JP2017044860A - Positive photosensitive resin composition, cured film and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition exhibiting an excellent balance between developability and adhesiveness.SOLUTION: The positive photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a photosensitive agent, and (C) a polyfunctional (meth)acrylate compound having a hydroxyl group and 2 or more and 4 or less (meth)acryl groups in the molecule.SELECTED DRAWING: None

Description

  The present invention relates to a positive photosensitive resin composition, a cured film, and an electronic device.

  As a cured film constituting an electronic device, a resin film obtained by exposing a photosensitive resin composition may be used. In relation to such a photosensitive resin composition, for example, a technique described in Patent Document 1 is known. Patent Document 1 describes a radiation-sensitive resin composition containing a specific alkali-soluble resin and a 1,2-quinonediazide compound. Further, according to this document, it is possible to easily form a patterned thin film having radiation sensitivity, high resolution, and excellent properties such as insulation, flatness, heat resistance, hardness, and transparency. It is said that the radiation sensitive resin composition which can be provided can be provided.

JP-A-8-262709

According to the said patent document 1, the flatness of the thin film obtained from a radiation sensitive resin composition is included by including the polymeric compound which has at least 1 ethylenically unsaturated double bond, such as a (meth) acrylate compound. In the examples, positive cured films having excellent resolution and heat resistance are obtained.
Here, in the case where such an ethylenically unsaturated double bond is included as a resin composition, since the unsaturated double bond contributes to the polymerization, it is possible to improve the developability. In addition, it is presumed that physical properties such as flatness, heat resistance and hardness are improved.

However, as a result of investigations by the present inventors, the ethylenically unsaturated double bond as described in Patent Document 1 is not necessarily sufficiently compatible with the alkali-soluble resin contained in the resin composition. As a result, when the resin composition is cured, the system becomes non-uniform, and there is a case where sufficient adhesion between the substrate and the resin film cannot be expressed.
That is, for example, when a polymerizable compound having an ethylenically unsaturated double bond is included in a positive photosensitive resin composition, improvement in developability and improvement in adhesion are in a trade-off relationship, There has been room for development of the resin composition in which both of these are achieved.

  This invention is made | formed in view of the said situation, and provides the positive photosensitive resin composition excellent in the balance of developability and adhesiveness.

  As a result of intensive studies by the present inventors, a positive photosensitive resin that can solve the above-mentioned problems by using a compound having a specific functional group as the (meth) acrylic compound contained in the photosensitive resin composition. It has been found that a functional resin composition can be provided.

That is, according to this invention, the positive photosensitive resin composition containing the following components (A), (B), (C) is provided.
(A) Alkali-soluble resin (B) Photosensitizer (C) Polyfunctional (meth) acrylate compound having a hydroxyl group and 2 or more and 4 or less (meth) acryl groups in the molecule

  Moreover, according to this invention, the cured film comprised with the hardened | cured material of the said positive photosensitive resin composition is provided.

  Moreover, according to this invention, an electronic apparatus provided with the said cured film is provided.

The polyfunctional (meth) acrylate compound contained in the positive photosensitive resin composition of the present invention has a hydroxyl group in the molecule and a specific number of (meth) acrylic groups. Although it is not certain, the (meth) acryl group contained in the polyfunctional (meth) acrylate compound improves the developability, and at the same time, the hydroxyl group contained in the polyfunctional (meth) acrylate compound is positive photosensitive. It is considered that the adhesiveness can be improved by exhibiting an appropriate affinity with the alkali-soluble resin contained in the resin composition.
That is, by employing such a polyfunctional (meth) acrylate compound, it is possible to realize a positive photosensitive resin composition excellent in the balance between developability and adhesion.

It is sectional drawing which shows an example of the electronic device of this embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.
In the present specification, “to” represents the following from the above unless otherwise specified.

(Positive photosensitive resin composition)
First, the positive photosensitive resin composition of this embodiment will be described.
The positive photosensitive resin composition of the present embodiment includes the following components (A), (B), and (C).
(A) Alkali-soluble resin (B) Photosensitizer (C) Polyfunctional (meth) acrylate compound having a hydroxyl group and 2 or more and 4 or less (meth) acryl groups in the molecule

First, the use of the positive photosensitive resin composition of the present embodiment will be described.
The positive photosensitive resin composition according to this embodiment can be used, for example, to form a permanent film. The permanent film is composed of a cured film obtained by curing a positive photosensitive resin composition. In this embodiment, for example, after a coating film composed of a positive photosensitive resin composition is patterned into a desired shape by exposure and development, a permanent film is formed by curing the coating film by heat treatment or the like. . On the other hand, the positive photosensitive resin composition may be used to form a photoresist used in a lithography process.

Examples of the permanent film formed using the positive photosensitive resin composition include an interlayer film, a surface protective film, a color filter, and a dam material. The permanent film can also be used as an optical material such as an optical lens. The application of the permanent film is not limited to these.
In addition to the permanent film of the positive photosensitive resin composition of the present embodiment, photoresists such as etching resists, microfabrication applications such as MEMS (Micro Electro Mechanical Systems), and the like can be mentioned.

