do.

As an unsaturated carboxylic acid and / or unsaturated carboxylic anhydride which has radical polymerizability which can be used for manufacture of component A ", For example, monocarboxylic acid, dicarboxylic acid, anhydride of dicarboxylic acid, mono ((meth) acryloyl of polyhydric carboxylic acid. The oxyalkyl) ester, the mono (meth) acrylate of the polymer which has a carboxyl group and a hydroxyl group at a sock end, the polycyclic compound which has a carboxyl group, its anhydride, etc. are mentioned.

As these specific examples, As monocarboxylic acid, For example, acrylic acid, methacrylic acid, crotonic acid, etc. which were mentioned above; As the dicarboxylic acid, for example, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like; As anhydride of dicarboxylic acid, For example, anhydride of the compound illustrated as said dicarboxylic acid; As mono [(meth) acryloyloxyalkyl] ester of polyhydric carboxylic acid, For example, succinic acid mono (2- (meth) acryloyloxyethyl), phthalic acid mono (2- (meth) acryloyloxyethyl), etc. Can be mentioned.

[Structural unit (a3 "-3) having an alicyclic structure]

It is preferable that component A "has a structural unit (a3" -3) which has an alicyclic structure from a viewpoint of an electrical property.

As a structural unit (a3 "-3) which has an alicyclic structure, it is preferable that it is a structural unit represented by a following formula (a3" -3).

(Wherein R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an alicyclic group, and L represents a single bond, an alkylene group or an alkyleneoxy group)

R ⁴ in the formula (a3 ″ -3) is preferably a methyl group from the viewpoint of uniformity of the polymerization rate of each monomer during polymerization.

It is preferable that R <^5> in said formula (a3 "-3) is a C5-C18 alicyclic group, It is more preferable that it is a C5-C12 alicyclic group, A cyclohexyl group, 2-methylcyclohexyl group, Tri It is especially preferable that it is a cyclo [5.2.1.0 ^2,6 ] decane-8-yl group or an isoboroyl group.

Moreover, it is preferable that the aliphatic ring in the said alicyclic group is a condensed ring and / or a temporary exchange, and it is especially preferable that it is a tricyclo [5.2.1.0 ^2,6 ] decane ring.

It is preferable that L in said Formula (a3 "-3) is a single bond, a C1-C10 alkylene group, an ethyleneoxy group, or a propyleneoxy group, and it is more preferable that it is a single bond, a methylene group, or an ethyleneoxy group.

As a monomer which forms the structural unit (a3 "-3) which has the said alicyclic structure, the (meth) acrylate compound which has alicyclic structure can be illustrated preferably, The compound represented by a following formula (a3'-3) is mentioned. More preferably, it can illustrate.

Equation ^{(a3'-3) R 4,} R 5 and L, and R ^4, R ⁵ and L respectively, and agree in the formula (a3 "-3) in the, as a preferred aspect.

Specific examples of the compound represented by formula (a3'-3) include cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl ( Meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethyl (meth) acrylate, isoboroyl (meth) acrylate, etc. are mentioned.

Especially, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate is the most preferable.

In addition, in this invention, "(meth) acryl" is the word containing either one of "acryl" and "methacryl", or both, and "(meth) acrylate" is "acrylate" And "methacrylate" means either one or both of them.

[Structural unit (a3 "-4) having a carboxylic acid alkyl ester residue]

It is preferable that component A "has a structural unit (a3" -4) which has a carboxylic acid alkyl ester residue from a transparency viewpoint.

As a structural unit (a3 "-4) which has a carboxylic acid alkyl ester residue, it is preferable that it is a structural unit represented by a following formula (a3" -4).

(In formula, R <^6> represents a hydrogen atom or a methyl group, and R <^7> represents a C1-C12 alkyl group.)

R ⁶ in the formula (a3 ″ -4) is preferably a methyl group from the viewpoint of the uniformity of the polymerization rate of each monomer during polymerization.

It is preferable that R <^7> in said formula (a3 "-4) is a C1-C8 alkyl group, It is more preferable that it is a C1-C4 alkyl group, It is especially preferable that it is a methyl group. Moreover, said R ⁷ The alkyl group in may be linear or may have a branch.

As a monomer which forms the structural unit (a3 "-4) which has the said carboxylic acid alkyl ester residue, an alkyl (meth) acrylate compound can be illustrated preferably, and the compound represented by a following formula (a3'-4) is more preferable. It can be illustrated preferably.

Equation (a3'-4) R ⁶ and R ⁷ in the can, and R ⁶ and R ⁷ and each agreement in the formula (a3 "-4), as a preferred aspect.

[Structural Unit (a3 "-5) Having Maleimide Residue]

It is preferable that component A "has a structural unit (a3" -5) which has a maleimide residue from a thermosetting viewpoint.

As a structural unit (a3 "-5) which has a maleimide residue, it is preferable that it is a structural unit represented by a following formula (a3" -5).

(In formula, R <^8> represents group represented by an alkyl group, a cycloalkyl group, an aryl group, or following formula (S ").)

(In formula, x represents the integer of 2-10, and a dashed part shows the bonding position of the nitrogen atom in Formula (a3 "-5).)

It is preferable that R <^8> in said Formula (a3 "-5) is group represented by a C1-C12 alkyl group, a C5-C12 cycloalkyl group, a C6-C12 aryl group, or the said Formula (S"). And it is more preferable that it is a group represented by a benzyl group, a cyclohexyl group, a phenyl group, or said Formula (S ").

It is preferable that it is 2-8, and, as for x in said Formula (S "), it is more preferable that it is 2-7.

As a monomer which forms the structural unit (a3 "-5) which has the said maleimide residue, the compound represented by a following formula (a3'-5) can be illustrated preferably.

Expression of the R ⁸ in (a3'-5) is, and R ⁸ and copper in the formula (a3 "-5), like a preferred embodiment.

Specific examples of the compound represented by formula (a3'-5) include phenylmaleimide, cyclohexyl maleimide, benzyl maleimide, N-succinimidyl-3-maleimide benzoate and N-succinimidyl-4-male Midbutylate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide and the like. Especially, N-cyclohexyl maleimide and N-phenylmaleimide are especially preferable.

[Structural Unit (a3 "-6) Having a Hydroxy Group]

It is preferable that component A "has the structural unit (a3" -6) which has a hydroxyl group from a developable viewpoint.

As a structural unit (a3 "-6) which has a hydroxyl group, it is preferable that it is a structural unit represented by a following formula (a3" -6).

(In formula, R <^9> represents a hydrogen atom or a methyl group, y represents the integer of 2-11.)

R ⁹ in the formula (a3 ″ -6) is preferably a methyl group from the viewpoint of uniformity of the polymerization rate of each monomer during polymerization.

It is preferable that it is an integer of 2-8, y in said Formula (a3 "-6) is more preferable, It is more preferable that it is an integer of 2-4, It is especially preferable that it is 2.

As a monomer which forms the structural unit (a3 "-6) which has the said hydroxyl group, the compound represented by a following formula (a3'-6) can be illustrated more preferable.

Formula R ⁹ and y in the (a3'-6) has, and R ⁹ and y and each agreement in the formula (a3 "-6), as a preferred aspect.

[Structural Unit (a3 "-7) Having Polyether Structure]

It is preferable that component A "has the structural unit (a3" -7) which has a polyether structure from a developable viewpoint.

As a structural unit (a3 "-7) which has a polyether structure, it is preferable that it is a structural unit represented by a following formula (a3" -7-1) or a formula (a3 "-7-2).