  The interlayer film refers to an insulating film provided in a multilayer structure, and the kind thereof is not particularly limited. Examples of the interlayer film include those used in semiconductor device applications such as an interlayer insulating film constituting a multilayer wiring structure of a semiconductor element, a buildup layer or a core layer constituting a circuit board. Further, as the interlayer film, for example, a flattening film that covers a thin film transistor (TFT) in the display device, a liquid crystal alignment film, and a protrusion provided on a color filter substrate of an MVA (Multi Domain Vertical Alignment) type liquid crystal display device Or what is used in display apparatus uses, such as a partition for forming the cathode of an organic EL element, is also mentioned. The surface protective film refers to an insulating film that is formed on the surface of an electronic component or an electronic device and protects the surface, and the type thereof is not particularly limited. Examples of such a surface protective film include a passivation film provided on a semiconductor element, a bump protective film or a buffer coat layer, or a cover coat provided on a flexible substrate. The dam material is a spacer used to form a hollow portion for arranging an optical element or the like on the substrate.

  Next, each component constituting the positive photosensitive resin composition of the present embodiment will be described.

((A) alkali-soluble resin)
(A) Examples of alkali-soluble resins include amide bonds such as acrylic resins such as phenol resins, hydroxystyrene resins, methacrylic acid resins, and methacrylic ester resins, cyclic olefin resins, polybenzoxazole precursors, and polyimide precursors. And a precursor containing a norbornene skeleton in the structure of a resin obtained by dehydrating and ring-closing the precursor, a copolymer represented by the following formula (1), and the like. From the viewpoint of improving the developability and curability of the positive photosensitive resin composition of the present embodiment and the mechanical strength of the cured film, a phenol resin, a hydroxystyrene resin, a precursor having an amide bond, or the following formula (1 It is preferable that the copolymer shown by this is included.
In addition, (A) the alkali-soluble resin preferably contains a carboxyl group in the structure in order to further increase the affinity with the later-described (C) polyfunctional (meth) acrylate compound.
Moreover, as (A) alkali-soluble resin, it is also preferable that the norbornene skeleton is included in the structure from a viewpoint of improving the heat resistance and transparency of a cured film. Here, the alkali-soluble resin containing a norbornene skeleton is, for example, a resin obtained by polymerizing a monomer having polymerizability in the alicyclic ring, such as a copolymer represented by the following formula (1), and a polymerizable group. May be a resin obtained by polymerizing a monomer having a norbornene skeleton at an isolated position (that is, a resin provided with a norbornene skeleton as a pendant).
(A) Alkali-soluble resin can contain the 1 type (s) or 2 or more types of these.

In the formula (1), l and m represent molar contents (molar ratio) in the copolymer, and l + m ≦ 1, 0.1 ≦ l ≦ 0.9, 0.1 ≦ m ≦ 0.9. . n is 0, 1 or 2.
R _a , R _b , R _c and R _d are each independently hydrogen or an organic group having 1 to 30 carbon atoms. R _a , R _b , R _c and R _d may be the same as or different from each other.
A is a structural unit represented by the following formula (2a), (2b), (2c), (2d) or (2e). The copolymer represented by the above formula (1) has one or more structural units A selected from the following formulas (2a), (2b), (2c), (2d) and (2e). included. In this embodiment, it is preferable that at least one or more structural units A selected from the following formulas (2a), (2b), (2c) and (2e) are included. The copolymer represented by the above formula (1) may or may not contain a structural unit derived from the norbornene-type monomer shown in the formula (1) and a structural unit other than the structural unit A. Not necessary.

式（２ａ）および式（２ｂ）中、Ｒ_ｅ、Ｒ_ｆおよびＲ_ｇは、それぞれ独立して炭素数１〜１８の有機基である。式（２ｅ）中、Ｒ_ｈは、水素、炭素数１〜１２のアルキル基、または炭素数３〜８のシクロアルキル基である。

In formula (2a) and formula (2b), R _e , R _f and R _g are each independently an organic group having 1 to 18 carbon atoms. In formula (2e), R _h is hydrogen, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms.

In the present embodiment, the copolymer represented by the above formula (1) preferably includes the structural unit A represented by the above formula (2a) and the structural unit A represented by the above formula (2c). Preferably includes the structural unit A represented by (2b). This makes it easy to adjust the solubility of the positive photosensitive resin composition in the alkaline developer in the photolithography process.
In particular, from the viewpoint of improving the heat resistance and strength of the cured film, the structural unit A represented by the above formula (2e) is more preferably contained in the copolymer represented by the above formula (1).

In this embodiment, examples of the organic group constituting R _a , R _b , R _c and R _d include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, Examples include an organic group having a carboxyl group and an organic group having a heterocycle, and can be selected from these. As the alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, An octyl group, a nonyl group, and a decyl group are mentioned. Examples of the alkenyl group include allyl group, pentenyl group, and vinyl group, and can be selected from these. An ethynyl group is mentioned as an alkynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the organic group having a heterocycle include an epoxy group and an organic group having an oxetanyl group.
Incidentally, R _{a, R b,} by including an alkyl group as R _c or R _d, it is possible to improve the film formability of the photosensitive resin composition. In addition, by including an aryl group as R _a , R _b , R _c, or R _d , film loss during development using an alkaline developer in the lithography process can be suppressed. Furthermore, R _{a, R b,} by including an organic group having an organic group or a hetero ring having a carboxyl group as R _c or R _d, it is possible to improve the heat resistance and strength of the cured film. From the viewpoint of particularly improving the heat resistance of the cured _film, heteroaryl as R _a, R b, a structural unit containing an organic group having a carboxyl group as _{R c} or _{R d, R a, R b} , R c or _{R d} It is more preferable that the structural unit containing an organic group having a ring is included in the copolymer represented by the above formula (1).

In addition, the above-described alkyl group, alkenyl group, alkynyl group, alkylidene group, aryl group, aralkyl group, alkaryl group, cycloalkyl group, organic group having a carboxyl group, and organic group having a heterocyclic ring are one or more hydrogen atoms. May be substituted with a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Among these, a haloalkyl group in which one or more hydrogen atoms of the alkyl group are substituted with a halogen atom is preferable. By using at least one of R _a , R _b , R _c and R _d as a haloalkyl group, the dielectric constant of the resin film formed using the photosensitive resin composition can be lowered.
In addition, from the viewpoint of increasing the light transmittance of the resin film formed using the photosensitive resin composition, any of R _a , R _b , R _c and R _d is preferably hydrogen, and R _a , More preferably, R _b , R _c and R _d are all hydrogen.

In this embodiment, examples of the organic group constituting R _e , R _f, and R _g include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, and a heterocyclic ring. And an organic group having the following can be selected from these. Here, as the alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl Groups, octyl groups, nonyl groups, and decyl groups. Examples of the alkenyl group include allyl group, pentenyl group, and vinyl group. An ethynyl group is mentioned as an alkynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the organic group having a heterocycle include an epoxy group and an organic group having an oxetanyl group.

  In addition, in the above-described organic group having an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, or a heterocyclic ring, one or more hydrogen atoms are substituted with a halogen atom. It may be. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Among these, a haloalkyl group in which one or more hydrogen atoms of the alkyl group are substituted with a halogen atom is preferable.

In this embodiment, examples of the alkyl group having 1 to 12 carbon atoms constituting R _h include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert group. -A butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. Examples of the cycloalkyl group having 3 to 8 carbon atoms constituting R _h include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. One or more hydrogen atoms contained in R _h may be substituted with a halogen atom such as fluorine, chlorine, bromine or iodine.

The copolymer represented by the above formula (1) includes, for example, a repeating unit derived from a norbornene type monomer represented by the following formula (3), a repeating unit derived from maleic anhydride represented by the following formula (4), and It is preferable that is an alternating copolymer in which are alternately arranged. The copolymer represented by the above formula (1) may be a random copolymer or a block copolymer. The repeating unit derived from maleic anhydride shown in the following formula (4) is a structural unit represented by the above formulas (2a) to (2d) in A in the above formula (1).
In the present embodiment, when the copolymer represented by the above formula (1) includes the structural unit A represented by the above formula (2e), for example, among R _a , R _b , R _c and R _d It is particularly preferable that at least one of these has a structural unit derived from a norbornene-type monomer that is an organic group having an oxetane ring.
In addition, (A) alkali-soluble resin may contain the 1 type (s) or 2 or more types of the monomers shown by following formula (3), (4) and (9) as a low molecular weight component.

式（３）中、ｎは０、１または２であり、Ｒ_ａ、Ｒ_ｂ、Ｒ_ｃおよびＲ_ｄはそれぞれ独立して水素または炭素数１〜３０の有機基である。式（９）中、Ｒ_ｈは、水素、炭素数１〜１２のアルキル基、または炭素数３〜８のシクロアルキル基である。

In formula (3), n is 0, 1 or 2, and R _a , R _b , R _c and R _d are each independently hydrogen or an organic group having 1 to 30 carbon atoms. In formula (9), R _h is hydrogen, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms.

  (A) As a precursor which has an amide bond in alkali-soluble resin, what has a repeating unit shown, for example by following General formula (5) can be used.

In formula (5), X and Y are organic groups. R ₁ is a hydroxyl group, —O—R ₃ , an alkyl group, an acyloxy group, or a cycloalkyl group, and when there are a plurality of R _{1 s} , they may be the same or different. R ₂ is a hydroxyl group, a carboxyl group, —O—R ₃ , or —COO—R ₃ , and when there are a plurality of R _{2 s} , they may be the same or different. R ₃ in R ₁ and R ₂ is an organic group having 1 to 15 carbon atoms. When R ₁ has no hydroxyl group, at least one of R ₂ is a carboxyl group. If there is no carboxyl group as R _2, at least one of R ₁ is a hydroxyl group. m is an integer of 0 to 8, and n is an integer of 0 to 8.
In the amide resin represented by the general formula (5), X, Y, R _{1 to} R ₃ , m and n may be the same for each repeating unit, or may be different from each other.