(Wherein R ¹⁰ represents a hydrogen atom or a methyl group, R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a phenyl group, X represents a single bond or a divalent linking group, and m and n each independently, Represents an integer from 0 to 50, except that m and n do not become 0 together)

R ¹⁰ in the formula (a3 "-7-1) and the formula (a3" -7-2), in terms of the uniformity of the polymerization rate of the monomers at the time of polymerization, a methyl group is preferred.

It is preferable that R <^11> in said Formula (a3 "-7-1) and said Formula (a3" -7-2) is a C1-C8 alkyl group or a phenyl group, It is more preferable that it is a C1-C4 alkyl group It is preferable and it is more preferable that it is a methyl group. In addition, the alkyl group in said R <^11> may be linear or may have a branch.

It is preferable that X in said Formula (a3 "-7-1) and said Formula (a3" -7-2) is a single bond or a C1-C50 bivalent coupling group, A single bond or C1-C20 It is more preferable that it is an alkylene group, and it is still more preferable that it is a single bond.

It is preferable that m and n in said Formula (a3 "-7-1) and said Formula (a3" -7-2) are each independently an integer of 0-40, and it is more preferable that it is an integer of 0-20. .

Further, the formula (a3 -C in the "-7-1) and the formula _{(a3" -7-2) 3 H 6} O- _{is, -CH (CH 3) CH 2} O- or -CH ₂ CH (CH ₃₎ O- is preferably a.

As a monomer which forms the structural unit (a3 "-7) which has the said polyether structure, the compound represented by a following formula (a3'-7-1) or a formula (a3'-7-2) can be illustrated more preferable. Can be.

R <^10> , R <^11> , X, m, and n in Formula (a3'-7-1) and Formula (a3'-7-2) are said Formula (a3 "-7-1) and Formula (a3" It is synonymous with R <^10> , R <^11> , X, m, and n in -7-2), and a preferable aspect is also the same.

[Structural unit (a3 "-8) having a furanyl group, tetrahydrofuranyl group, pyranyl group or tetrahydropyranyl group]

It is preferable that component A "has structural unit (a3" -8) which has furanyl group, tetrahydrofuranyl group, pyranyl group, or tetrahydropyranyl group other than the said structural unit (a1 ").

As furanyl group, tetrahydrofuranyl group, pyranyl group, or tetrahydropyranyl group in the said structural unit (a3 "-8), 2-furanyl group, 3-furanyl group, furfuryl group, tetrahydrofurfuryl group, 3 -Tetrahydrofuranyl group, 2-4H-pyranyl group, 3-2H-pyranyl group, 3-4H-pyranyl group, 4-2H-pyranyl group, 4-4H-pyranyl group, 3-tetrahydrofuranyl group, and, 4-tetrahydrofuranyl group etc. are mentioned.

As a monomer which forms the said structural unit (a3 "-8), the ethylenically unsaturated compound which has at least 1 frame | skeleton selected from the group which consists of a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, and a pyran skeleton is mentioned. have.

Specifically, for example, as an ethylenically unsaturated compound which has a tetrahydrofuran skeleton, tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy propionate tetrahydrofurfuryl ester, (meth) acrylic acid tetrahydrofuran 3-yl ester, etc .;

As an ethylenically unsaturated compound which has a furan skeleton, 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1- (2-furanyl) butane-3- En-2-one, 1- (2-furanyl) butan-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6 Furan-2-ylhex-1-en-3-one, acrylic acid 2-furan-2-yl-1-methylethylester, 6- (2-furyl) -6-methyl-1-hepten-3-one Etc;

As an unsaturated compound containing a tetrahydropyran skeleton, (tetrahydropyran-2-yl) methylmethacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) octo-1-ene-3 -One, 2-methacrylic acid tetrahydropyran-2-yl ester, 1- (tetrahydropyran-2-oxy) butyl-3-en-2-one and the like;

Unsaturated compounds containing a pyran skeleton include 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyrone and 4- (1,5-dioxa-6-oxo -7-octenyl) -6-methyl-2-pyrone etc. are mentioned.

Among these, tetrahydrofurfuryl (meth) acrylate is preferable and tetrahydrofurfuryl methacrylate is more preferable.

These structural units (a3 ") may be used individually by 1 type in component A", or may have 2 or more types.

From a viewpoint of storage stability and dry etching tolerance, it is preferable that content of the monomer unit which forms the structural unit (a1 ")-structural unit (a3") in component A "is the following range.

10-80 mol% is preferable and, as for the content rate of the monomer unit which forms a structural unit (a1 ") among all the monomer units which comprise component A", 30-80 mol% is more preferable.

10-60 mol% is preferable and, as for the content rate of the monomer unit which forms a structural unit (a2 ") among all the monomer units which comprise component A", 20-60 mol% is more preferable.

In all the monomer units which comprise component A ", 0-50 mol% is preferable and, as for the content rate of the monomer unit which forms a structural unit (a3"), 10-45 mol% is more preferable.

Moreover, it is preferable that it is 2,000-100,000, as for the polystyrene conversion weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) of component A ", 3,000-50,000 are more preferable, 4,000-30,000 are especially preferable.

The photosensitive resin composition in 2nd aspect of this invention can contain component A "individually by 1 type or in combination of 2 or more types.

It is preferable that content of component A "in the photosensitive resin composition in 2nd aspect of this invention is 20 to 90 weight% with respect to the total solid of the photosensitive resin composition, and it is more that it is 30 to 70 weight% Moreover, solid content of the photosensitive resin composition represents the quantity except volatile components, such as a solvent.

Moreover, the photosensitive resin composition in 2nd Embodiment of this invention may use together resin other than component A "and component C" in the range which does not prevent the effect of this invention. However, it is preferable that content of resin other than component A "and the component C" is smaller than content of component A "and content of component C" from a developable viewpoint.

(Component B ") Photoacid Generator

The photosensitive resin composition in 2nd aspect of this invention contains the (component B ") photo-acid generator (it is only called" photo acid generator ").

As a photo-acid generator used by this invention, although the compound which responds to actinic light of wavelength 300nm or more, Preferably wavelength 300-450nm, and produces | generates an acid is preferable, It is not limited to the chemical structure. Moreover, also about the photo-acid generator which does not directly react to actinic light of wavelength 300nm or more, if it is a compound which responds to actinic light of wavelength 300nm or more by using together with a sensitizer and produces | generates an acid, it will be used conveniently in combination with a sensitizer. Can be.

As the photoacid generator used in the present invention, a photoacid generator that generates an acid having an acid decomposition constant (pKa) of 4 or less is preferable, and a photoacid generator that generates an acid of 3 or less pKa is more preferable.

Moreover, about pKa, a value can be calculated | required by a well-known measuring method, a well-known calculation method, and / or a literature value.

Examples of photoacid generators having a pKa of the generated acid of 4 or less include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imidesulfonate compounds, and oximes. Sulfonate compounds; and the like. Among these, it is preferable to use an oxime sulfonate compound from an insulating viewpoint. These photoacid generators can be used individually by 1 type or in combination of 2 or more types.

As these specific examples, the compound illustrated in the said component B can be illustrated similarly also in the component B ", and the same also about a preferable compound.

It is preferable that content of the (component B ") photoacid generator in the photosensitive resin composition in 2nd aspect of this invention is 0.1-10 weight part with respect to 100 weight part of component A", and it is 0.5-10 weight part More preferably, it is more preferable that it is 2-7 weight part.