  In a precursor having an amide bond having a structure represented by the general formula (5), a polyimide resin or a polybenzoxazole resin, or an imide bond and an oxazole ring can be formed by causing a heat dehydration or a dehydration reaction using a catalyst. A copolymer containing is produced. (A) When using the precursor which has an amide bond as alkali-soluble resin, (A) alkali-soluble resin may further contain one or both of polyimide resin and polybenzoxazole resin.

When the precursor having an amide bond represented by the general formula (5) is a polybenzoxazole precursor, at least one of R ₁ is a hydroxyl group. In this case, a dehydration ring closure occurs between R ₁ and the amide structure by heat dehydration or a dehydration reaction using a catalyst, and a polybenzoxazole resin having an oxazole ring is generated. At this time, (A) alkali-soluble resin contains at least one of a polybenzoxazole precursor or a polybenzoxazole resin.
Also, if the precursor having an amide bond represented by the general formula (5) is a polyimide precursor, at least one of R ₂ is a carboxyl group. In this case, dehydration ring closure (imidization) occurs between R ₂ and the amide structure by heat dehydration or a dehydration reaction using a catalyst, and a polyimide resin is generated. At this time, (A) alkali-soluble resin will contain at least one of a polyimide precursor or a polyimide resin.

In the precursor having an amide bond having a repeating unit represented by the general formula (5), R ₁ and R ₂ are a hydroxyl group or a carboxyl group for adjusting the solubility of the precursor having an amide bond in an alkaline aqueous solution. The group can include a group protected with a protecting group R ₃ . As such R ₁ , —O—R ₃ can be used, and as R ₂ , —O—R ₃ or —COO—R ₃ can be used. Examples of the organic group having 1 to 15 carbon atoms as R ₃ include formyl group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, tertiary butoxycarbonyl group, phenyl group, benzyl group and tetrahydrofuranyl group. Groups, and tetrahydropyranyl groups.

  The organic group as X of the precursor having an amide bond having the structure represented by the general formula (5) is not particularly limited, but for example, an aromatic having a structure such as a benzene ring, a naphthalene ring or a bisphenol structure. A heterocyclic organic group having a structure such as a group, a pyrrole ring or a furan ring, and a siloxane group. More specifically, those shown below are preferable. These can be used alone or in combination of two or more.

（＊は、一般式（５）におけるＮＨ基に結合することを示す。Ａは、アルキレン基、置換アルキレン基、−Ｏ−Ｃ_６Ｈ_４−Ｏ−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）−または単結合である。Ｒ_４は、アルキル基、アルキルエステル基およびハロゲン原子からなる群から選ばれた１つを示し、繰り返し単位毎に同一であっても異なっていてもよい。Ｒ_５は、水素原子、アルキル基、アルキルエステル基およびハロゲン原子からなる群から選ばれた１つを示す。ｓは０〜４の整数である。Ｒ_６〜Ｒ_９はそれぞれ有機基である。ここでは、一般式（５）に示すＸの置換基Ｒ_１は省略している）

(* Indicates bonding to the NH group in the general formula (5). A represents an alkylene group, a substituted alkylene group, —O—C ₆ H ₄ —O—, —O—, —S—, —SO. _2- , -C (= O)-, -NHC (= O)-or a single bond, R ₄ represents one selected from the group consisting of an alkyl group, an alkyl ester group and a halogen atom, and Each unit may be the same or different, and R ₅ represents one selected from the group consisting of a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom, and s is an integer of 0 to 4. R _{6 to} R ₉ are each an organic group (here, the substituent R _{1 of} X shown in the general formula (5) is omitted)

  Y in the precursor having an amide bond having a structure represented by the general formula (5) is an organic group, and examples of such an organic group include those similar to X. Y in the general formula (5) is, for example, an aromatic group having a structure such as a benzene ring, a naphthalene ring or a bisphenol structure, a heterocyclic organic group having a structure such as a pyrrole ring, a pyridine ring or a furan ring, and a siloxane group. Etc. More specifically, those shown below are preferable. These can be used alone or in combination of two or more.

（＊は、一般式（５）におけるＣ＝Ｏ基に結合することを示す。Ｊは、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）−、−Ｃ（ＣＦ_３）_２−または単結合である。Ｒ_１３は、アルキル基、アルキルエステル基、アルキルエーテル基、ベンジルエーテル基およびハロゲン原子からなる群から選ばれた１つを示し、繰り返し単位毎に同じでも異なってもよい。Ｒ_１４は、水素原子、アルキル基、アルキルエステル基およびハロゲン原子からなる群から選ばれた１つを示す。ｔは０以上２以下の整数である。Ｒ_１５〜Ｒ_１８は、有機基である。ここでは、一般式（５）に示すＹの置換基Ｒ_２は省略している）

(* Indicates bonding to the C═O group in the general formula (5). J represents —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —. , —C (═O) —, —NHC (═O) —, —C (CF ₃ ) ₂ — or a single bond, R ₁₃ represents an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group, and 1 is selected from the group consisting of halogen atoms, and may be the same or different for each repeating unit, and R ₁₄ is one selected from the group consisting of a hydrogen atom, an alkyl group, an alkyl ester group and a halogen atom. T is an integer of 0 to 2. R _{15 to} R ₁₈ are organic groups.Here, the substituent R _{2 of} Y shown in the general formula (5) is omitted).