(Component C ") A polymer having a structural unit represented by formula (1)

The photosensitive resin composition in the 2nd aspect of this invention contains the polymer which has a structural unit (structural unit (1)) represented by (component C ") Formula (1).

In addition, component A "does not have a structural unit represented by Formula (1).

(In formula, R <^1> represents a hydrogen atom or a methyl group, R <^2> represents a C1-C6 alkyl group, a C1-C6 alkoxy group, a hydroxyl group, or a 2, 3- epoxy propoxymethyl group each independently, and n Represents an integer of 1 to 5)

As R <^1> in Formula (1), it is preferable that it is a hydrogen atom from a viewpoint of reactivity and cost.

As R <^2> in Formula (1), a C1-C6 alkoxy group, a hydroxyl group, or a 2, 3- epoxy propoxymethyl group is preferable, A methoxy group, a hydroxyl group, or a 2, 3- epoxy propoxymethyl group is more preferable. And, 2,3-epoxypropoxymethyl group is particularly preferred.

In addition, although the o-position, m-position, or p-position may be sufficient with respect to the benzene ring which the carbon atom which R <^1> couple | bonded bonds with R <^2> in Formula (1), it is preferable that it is p-position.

As n in Formula (1), it is preferable that it is 1-3, It is more preferable that it is 1 or 2, It is especially preferable that it is 1.

Among these, it is preferable that it is a structural unit represented by following formula (1-1) as a structural unit represented by Formula (1).

(Wherein R ¹ represents a hydrogen atom or a methyl group)

As R <^1> in Formula (1-1), it is preferable that it is a hydrogen atom from a viewpoint of reactivity and cost.

<Other structural units>

Component C "may be a structural unit other than the structural unit represented by Formula (1), and may have structural unit (a1")-structural unit (a3 ") mentioned above in component A".

It is preferable that component C "contains the structural unit (a3" -2-1) which has the said carboxyl group from a developable viewpoint.

0-40 mol% is preferable and, as for the content rate of the monomeric unit which forms the structural unit (a3 "-2-1) which has a carboxy group among all the monomeric units which comprise component C", 1-20 mol% is more preferable. Do.

In addition, component C "is another structural unit, The structural unit (a1") which has an acidic group protected by an acid-decomposable group, The structural unit (a2 ") which has an epoxy group or an oxetanyl group, and the structural unit (a3) which has a styrene structure "-1), structural unit (a3" -3) which has alicyclic structure, structural unit (a3 "-4) which has a carboxylic acid alkyl ester residue, structural unit (a3" -6) which has a hydroxyl group, and furanyl group, It is preferable to have at least 1 structural unit selected from the group which consists of a structural unit (a3 "-8) which has a tetrahydrofuranyl group, a pyranyl group, or a tetrahydropyranyl group.

From the viewpoint of storage stability and dry etching resistance, the content of the monomer unit forming the structural unit (1) in the component C "is preferably in the following ranges. The component C " Even if it has only a species, you may have a 2 or more types of structural unit (1).

20-100 mol% is preferable and, as for the content rate of the monomer unit which forms the structural unit (1) among all the monomer units which comprise component A ", 30-80 mol% is more preferable.

The photosensitive resin composition in 2nd aspect of this invention can contain component C "individually by 1 type or in combination of 2 or more types.

As for content of component C "in the photosensitive resin composition in 2nd aspect of this invention, 1-2,000 weight part is preferable with respect to 100 weight part of component A", 5-200 weight part is more preferable, 8- 150 parts by weight is most preferred.

(Component D ") Solvent

The photosensitive resin composition in the 2nd aspect of this invention contains the (component D ") solvent.

It is preferable that the photosensitive resin composition in 2nd Embodiment of this invention is prepared as the solution which melt | dissolved the component A "-component C" which are essential components, and the optional component mentioned later in the (component D ") solvent. .

As a solvent used for the photosensitive resin composition of this invention, a well-known solvent can be used and the solvent illustrated in the said component D can be illustrated similarly.

Especially, propylene glycol monoalkyl ether acetates and diethylene glycol dialkyl ethers are preferable.

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

The solvent which can be used for this invention can use together single 1 type or 2 types.

It is preferable that content of component D "in the photosensitive resin composition in 2nd aspect of this invention is 50-3,000 weight part with respect to 100 weight part of component A", It is more preferable that it is 100-2,000 weight part, 150 It is more preferable that it is-1500 parts by weight.

The photosensitive resin composition in 2nd Embodiment of this invention may contain other components arbitrary as said component A "-component D" as an essential component. Optional components include (component E '') sensitizer, (component F ") crosslinking agent, (component G") surfactant, (component H ") adhesion improving agent, (component I") basic compound, and (component J ") development An accelerator, a (component K ") antioxidant, a (component L") plasticizer, etc. are mentioned. The additive that can be used in the present invention is not limited to these, and various additives known in the art may be used.

(Component E ") sensitizer

In the combination with the above-mentioned component B ", the photosensitive resin composition of this invention may add a (component E") sensitizer in order to accelerate the decomposition | disassembly.

A sensitizer absorbs actinic light or a radiation and will be in an electronic excited state. The sensitizer which has become an electron-excited state is brought into contact with photoacid generators such as component B "to cause electron transfer, energy transfer, heat generation, etc. As a result, the photoacid generator produces a chemical change and decomposes to generate an acid. do.

As an example of a preferable sensitizer, the compound illustrated as said component D can be illustrated similarly, and a preferable compound is also the same.

A sensitizer may use a commercially available thing and may be synthesize | combined by a well-known synthetic method.

The addition amount of the sensitizer is preferably 20 to 300 parts by weight, and particularly preferably 30 to 200 parts by weight with respect to 100 parts by weight of component B '' from the viewpoint of both sensitivity and transparency.

(Component F ") Crosslinking Agent

It is preferable that the photosensitive resin composition in 2nd aspect of this invention contains a (component F ") crosslinking agent as needed. (Component F") The film which hardened a cured film by adding a crosslinking agent. You can do

(Component F ") As a crosslinking agent, the compound which has two or more epoxy groups or oxetanyl group in a molecule | numerator, the alkoxy methyl group containing crosslinking agent, or the compound which has at least 1 ethylenically unsaturated double bond can be added, for example.

Among these crosslinking agents, particularly preferred are compounds having two or more epoxy groups or oxetanyl groups in the molecule.

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

As a specific example of the compound which has two or more epoxy groups in a molecule | numerator, a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, an aliphatic epoxy resin, etc. are mentioned.

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

1-50 weight part is preferable with respect to 100 weight part of component A ", and, as for the addition amount of the compound which has two or more epoxy groups or an oxetanyl group in a molecule | numerator, 3-30 weight part is more preferable.

<Alkoxymethyl group-containing crosslinking agent>

As the alkoxy methyl group-containing crosslinking agent, alkoxy methylated melamine, alkoxy methylated benzoguanamine, alkoxy methylated glycoluril, alkoxy methylated urea and the like are preferable.

It is preferable that the addition amount of the alkoxy methyl group containing crosslinking agent at the time of using an alkoxy methyl group containing crosslinking agent in the photosensitive resin composition in 2nd aspect of this invention is 0.05-50 weight part with respect to 100 weight part of components A ", and is 0.5 It is more preferable that it is-10 weight parts By adding in this range, preferable alkali solubility at the time of image development and the solvent resistance used as the 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 suitably. have.

(Component G ") Surfactant (Fluorine-type surfactant, Silicone type surfactant, etc.)

It is preferable that the photosensitive resin composition in 2nd Embodiment of this invention contains (component G ") surfactant (fluorine-type surfactant, silicone type surfactant, etc.).

Specific examples of fluorine-based surfactants and silicone-based surfactants include JP 62-36663, JP 61-226746, JP 61-226745, JP 62-170950, JP 63. Surfactants described in each publication, such as -34540, Japanese Patent Laid-Open No. 7-230165, Japanese Patent Laid-Open No. 8-62834, Japanese Patent Laid-Open No. 9-54432, Japanese Patent Laid-Open No. 9-5988, Japanese Patent Laid-Open No. 2001-330953, etc. These may be mentioned, and a commercially available surfactant can also be used. As a commercially available surfactant which can be used, F-top EF301, EF303 (above, Mitsubishi Material Denshi Chemical Co., Ltd.), fluoride FC430, 431 (above, Sumitomo 3M Co., Ltd. product), mega Pack F171, F173, F176, F189, R08 (above, made by DIC Corporation), Supron S-382, SC101, 102, 103, 104, 105, 106 (above, made by Asahi Glass Co., Ltd.), PolyFox And fluorine-based surfactants such as series (manufactured by OMNOVA) or silicone-based surfactants. Moreover, polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone type surfactant.

These surfactant can be used individually by 1 type or in mixture of 2 or more types. Moreover, you may use together a fluorochemical surfactant and silicone type surfactant.

The addition amount of (component G ") surfactant (fluorine-type surfactant, silicone type surfactant, etc.) in the photosensitive resin composition in 2nd aspect of this invention is 10 weight part or less with respect to 100 weight part of component A". It is preferable, it is more preferable that it is 0.01-10 weight part, and it is more preferable that it is 0.01-1 weight part.

(Component H ")

It is preferable that the photosensitive resin composition in 2nd Embodiment of this invention contains the (component H ") adhesion | attachment improving agent.

The (component H ") adhesion improving agent which can be used for the photosensitive resin composition in 2nd aspect of this invention is an inorganic substance used as a board | substrate, for example, silicon compounds, such as a silicon, a silicon oxide, a silicon nitride, gold, copper And a compound which improves the adhesion between a metal such as aluminum and an insulating film, and specifically, a silane coupling agent, a thiol-based compound, etc. The silane coupling agent as the (component H) adhesion improving agent used in the present invention is an interface. It aims at reforming of, It does not specifically limit, A well-known thing can be used.

As a preferable silane coupling agent, (gamma) -glycidoxy propyltrialkoxysilane and (gamma) -methacryloxypropyl trialkoxysilane are more preferable, for example, (gamma) -glycidoxy propyl trimethoxysilane is more preferable. .

These may be used alone or in combination of two or more. These materials are effective for improving adhesion to the substrate and also for adjusting the taper angle with the substrate.

0.1-20 weight part is preferable with respect to 100 weight part of component A ", and, as for content of the (component H") adhesion improving agent in the photosensitive resin composition of this invention, 0.5-10 weight part is more preferable.

(Component I ") Basic Compound

It is preferable that the photosensitive resin composition in 2nd Embodiment of this invention contains a (component I ") basic compound.

(Component I ") It can be used, selecting arbitrarily as a basic compound from what is used by a chemical amplification register. For example, an aliphatic amine, an aromatic amine, a heterocyclic amine, a quaternary ammonium hydroxide, and a carboxylic acid are used. Quaternary ammonium salts; and the like.

As a heterocyclic amine, the compound which has an imidazole skeleton is preferable, and, as a specific example, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenyl imida Sol and the like.

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, Heterocyclic amine 2 It is more preferable to use together a species.

It is preferable that content of the (component I ") basic compound in the photosensitive resin composition in 2nd aspect of this invention is 0.001-1 weight part with respect to 100 weight part of component A", and it is 0.002-0.5 weight part It is more preferable.

(Component J ") development accelerator

It is preferable that the photosensitive resin composition in 2nd Embodiment of this invention contains the (component J ") image development promoter.

(Component J ") As the development accelerator, any compound having an image development promoting effect can be used, but it is preferable that the compound has at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group. , A compound having a carboxyl group or a phenolic hydroxyl group is more preferable, and a compound having a phenolic hydroxyl group is particularly preferable.

Moreover, 100-2,000 are preferable, as for the molecular weight of (component J ") image development promoter, 150-1,500 are more preferable, 150-1,000 are especially preferable.

(Component J ") The image development promoter may be used individually by 1 type, and can also use 2 or more types together.

The addition amount of the (component J ") image development promoter in the photosensitive resin composition in 2nd aspect of this invention is 0.1-30 weight part with respect to 100 weight part of components A" from a viewpoint of a sensitivity and a residual film ratio. 0.2-20 weight part is more preferable, and it is especially preferable that it is 0.5-10 weight part.

(Component K ") Antioxidant

The photosensitive resin composition in the 2nd Embodiment of this invention may contain the (component K ") antioxidant.

(Component K ") Antioxidant can contain a well-known antioxidant. (Component K) By adding antioxidant, coloring of a cured film can be prevented or the film thickness decrease by decomposition is reduced. In addition, it has the advantage of being excellent in heat resistance transparency.

As such an antioxidant, the compound illustrated as said component J can be illustrated similarly, and a preferable compound is also the same.

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

In addition, as an additive other than antioxidant, you may add the various ultraviolet absorbers, metal deactivator, etc. which were described in "New development of polymer additive (Nikkan Kogyo Co., Ltd.)", etc. to the photosensitive resin composition of this invention.

(Component L ") Plasticizer

The photosensitive resin composition in 2nd Embodiment of this invention may contain the (component L ") plasticizer.

(Component L ") As a plasticizer, dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethyleneglycol, glycerin, dimethyl glycerol phthalate, dibutyl tartarate, dioctyl adipic acid, triacetyl glycerine, etc. are mentioned, for example. .

It is preferable that it is 0.1-30 weight part with respect to 100 weight part of component A ", and, as for content of the (component L") plasticizer in the photosensitive resin composition in 2nd aspect of this invention, it is more preferable that it is 1-10 weight part. Do.

(Formation method of hardened film)

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

The formation method of the cured film in this invention forms a film | membrane using the photosensitive resin composition in the 1st aspect of this invention, or the photosensitive resin composition (photosensitive resin composition of this invention) in 2nd aspect of this invention. Although it will not restrict | limit especially if it is a method of producing and providing at least one of light and a heat | fever, and forming a cured film, It is preferable to include the process of the following (1)-(5).

(1) Coating process of apply | coating photosensitive resin composition of this invention on board | substrate

(2) Solvent removal process which removes solvent from apply | coated photosensitive resin composition

(3) Exposure process of exposing photosensitive resin composition from which solvent was removed by actinic light

(4) A developing step of developing the exposed photosensitive resin composition with an aqueous developer

(5) Post-baking process of thermosetting the developed photosensitive resin composition

Each process is demonstrated sequentially below.

In the application | coating process of (1), it is set as the wet film which apply | coats the photosensitive resin composition of this invention on a board | substrate, and puts a solvent.

In the solvent removal process of (2), it is preferable to remove a solvent and to form a dry coating film on a board | substrate by pressure reduction (backing) and / or heating from said apply | coated film | membrane.

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, component B or component B "decomposes and an acid is generated. The acid-decomposable group in structural unit (a1) contained in component A or the structural unit contained in component A" by the catalysis of the generated acid. The acid-decomposable group in (a1 ") is decomposed and a carboxyl group is produced.