In the case of a precursor having an amide bond represented by the general formula (5), an amino group at the terminal of the precursor is converted to an alkenyl group so as not to affect the mechanical properties and heat resistance of the cured product cured at low temperature. Alternatively, it can be end-capped as an amide using an acid anhydride or monocarboxylic acid containing an aliphatic group or a cyclic compound group having at least one alkynyl group.
Examples of the acid anhydride or monocarboxylic acid containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group include maleic anhydride, citraconic anhydride, and 2,3-dimethylmaleic anhydride. 4-cyclohexene-1,2-dicarboxylic acid anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, methyl -5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, het acid anhydride, 5-norbornene-2-carboxylic acid, 4-ethynylphthalic anhydride, and 4-phenylethynylphthalic anhydride Can be mentioned. These may be used alone or in combination of two or more, and a part of the end-capped amide moiety may be dehydrated and closed.

  In the case of a precursor having an amide bond represented by the general formula (5), an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group as the terminal carboxylic acid residue of the precursor. An amine derivative containing can be used to end-cleave as an amide.

  In the case of a precursor having an amide bond represented by the general formula (5), at least one of the terminals is terminated with a nitrogen-containing cyclic compound to such an extent that the mechanical properties and heat resistance of the cured product cured at low temperature are not affected. You may have the group sealed. Thereby, adhesiveness with a metal wiring (especially copper wiring) etc. can be improved. Examples of the nitrogen-containing cyclic compound include 1- (5-1H-triazoyl) methylamino group, 3- (1H-pyrazoyl) amino group, 4- (1H-pyrazoyl) amino group, and 5- (1H-pyrazoyl) amino group. 1- (3-1H-pyrazolyl) methylamino group, 1- (4-1H-pyrazoyl) methylamino group, 1- (5-1H-pyrazoyl) methylamino group, (1H-tetrazol-5-yl) amino Groups, 1- (1H-tetrazol-5-yl) methyl-amino group, and 3- (1H-tetrazol-5-yl) benz-amino group.

  The precursor having an amide bond having a structure represented by the general formula (5) is, for example, a compound selected from diamine containing X in the general formula (5), bis (aminophenol), 2,4-diaminophenol, and the like. , Y-containing tetracarboxylic dianhydride, trimellitic anhydride, dicarboxylic acid, dicarboxylic acid dichloride or dicarboxylic acid derivative and the like can be reacted to synthesize. In the case of using a dicarboxylic acid, an active ester type dicarboxylic acid obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like with dicarboxylic acid in advance in order to increase the reaction yield of the precursor having an amide bond. Derivatives may be used.

  (A) As the phenol resin in the alkali-soluble resin, for example, a reaction product of a phenol compound typified by a novolac type phenol resin and an aldehyde compound can be used. By using a phenol resin obtained by reacting such a phenol compound and an aldehyde compound, film loss in the development process can be suppressed, and the manufacturing cost can be reduced.

  Although it does not specifically limit as a phenol compound, For example, cresols, such as phenol, o-cresol, m-cresol, or p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6 -Xylenols such as xylenol, 3,4-xylenol or 3,5-xylenol, ethylphenols such as o-ethylphenol, m-ethylphenol or p-ethylphenol, isopropylphenol, butylphenol or p-tert-butylphenol Or polyphenols such as resorcin, catechol, hydroquinone, pyrogallol or phloroglucin can be used. These phenol compounds can be used alone or in combination of two or more.

The aldehyde compound is not particularly limited as long as it is an organic group having an aldehyde group. For example, formalin, paraformaldehyde, acetaldehyde, benzaldehyde, or salicylaldehyde can be used. As the benzaldehyde, one substituted with at least one of an alkyl group, an alkoxy group or a hydroxy group, or an unsubstituted one can be used. These aldehyde compounds can be used alone or in combination of two or more.
In the present embodiment, for example, by synthesizing the phenol compound and the aldehyde compound by reacting them in the presence of an acid catalyst, (A) a phenol resin that is an alkali-soluble resin is obtained. The acid catalyst is not particularly limited, and for example, oxalic acid, nitric acid, sulfuric acid, diethyl sulfate, acetic acid, p-toluenesulfonic acid, phenolsulfonic acid, or benzenesulfonic acid can be used.

  (A) As a hydroxystyrene resin in an alkali-soluble resin, a polymerization reaction product or a copolymerization reaction product obtained by radical polymerization, cation polymerization, or anion polymerization of hydroxystyrene, styrene, or a derivative thereof can be used. .