In the generated region of the acid catalyst, PEB (post-exposure heat treatment) can be performed as necessary in order to accelerate the decomposition reaction. PEB can promote carboxyl production from acid-decomposable groups. 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 90 degrees C or less are especially preferable.

In the developing process of (4), it is preferable to develop component A or component A "which has advantageous carboxyl group using alkaline developing solution. The exposure part containing resin composition which has acidic radicals, such as a carboxyl group, which is easy to melt | dissolve in an alkaline developing solution. By removing the region, a positive image is formed.

In the post-baking process of (5), by heating the obtained positive image, an acid-decomposable group in a structural unit (a1) or a structural unit (a1 ") is thermally decomposed to generate an acid group such as a carboxyl group, and an epoxy group and A cured film can be formed by bridge | crosslinking an oxetanyl group, It is preferable to heat this heating at 150 degreeC or more high temperature, It is more preferable to heat at 180-250 degreeC, and to 200-250 degreeC It is particularly preferable to heat the heating time, although the heat time can be appropriately set depending on the heating temperature and the like, but preferably within the range of 10 to 90 minutes.

If a step of totally irradiating the active light, preferably ultraviolet rays, to the developing pattern before the post-baking step, the crosslinking reaction can be promoted by the acid generated by the irradiation of the active light.

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>

Optional components of component A to component C or components A "to D", and optional components such as component D to component N, or component E "to component L", may be optionally By mixing, stirring and dissolving to prepare a photosensitive resin composition. The photosensitive resin composition thus prepared may be used for use after being filtered using a filter having a pore size of about 0.1 μm or the like.

<Application process and solvent removal process>

The desired dry coating film can be formed by apply | coating the photosensitive resin composition to a predetermined board | substrate, and removing a solvent by pressure reduction and / or heating (prebaking). As said board | substrate, for example, in manufacture of a liquid crystal display device, the polarizing plate and the glass plate etc. which provided the black matrix layer and a color filter layer further as needed, and further provided the transparent conductive circuit layer can be illustrated.

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 the magnitude | size of 1 m or more in each side.

In addition, (2) The heating conditions of a solvent removal process decompose an acid-decomposable group in the structural unit (a1) in the component A in the unexposed part, or the structural unit (a1 "in the component A", and, in addition, the component A or It is a range which does not make component A "soluble in an alkaline developing solution, and although it changes also with the kind and compounding ratio of each component, it is preferable that it is about 30 to 300 second at 70-120 degreeC.

Exposure process

(3) In an exposure process, actinic light of a predetermined pattern is irradiated to the board | substrate which provided the dry coating film. Exposure may be performed through a mask and you may draw a predetermined pattern directly. Active rays having a wavelength of 300 nm or more and 450 nm or less can be preferably used. After an exposure process, PEB is performed as needed.

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

When using a mercury lamp, actinic light which has wavelength, such as g line | wire (436 nm), i line | wire (365 nm), and h line | wire (405 nm), can be used preferably. Mercury lamps are preferred in that they are suitable for exposure to large areas compared to lasers.

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

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

In addition, it is preferable that pulse width is 0.1nsec or more and 30,000nsec or less. In order not to decompose a chromatic film by the ablation phenomenon, 0.5 nsec or more is more preferable, 1 nsec or more is most preferable, In order to improve the alignment precision at the time of scanning exposure, 1,000 nsec or less is more preferable, and 50 nsec or less Most preferred.

The frequency of the laser is preferably 1 Hz or more and 50,000 Hz or less. In order to shorten an exposure process time, 10 microseconds or more are more preferable, 100 microseconds or more are the most preferable, In order to improve fitting accuracy at the time of scan exposure, 10,000 micrometers or less are more preferable, and 1,000 microseconds or less are the most preferable. .

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

Although there is no restriction | limiting in particular as an exposure apparatus which can be used for this invention, As what is marketed, Callisto (made by V technology), AEGIS (made by V technology), and DF2200G (Dainippon screen sash ( Note) etc. can be used. Moreover, the apparatus of that excepting the above is also used suitably.

In addition, irradiated light can also be adjusted through spectroscopic filters, such as a long wavelength cut filter, a short wavelength cut filter, and a bandpass filter, as needed.

Development Process

(4) In the developing step, it is preferable to form an image pattern by removing the exposed portion region using a basic developer. 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, such as methanol and ethanol, and surfactant 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.

It is preferable that developing time is 30 to 180 second, and the method of image development may be any of a liquid method, a dip method, a shower method, etc. After development, flowing water can be washed for 10 to 90 seconds to form a desired pattern.

<Post Baking Process (Crosslinking Process)>

With respect to the pattern corresponding to the unexposed area obtained by development, using a heating device such as a hot plate or an oven, at a predetermined temperature, for example, 180 to 250 ° C., for a predetermined time, for example, on a hot plate If it is 5 to 60 minutes if it is an oven and it is 30 to 90 minutes, it heat-processes and decomposes the acid-decomposable group in component A or component A ", produces | generates acidic groups, such as a carboxyl group, and the epoxy group in component A or component A", and By reacting with a crosslinkable group which is an oxetanyl group, and making it crosslink, it is possible to form a protective film or an interlayer insulating film excellent in heat resistance and hardness. In addition, when performing heat processing, transparency can also be improved by performing in nitrogen atmosphere.

In addition, prior to the heat treatment, after re-exposure to the substrate on which the pattern is formed by actinic light, post-baking (re-exposure / post-baking) generates an acid from the component B present in the unexposed portion, thereby crosslinking. It is preferable to function as a catalyst for promoting the reaction.

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 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 with respect to the side in which the film | membrane was formed by the photosensitive resin composition of this invention of a board | substrate. As an exposure amount of a re-exposure process, it is preferable that it is 100-1,000 mJ / cm <2>.

The organic EL (electroluminescence) display device or the liquid crystal display device of the present invention is not particularly limited except having a planarization film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention. Various organic EL display devices and liquid crystal display devices.

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 use. For example, in addition to the planarization film and the interlayer insulation film, it is suitable for a protective film of a color filter, a spacer for keeping the thickness of the liquid crystal layer in a liquid crystal display device constant, or a micro lens provided on the color filter in a solid-state image sensor. Can be used.

1: is typical sectional drawing which shows the structure of an example of the organic electroluminescent display which applied the cured film using the photosensitive resin composition of this invention as an insulating film and a planarization film.

The organic EL display device shown in FIG. 1 is a bottom emission type organic EL display device.

Of Figure 1, insulating film 3 is formed on a TFT (1) formed on the glass substrate 6, a bottom gate type, formed in a state covering the TFT (1) to the Si ₃ N ₄ is formed. After the contact holes (not shown) are formed in the insulating film 3, the wiring 2 (1.0 μm in height) connected to the TFT 1 through the contact holes is formed on the insulating film 3. It is formed in. The wiring 2 is for connecting the organic EL element and the TFT 1 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 film 4 is formed on the insulating film 3 in the state of embedding the unevenness by the wiring 2.

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 via the contact hole 7, and is formed. 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 by providing this insulating film 8, between the 1st electrode 5 and the 2nd electrode formed in a subsequent process is provided. Short can be prevented.

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, for sealing. It seals by bonding together using a glass plate and an ultraviolet curable epoxy resin, and the active-matrix organic electroluminescent display apparatus by which the TFT 1 for driving this is connected to each organic EL element is obtained.