In the present embodiment, the content of the (A) alkali-soluble resin in the positive photosensitive resin composition is 50 parts by mass or more with respect to 100 parts by mass as a whole of the solid content of the positive photosensitive resin composition. Is preferably 60 parts by mass or more, and more preferably 65 parts by mass or more. Further, the content of the (A) alkali-soluble resin in the positive photosensitive resin composition is preferably 95 parts by mass or less with respect to 100 parts by mass as a whole of the solid content of the positive photosensitive resin composition. The amount is more preferably 92 parts by mass or less, and still more preferably 90 parts by mass or less. (A) By making content of alkali-soluble resin more than the said lower limit, sclerosis | hardenability of positive type photosensitive resin composition can be improved. Thereby, the heat resistance of a cured film formed using a photosensitive resin material, mechanical strength, and durability can be improved. (A) By making content of alkali-soluble resin below the said upper limit, the resolution in lithography can be improved.
In addition, the ratio (mass%) of solid content in a positive photosensitive resin composition can be measured as follows, for example. First, 1.0 g of a positive photosensitive resin composition is weighed out as a sample in an aluminum cup whose weight (w ₀ ) has been measured. In this case, the total weight of the sample and the aluminum cup and w _1. Next, the aluminum cup is kept in a hot air dryer adjusted to 210 ° C. under normal pressure for 1 hour, and then taken out of the hot air dryer and cooled to room temperature. Next, the total weight (w ₂ ) of the cooled sample and the aluminum cup is measured. And the ratio (mass%) of solid content in a positive photosensitive resin composition is computed from the following formula | equation.
Nonvolatile content (mass%) = (w ₂ −w ₀ ) / (w ₁ −w ₀ ) × 100

((B) Photosensitizer)
The positive photosensitive resin composition of this embodiment contains (B) a photosensitive agent. As the photosensitizer (B), known ones can be employed, and are not particularly limited. For example, a diazoquinone compound can be employed. Examples of the diazoquinone compound used as the photosensitizer include those exemplified below.

  In each of the above compounds, Q is any one of the structures (a), (b) and (c) shown below, or a hydrogen atom. However, at least one of Q contained in each compound is one of the following structure (a), structure (b), and structure (c). From the viewpoint of the transparency and dielectric constant of the photosensitive resin composition, an o-naphthoquinonediazidesulfonic acid derivative in which Q is the structure (a) or the structure (b) is more preferable.

The content of the photosensitive agent (B) in the positive photosensitive resin composition of the present embodiment is preferably 1.5 parts by mass or more with respect to 100 parts by mass of the (A) alkali-soluble resin. The amount is more preferably 5 parts by mass or more, and further preferably 4 parts by mass or more. Moreover, it is preferable that content of (B) photosensitive agent in positive type photosensitive resin composition is 25 mass parts or less with respect to 100 mass parts of (A) alkali-soluble resin, and is 18 mass parts or less. More preferably, the amount is 15 parts by mass or less.
Further, the content of (B) the photosensitizer is preferably 1 part by mass or more, more preferably 2 parts by mass or more, based on 100 parts by mass of the total solid content of the positive photosensitive resin composition. More preferably, it is 3 parts by mass or more. In addition, the content of (B) the photosensitive agent is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, based on 100 parts by mass of the total solid content of the positive photosensitive resin composition. More preferably, it is 10 parts by mass or less.
This makes it possible to effectively improve the balance of reactivity, stability over time, and developability in the positive photosensitive resin composition.

((C) polyfunctional (meth) acrylate compound)
The positive photosensitive resin composition of the present embodiment comprises (C) a polyfunctional (meth) acrylate compound having a hydroxyl group and 2 or more and 4 or less (meth) acryl groups in the molecule (in the present specification, And “(C) polyfunctional (meth) acrylate compound”).
In the present embodiment, by using the (meth) acrylate compound having this specific structure, it is possible to improve the balance between developability and adhesion as the positive photosensitive resin composition.
In the present specification, the (meth) acrylate compound is a methacrylate compound and an acrylate compound, and the (meth) acryl group is a generic name for a methacryl group and an acryl group.

  Specifically, as this (C) polyfunctional (meth) acrylate compound, a compound having a specific amount of (meth) acrylic group is used, and by this (meth) acrylic group, appropriate developability is improved. It is thought that you can. The (meth) acryl group is provided in the compound in an amount of 2 or more and 4 or less, and more preferably 2 or more and 3 or less from the viewpoint of adjusting reactivity. (C) By making the number of (meth) acrylic groups in the polyfunctional (meth) acrylate compound equal to or higher than this lower limit value, the boiling point of the compound increases, so that it remains in the film after pre-baking and the adhesion improving effect is further improved. When the number of (meth) acrylic groups is less than or equal to this upper limit value, it is possible to suppress a decrease in developability.