It is typical sectional drawing which shows the structure which shows an example of the liquid crystal display device which applied the cured film using the photosensitive resin composition of this invention.

The liquid crystal display device shown in FIG. 2 is an active matrix liquid crystal display device.

In FIG. 2, the liquid crystal display device 10 is a liquid crystal panel which has the backlight unit 12 in the back surface, The said liquid crystal panel is arrange | positioned between two glass substrates 14 and 15 in which the polarizing film was affixed. Elements of the TFT 16 corresponding to all the pixels are arranged. In each element formed on the glass substrate, the ITO transparent electrode 19 which forms a pixel electrode is wired through the contact hole 18 formed in the cured film 17. As shown in FIG. 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]

Next, the present invention will be described in more detail with reference to Examples. However, this invention is not limited by these Examples. In addition, "part" and "%" are basis of weights unless there is particular notice.

Synthesis Example 1-1

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added. 61.5 parts by weight of 1-ethoxyethyl methacrylate, 20.1 parts by weight of styrene, 27.6 parts by weight of p-vinylbenzyl glycidyl ether, and methacrylic acid (tricyclo [5.2.1.0 ^2,6 ] decane-8-yl) 32.1 weight part and 3 weight part of (alpha)-methylstyrene dimers were thrown in, and nitrogen was substituted, and stirring was started gently. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A-1). The polystyrene reduced weight average molecular weight (Mw) of the copolymer (A-1) was 12,000.

The composition ratio (mol%) of the synthesized copolymer is shown in Table 1.

<Synthesis example 1-2-2>

The copolymers (A-2) to (A-28) and (a-1) to (a-6) shown in Table 1 were prepared in the same manner as in Synthesis Example 1-1, except that the monomers used and the amount thereof were changed. Respectively synthesized. The composition ratio (mol%) and Mw of each synthesize | combined copolymer are as showing in Table 1.

[Table 1]

The symbol of Table 1 is as follows.

MAEVE: 1-ethoxyethyl methacrylate

MACHOE: 1- (cyclohexyloxy) ethyl methacrylate

MATHF: Tetrahydrofuran-2-yl methacrylate

MATHP: tetrahydro-2H-pyran-2-yl methacrylate

p-VBGE: p-vinylbenzyl glycidyl ether

St: Styrene

α-MeSt: α-methylstyrene

DCPM: Methacrylic acid (tricyclo [5.2.1.0 ^2,6 ] decane-8-yl)

GMA: glycidyl methacrylate

Oxe-30: methacrylic acid (3-ethyloxetan-3-yl) methyl (manufactured by Osaka Yuki Chemical Co., Ltd.)

THFFMA: Tetrahydrofurfuryl methacrylate

HEMA: 2-ethylhexyl methacrylate

HEA: 2-ethylhexyl acrylate

HBMA: 2-hydroxy-2-methylpropylmethacrylate

HBA: 2-hydroxy-2-methylpropylacrylate

MAA: methacrylic acid

MMA: methyl methacrylate

BzMA: Benzyl methacrylate

n-HMA: n-hexyl methacrylate

(Examples 1 to 36 and Comparative Examples 1 to 9)

The amount (solid content) shown in Table 2 was dissolved in a mixed solvent of diethylene glycol methyl ethyl ether: propylene glycol monomethyl ether acetate = 1: 1 (weight ratio) so that the solid content concentration was 20% by weight, and then the pore size was 0.2 µm. It filtered with the membrane filter of and prepared the photosensitive resin composition of Examples 1-36 and Comparative Examples 1-9. In addition, the unit of the quantity of each component in Table 2 is a weight part.

[Table 2]

In the said Table 2, the symbol of various additives is as follows. Moreover, pKa of the generated acid of B-1-B-4 is four or less.

B-1: CGI-1397 (manufactured by BASF Corporation)

B-2: The compound of the following structure (it synthesize | combined according to the method of Paragraph 0108 of Unexamined-Japanese-Patent No. 2002-528451).

B-3: PAI-1001 (made by Midori Chemical Co., Ltd.)

B-4: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate

b-1: 4,4 '-{1- {4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene} bisphenol (1.0 molar equivalent) and 1,2-naphthoquinone Condensate of diazide-5-sulfonic acid chloride (2.0 molar equivalents) (pKa of generated acid = 4.5)

D-1: DBA (9,10-dibutoxy anthracene and the Kawasaki Chemical Co., Ltd. product)

E-1: 1,5-diazabicyclo [4,3,0] -5-nonene (made by Tokyo Kasei Kogyo Co., Ltd.)

F-1: JER150S65 (Mitsubishi Chemical Co., Ltd.)

G-1: 3-glycidoxy propyl trimethoxysilane (KBM-403, Shin-Etsu Chemical Co., Ltd. make)

H-1: Compound of the following structure

<Evaluation of Volume Resistivity>

After apply | coating the photosensitive resin composition solution on an aluminum substrate, it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the photosensitive resin composition layer of 6.0 micrometers in film thickness. The obtained photosensitive resin composition was exposed to a total irradiation amount of 300 mJ / cm 2 (roughness: 20 kW / cm 2) with a PLA-501F exposure machine (ultra high pressure mercury lamp) manufactured by Canon Corporation, and the substrate was exposed to an oven at 220 ° C. for 1 hour. The cured film was obtained by heating. The volume resistivity of the obtained cured film was measured by ULTRA HIGH RESISTANCE METER R8252 (made by ACDC). Measurement temperature was set to room temperature (25 degreeC), and the applied voltage was 100V. Table 3 shows the values of the volume resistivity. The higher the value of the volume resistivity, the higher the electrical stability of the insulating film, and the better, and A and B are levels that have no problem in practical use.

A: 2.0 × 10 ¹⁶ Ωcm or more

B: 1.0 × 10 ¹⁶ Ω · cm or more Less than 2.0 × 10 ¹⁶ Ω · cm

C: less than 1.0 × 10 ¹⁶ Ω · cm

<Evaluation of dielectric breakdown voltage>

On the bare wafer (N-type low resistance) (manufactured by SUMCO), the photosensitive resin composition solution was slit-coated and then prebaked at 90 ° C. for 2 minutes on a hot plate to form a photosensitive resin composition layer having a film thickness of 3.0 μm. did. The obtained photosensitive resin composition was exposed to a total irradiation amount of 300 mJ / cm 2 (roughness: 20 kW / cm 2) with a PLA-501F exposure machine (ultra high pressure mercury lamp) manufactured by Canon Corporation, and the substrate was exposed to an oven at 220 ° C. for 1 hour. The cured film was obtained by heating.

About this cured film, the dielectric breakdown voltage was measured using CVmap92A (made by Four Dimensions Inc.). Table 3 shows the values of the dielectric breakdown voltages. The higher the value of the dielectric breakdown voltage is, the higher the electrical stability of the insulating film is, and the better the A and B levels are practically without problems.

A: 300V / ㎛ or more

B: 100 V / μm or more and less than 300 V / μm

C: less than 100V / μm

[Table 3]

As shown in Table 3, according to the photosensitive resin composition of this invention, it turned out that the cured film with high volume resistivity and dielectric breakdown voltage, and high electrical stability can be obtained.

(Example 1-31)

<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).