Moreover, as this (C) polyfunctional (meth) acrylate compound, it has a hydroxyl group in a molecule | numerator, and this can exhibit affinity with (A) alkali-soluble resin, and this improves adhesiveness. Can be planned.
That is, the positive photosensitive resin composition of the present embodiment can exhibit a desired effect due to the synergistic effect of the (meth) acryl group and the hydroxyl group.
Here, the number of hydroxyl groups in the (C) polyfunctional (meth) acrylate compound is not particularly limited. For example, the number of hydroxyl groups in the molecule is preferably 1 to 5 and preferably 1 to 4 in the molecule. Is more preferable, having 1 to 3 in the molecule is more preferable, and it is particularly preferable to have 1 or 2 in the molecule. (C) By setting the number of hydroxyl groups in the polyfunctional (meth) acrylate compound to be equal to or higher than this lower limit, affinity with the alkali-soluble resin can be exhibited, and by setting this number to the upper limit or lower, Solubility can be ensured.

This (C) polyfunctional (meth) acrylate compound can be appropriately selected from the above-mentioned compounds having a (meth) acryl group and a hydroxyl group.
More specifically, this (C) polyfunctional (meth) acrylate compound is obtained by esterifying a polyol compound having three or more hydroxyl groups by allowing acrylic acid or methacrylic acid to act and leaving some hydroxyl groups remaining. Can do. In addition, a compound in which all hydroxyl groups are (meth) acrylated is converted to an ester partially converted to hydroxyl groups by applying a predetermined amount of base (sodium hydroxide, potassium hydroxide, etc.). You can also.
In addition, commercially available products that are distributed in the market can be used, and are composed of glycerin diacrylate, glycerin dimethacrylate, tetramethylol triacrylate, and tetramethylol trimethacrylate because of its high availability and high handling during production. One or more compounds selected from the group are preferred.

The content of the (C) polyfunctional (meth) acrylate compound in the positive photosensitive resin composition of the present embodiment is 0.01 parts by mass or more with respect to 100 parts by mass of the (A) alkali-soluble resin. Is preferably 0.03 parts by mass or more, more preferably 0.1 parts by mass or more, and particularly preferably 0.5 parts by mass or more. In addition, the content of the (C) polyfunctional (meth) acrylate compound in the positive photosensitive resin composition is preferably 10 parts by mass or less with respect to 100 parts by mass of the (A) alkali-soluble resin. The amount is more preferably at most 6 parts by mass, even more preferably at most 6 parts by mass. (C) Adhesion can be improved by setting the content of the polyfunctional (meth) acrylate compound to be equal to or higher than the lower limit, and resolution can be maintained by setting the content to be equal to or lower than the upper limit.
Moreover, it is preferable that content of (C) polyfunctional (meth) acrylate compound is 0.005 mass part or more with respect to 100 mass parts of solid content whole of positive photosensitive resin composition, and 0.02 mass It is more preferably at least 0.1 part by mass, even more preferably at least 0.1 part by mass, and particularly preferably at least 0.3 part by mass. Moreover, it is preferable that content of (C) polyfunctional (meth) acrylate compound is 8 mass parts or less with respect to 100 mass parts of solid content whole of a positive photosensitive resin composition, and is 6 mass parts or less. More preferred is 5 parts by mass or less. (C) The adhesiveness of a cured film can be improved by making content of a polyfunctional (meth) acrylate compound more than this lower limit, and resolution can be maintained by making it below this upper limit. it can.

((D) Adhesion aid)
The photosensitive resin composition of this embodiment may contain (D) adhesion assistant. (D) The adhesion assistant is not particularly limited, but may include, for example, a silane coupling agent such as aminosilane, epoxy silane, acrylic silane, mercaptosilane, vinyl silane, ureido silane, or sulfide silane. These may be used alone or in combination of two or more. Among these, it is more preferable to use epoxysilane from the viewpoint of effectively improving the adhesion to other members.

  Examples of aminosilanes include bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, and γ-aminopropyl. Methyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N -Β (aminoethyl) γ-aminopropylmethyldiethoxysilane, and N-phenyl-γ-amino-propyltrimethoxysilane. Examples of the epoxy silane include γ-glycidoxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane), γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, and β. -(3,4-epoxycyclohexyl) ethyltrimethoxysilane. Examples of the acrylic silane include γ- (methacryloxypropyl) trimethoxysilane, γ- (methacryloxypropyl) methyldimethoxysilane, and γ- (methacryloxypropyl) methyldiethoxysilane. An example of mercaptosilane is γ-mercaptopropyltrimethoxysilane. Examples of the vinyl silane include vinyl tris (β methoxyethoxy) silane, vinyl triethoxy silane, and vinyl trimethoxy silane. Examples of ureidosilane include 3-ureidopropyltriethoxysilane. Examples of the sulfide silane include bis (3- (triethoxysilyl) propyl) disulfide and bis (3- (triethoxysilyl) propyl) tetrasulfide.