Forming a TFT (1) of the bottom gate type on a glass substrate 6, thereby forming the insulating film 3 made of Si ₃ N ₄ in a state covering the TFT (1). Next, a contact hole (not shown here) is formed in the insulating film 3, and then the wiring 2 (1.0 mu m in height) connected to the TFT 1 through the contact hole is formed on the insulating film 3. Formed in. This wiring 2 is for connecting the organic EL element and the TFT 1 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 in the state of embedding the unevenness by the wiring 2. Formation of the planarizing film 4 on the insulating film 3 is carried out by spin-coating the photosensitive resin composition of Example 1-1 on a board | substrate, prebaking (90 degreeCx 2 minutes) on a hotplate, and then on a mask. After irradiating i line | wire (365 nm) with 30 mJ / cm <2> (roughness 20 mW / cm <2>) using a high pressure mercury lamp, it developed with aqueous alkali solution, the pattern was formed, and it heat-processed at 230 degreeC for 60 minutes. The applicability | paintability at the time of apply | coating the said photosensitive resin composition 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 EL device was formed on the obtained planarization film 4. First, on the planarization film 4, the 1st electrode 5 which consists of ITO 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. Using this resist pattern as a mask, pattern processing was performed by wet etching using ITO etchant. Thereafter, the resist pattern was stripped using a resist stripping solution (a mixture 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 1-7 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.

In addition, the hole transport layer, the organic light emitting layer, and the electron transport layer were sequentially deposited through a desired pattern mask in the vacuum vapor deposition apparatus. 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 bonding together using the sealing glass plate and an ultraviolet curable epoxy resin.

As described above, an active matrix organic EL display device obtained by connecting the TFT 1 for driving this to each organic EL element was obtained. It turned out that it is an organic electroluminescence display with high reliability showing the favorable display characteristic where the voltage was applied through the drive circuit.

Synthesis Example 2-1

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added. Subsequently, 63.3 parts by weight of 1-ethoxyethyl methacrylate, 20.8 parts by weight of styrene, 56.8 parts by weight of glycidyl methacrylate, and 3 parts by weight of? -Methylstyrene dimer were added to replace the nitrogen, followed by gentle stirring. did. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A1). The polystyrene reduced weight average molecular weight (Mw) of the copolymer (A1) was 12,000.

The composition ratio (mol%) of the synthesized copolymer is shown in Table 4.

<Synthesis Example 2-2-25>

The copolymers (A2) to (A5) and (A'1) to (A'3) and (C1) shown in Table 4 were used in the same manner as in Synthesis example 2-1, except that the used monomer and the amount thereof were changed. (C4), (C'1) and (C'2) were synthesized, respectively. The composition ratio (mol%) and Mw of each synthesize | combined copolymer are as showing in Table 4.

[Table 4]

The symbol of Table 4 is as follows.

MAEVE: 1-ethoxyethyl methacrylate

MACHOE: 1- (cyclohexyloxy) ethyl methacrylate

GMA: glycidyl methacrylate (made by Wako Pure Chemical Industries, Ltd.)

Oxe-30: methacrylic acid (3-ethyloxetan-3-yl) methyl (manufactured by Osaka Yuki Chemical Co., Ltd.)

St: Styrene (made by Wako Pure Chemical Industries, Ltd.)

MAA: Methacrylic acid (made by Wako Pure Chemical Industries, Ltd.)

DCPM: methacrylic acid (tricyclo [5.2.1.0 ^2,6 ] decane-8-yl) (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

CHMI: N-cyclohexylmaleimide

THFFMA: Tetrahydrofurfuryl methacrylate

PME: methoxy polyethylene glycol methacrylate (Nichi Oil Co., Ltd., Blemmer PME-200)

MMA: methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

BVGE: p-vinylbenzyl glycidyl ether

StCOOEVE: the following compound

StCOOH: the following compound (p-vinylbenzoic acid)

(Examples 2-1 to 10 and Comparative Examples 2-1 to 5)

The amount (solid content) described in Table 5 was dissolved in a mixed solvent of diethylene glycol methyl ethyl ether: propylene glycol monomethyl ether acetate = 1: 4 (weight ratio) so that the solid content concentration was 20% by weight, and the diameter was 0.2 µm. It filtered with the membrane filter of and prepared the photosensitive resin composition of Examples 2-1-10 and Comparative Examples 2-1-5, respectively.

[Table 5]

The unit of the usage-amount in each component of Table 5 is a weight part.

In addition, the symbol of Table 5 is as follows.

A1 to A5 and A'1 to A'3, and C1 to C4, C'1 and C'2 are the copolymers (A1) to (A5) and (A'1) to (A'3), respectively. , And (C1) to (C4), (C'1) and (C'2) were used.

B1: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate

B2: 2- (4-methoxy-β-styryl) -4,6-bis (trichloroethyl) -s-triazine

NQD: 4,4 '-{1- {4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene} bisphenol (1.0 molar equivalent) and 1,2-naphthoquinone diazide A condensate of -5-sulfonic acid chloride (2.0 molar equivalents)

PAG103: IRGACURE PAG103 (product of BASF Corporation)

PAI-1001: the following compound (manufactured by Midori Chemical Co., Ltd.)

E1: dibutoxy anthracene (made by Kawasaki Chemical Co., Ltd.)

F1: JER-157S70 (polyfunctional novolac epoxy resin (epoxy equivalent 200-220 g / eq), manufactured by Japan Epoxy Resin Co., Ltd.)

PF-6320: PolyFox PF-6320 (fluorine-based surfactant, manufactured by OMNOVA)

C1-A: A compound _{C1-A (Rf = nC 6} F 13) of the structure

KF-6012: Polyether Modified Silicone Surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.)

F780F: Fluorine-based surfactant (Megapack F780F, manufactured by DIC Corporation)

KF-6012: Polyether Modified Silicone Surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.)

KBM-403: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

The obtained photosensitive resin compositions of Examples 2-1 to 10 and Comparative Examples 2-1 to 5 were each evaluated by the following evaluation methods. Table 6 summarizes the results of the evaluation.

<Evaluation of dry etching resistance>

After slit-coating each photosensitive resin composition on a glass substrate (Corning 1737, 0.7 mm thickness (made by Corning Corporation)), a solvent is removed by heating on a 90 degreeC / 120 second hotplate, and the photosensitive resin of 3.0 micrometers of film thicknesses The composition layer was formed.

The obtained photosensitive resin composition layer was exposed to a total irradiation amount of 100 mJ / cm 2 (roughness: 20 kW / cm 2, i-line) with a Canon PLA-501F exposure machine (ultra high pressure mercury lamp), and then the substrate was exposed thereafter. It heated at 230 degreeC in oven for 1 hour, and obtained the cured film. Using the dry etching apparatus "CDE-80N (manufactured by Shibaura Mechatronics)" for the cured film, CF ₄ 50 ml / min, O ₂ 10 ml / min, output 400 kPa, etching time 90 seconds as an etching gas. Dry etching was performed at, and the film thicknesses before and after the treatment were measured to calculate the film reduction amount by dry etching. In addition, evaluation criteria are as follows. A and B are practical ranges, and C is not practical.

A: less than 0.2 μm

B: 0.2 µm or more and less than 0.4 µm

C: 0.4 µm or more

<Evaluation of surface roughness after dry etching>

The surface roughness (Ra, unit nm) of the surface (surface of the photosensitive resin composition layer) of the board | substrate which evaluated dry etching tolerance was measured using the atomic force microscope (AFM). The smaller the value, the smoother the surface.

Ranks were determined based on the following criteria. A-C is a practical range, and D is not practical.

A: less than 2.0 nm

B: 2.0 nm or more and less than 4.0 nm

C: 4.0 nm or more and less than 7.0 nm

D: 7.0 nm or more

<Evaluation of Surface Hardness>

About the cured film obtained by evaluating the said dry etching tolerance, pencil hardness was measured according to JISK5600-5-4. From the standpoint of scratch resistance, the harder side is preferred.

A: 6H or more (hard)

B: 4H-5H

C: 3H or less (soft)

<Evaluation of Preservation Stability>

Viscosity was measured immediately after each composition was prepared, it was preserve | saved at 23 degreeC after that, and the viscosity was measured after 3 days.

A: viscosity change is less than 3%

B: viscosity change is 3% or more but less than 5% (viscosity increase)

C: Viscosity change is 5% or more

<Evaluation of display nonuniformity in a liquid crystal display device>

According to Japanese Patent No. 3362008, a liquid crystal display device was produced using each of the photosensitive resin compositions of Examples and Comparative Examples as an interlayer insulating film.

Gray was displayed on the produced liquid crystal display device, the presence or absence of the nonuniformity was visually observed, and the following references | standards evaluated.

A: No stain is observed

B: Stain is slightly observed (acceptable range)

C: stain is observed (not acceptable)

TABLE 6

DESCRIPTION OF SYMBOLS 1 TFT (thin film transistor), 2 wiring, 3 insulating film, 4 planarization film, 5 1st electrode, 6 glass substrate, 7 contact hole, 8 insulating film, 10 liquid crystal display device, 12 backlight Unit, 14, 15: glass substrate, 16: TFT, 17: cured film, 18: contact hole, 19: ITO transparent electrode, 20: liquid crystal, 22: color filter

Claims (26)

(Component A) Air having a structural unit represented by formula (a1), a structural unit represented by formula (a2), a structural unit represented by formula (a3) and / or a structural unit represented by formula (a4) coalescence,
(Component B) a photoacid generator having a pKa of 4 or less of a generated acid, and
(Component C) containing a solvent, characterized by
Photosensitive resin composition.

(In formula, R <^1> represents a hydrogen atom or a methyl group, R <^2> represents a C1-C6 alkyl group, R <^3> represents a C1-C6 alkyl group or a C4-C7 cycloalkyl group, and R <^2> and R ³ may bond and form a ring, R <^4> represents a hydrogen atom or a methyl group, R <^5> represents a hydrogen atom or a methyl group, R <^6> represents a hydrogen atom or a methyl group, X is a single bond, C1-C4 An alkylene group or an alkyleneoxy group having 2 to 4 carbon atoms, and A represents a carbon 5-membered ring having one saturated carbon 5-membered ring or an unsaturated double bond) The method of claim 1,
The photosensitive resin composition which component A further has another structural unit (a5) containing a crosslinkable group other than the structural unit represented by said formula (a2). The method according to claim 1 or 2,
The photosensitive resin composition whose said structural unit (a5) is a structural unit represented by a following formula (a5-1) or (a5-2).

(Wherein R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents a hydrogen atom or a methyl group) The method according to claim 1 or 2,
The photosensitive resin composition which component A further has a structural unit represented by a following formula (a6).

(Wherein R ⁹ represents a hydrogen atom or a methyl group) The method according to claim 1 or 2,
The said photosensitive resin composition whose R <^3> is an ethyl group or a cyclohexyl group. The method according to claim 1 or 2,
Photosensitive resin composition whose component B is an oxime sulfonate compound which has at least 1 of the oxime sulfonate residue represented by a following formula (B-0).

(Wherein, the broken line portion indicates the bonding position with other structures) The method according to claim 6,
The photosensitive resin composition whose oxime sulfonate compound which has at least 1 of the oxime sulfonate residue represented by said formula (B-0) is an oxime sulfonate compound represented by a following formula (B-1).

(Wherein, R ^B4 represents a hydrogen atom or a methyl group, R ^B5 represents an alkyl group having 1 to 8 carbon atoms, p-toluyl group, phenyl group, camphoryl group, trifluoromethyl group or nonafluorobutyl group) The method according to claim 6,
The photosensitive resin composition whose oxime sulfonate compound which has at least 1 of the oxime sulfonate residue represented by said formula (B-0) is an oxime sulfonate compound represented by a following formula (B-2).

(Wherein, R ^B1 represents an alkyl group, an alkoxy group or a halogen atom, and R ^B2 represents an alkyl group or an aryl group) The method according to claim 1 or 2,
The photosensitive resin composition containing a photosensitizer further. (1) an application step of applying the photosensitive resin composition according to claim 1 or 2 on a substrate;
(2) a solvent removal step of removing the solvent from the applied photosensitive resin composition,
(3) an exposure step of exposing the photosensitive resin composition from which the solvent is removed by actinic light;
(4) a developing step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) Post-baking process of thermosetting the developed photosensitive resin composition
Formation method of the cured film containing a. The method of claim 10,
A method of forming a cured film comprising a step of exposing the entire surface of the developed photosensitive resin composition after the developing step and before the postbaking step. The cured film formed by the formation method of the cured film of Claim 10. The method of claim 12,
Cured film which is an interlayer insulation film. The organic electroluminescence display provided with the cured film of Claim 12. The liquid crystal display device provided with the cured film of Claim 12. (Component A ") It has a structural unit (a1") which has an acidic group protected by an acid-decomposable group, and a structural unit (a2 ") which has an epoxy group or an oxetanyl group, and does not have a structural unit represented by following formula (1) Copolymer,
(Component B ") photoacid generator,
(Component C ") A polymer having a structural unit represented by the following formula (1), and
(Component D ") characterized by containing a solvent
Photosensitive resin composition.

(In formula, R <^1> represents a hydrogen atom or a methyl group, R <^2> represents a C1-C6 alkyl group, a C1-C6 alkoxy group, a hydroxyl group, or a 2, 3- epoxy propoxymethyl group each independently, and n Represents an integer of 1 to 5) 17. The method of claim 16,
The photosensitive resin composition which is a chemically amplified positive type photosensitive resin composition. 18. The method according to claim 16 or 17,
The photosensitive resin composition whose structural unit represented by said formula (1) is a structural unit represented by following formula (1-1).

(Wherein R ¹ represents a hydrogen atom or a methyl group) 18. The method according to claim 16 or 17,
The photosensitive resin composition whose said structural unit (a1 ") is a structural unit represented by Formula (A2).

(In formula (A2), R <^1> and R <^2> represents a hydrogen atom, an alkyl group, or an aryl group each independently, At least one of R <^1> and R <^2> is an alkyl group or an aryl group, and R <^3> may have a substituent An alkyl group, a cycloalkyl group, or an aryl group, R ¹ or R ² and R ³ may be linked to each other to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group. 18. The method according to claim 16 or 17,
The photosensitive resin composition whose component B "is a compound which has an oxime sulfonate residue. (1) an application step of applying the photosensitive resin composition according to claim 16 or 17 on a substrate;
(2) a drying step of removing the solvent from the applied photosensitive resin composition,
(3) an exposure step of exposing the photosensitive resin composition from which the solvent is removed by actinic light;
(4) a developing step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) Post-baking process of thermosetting the developed photosensitive resin composition
Formation method of the cured film containing a. The method of claim 21,
A method of forming a cured film comprising a step of exposing the entire surface of the developed photosensitive resin composition after the developing step and before the postbaking step. The cured film formed by the formation method of the cured film of Claim 21. 24. The method of claim 23,
Cured film which is an interlayer insulation film. The organic electroluminescence display provided with the cured film of Claim 23. The liquid crystal display device provided with the cured film of Claim 23.

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