In the case where (D) the adhesion assistant is included in the positive photosensitive resin composition of the present embodiment, the content thereof is 0.1 parts by mass or more with respect to 100 parts by mass of (A) the alkali-soluble resin. It is preferably 1 part by mass or more, more preferably 2 parts by mass or more. Further, the content of the (D) adhesion assistant in the positive photosensitive resin composition is preferably 30 parts by mass or less, and 20 parts by mass or less with respect to 100 parts by mass of the (A) alkali-soluble resin. More preferably, it is more preferably 10 parts by mass or less.
Moreover, when (D) adhesion assistant is included in the positive photosensitive resin composition, the content thereof is 0.05 parts by mass or more with respect to 100 parts by mass as a whole of the solid content of the positive photosensitive resin composition. Preferably, it is 0.8 parts by mass or more, more preferably 1.5 parts by mass or more. In addition, the content of the (D) adhesion assistant is preferably 25 parts by mass or less, more preferably 15 parts by mass or less, with respect to 100 parts by mass as a whole of the solid content of the positive photosensitive resin composition. More preferably, it is 10 parts by mass or less.
(D) By adjusting the content of the adhesion assistant to such a range, the adhesion of the cured film formed using the positive photosensitive resin composition to other members is more effectively improved. be able to.

  When (D) adhesion assistant is included in the positive photosensitive resin composition of the present embodiment, the ratio of the content of (C) polyfunctional (meth) acrylate compound to the content of (D) adhesion assistant However, it is preferably 0.0001 or more, more preferably 0.001 or more, and further preferably 0.002 or more. Further, the ratio of the content of the (C) polyfunctional (meth) acrylate compound to the content of the (D) adhesion assistant is preferably 10 or less, more preferably 5 or less, and 3 or less. More preferably it is. (D) The adhesiveness of a cured film can be improved by setting the ratio of the content of the (C) polyfunctional (meth) acrylate compound to the content of the adhesion assistant above this lower limit, and this upper limit. The resolution can be maintained by the following.

((E) a compound having a glycidyl group or a compound having an oxetanyl group)
The positive photosensitive resin composition of the present embodiment may contain (E) a compound having a glycidyl group or a compound having an oxetanyl group as a crosslinking agent. Thereby, the further improvement of sclerosis | hardenability can be aimed at and it can contribute to the improvement of the mechanical characteristic of a cured film.

  An example of the compound having a glycidyl group used as a crosslinking agent is an epoxy compound. Examples of the epoxy compound include n-butyl glycidyl ether, 2-ethoxyhexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether. Glycidyl ether such as sorbitol polyglycidyl ether, glycidyl ether of bisphenol A (or F), glycidyl ester such as adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, 3,4-epoxycyclohexylmethyl (3,4) -Epoxycyclohexane) carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl (3,4-epoxy) -6-methylcyclohexane) carboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentanediene oxide, bis (2,3-epoxycyclopentyl) ether, and Celoxide manufactured by Daicel Corporation 2021, celoxide 2081, ceroxide 2083, celoxide 2085, celoxide 8000, epoxide GT401, and the like, 2,2 '-((((1- (4- (2- (4- (oxiran-2-ylmethoxy) Phenyl) propan-2-yl) phenyl) ethane-1,1-diyl) bis (4,1-phenylene)) bis (oxy)) bis (methylene)) bis (oxirane) (eg Techmore VG3101L, Inc.) Printec)), Epolite Aliphatic polyglycidyl ethers such as 00MF (manufactured by Kyoeisha Chemical Industry Co., Ltd.), Epiol TMP (manufactured by NOF Corporation), 1,1,3,3,5,5-hexamethyl-1,5-bis (3 -(Oxiran-2-ylmethoxy) propyl) tri-siloxane (for example, DMS-E09 (manufactured by Gerest)) or the like can be used.

In addition, bisphenols such as LX-01 (manufactured by Daiso Corporation), jER1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 (trade names; manufactured by Mitsubishi Chemical Corporation) A type epoxy resin, bisphenol F type epoxy resin such as jER807 (trade name; manufactured by Mitsubishi Chemical Corporation), jER152, 154 (trade name; manufactured by Mitsubishi Chemical Corporation), EPPN201, 202 (trade name; Japan) Phenolic novolak type epoxy resins such as EOCN102, 103S, 104S, 1020, 1025, 1027 (trade name; manufactured by Nippon Kayaku Co., Ltd.), jER157S70 (trade name; Mitsubishi Chemical Corporation) Cresol novolac type epoxy resin, Araldite CY179, 184 (trade name; Hunts) Advanced Materials, Inc.), ERL-4206, 4221, 4234, 4299 (trade name; manufactured by Dow Chemical Co.), Epicron 200, 400 (trade name; manufactured by DIC Corporation), jER871, 872 (trade name; Cyclic aliphatic epoxy resin such as Mitsubishi Chemical Co., Ltd., Poly [(2-oxylanyl) -1,2-cyclohexanediol] 2-ethyl-2- (hydroxymethyl) -1,3-propaneether (3: 1) Polyfunctional alicyclic epoxy resins such as EHPE-3150 (manufactured by Daicel Corporation) can also be used.
In addition, the positive photosensitive resin composition in this embodiment can contain 1 type, or 2 or more types of the epoxy compound illustrated above.

  Examples of the compound having an oxetanyl group used as a crosslinking agent include 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, bis [1-ethyl (3-oxetanyl)] methyl ether, 4 , 4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 4,4′-bis (3-ethyl-3-oxetanylmethoxy) biphenyl, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ) Ether, diethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) diphenate, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis ( 3-ethyl-3-oki Tanylmethyl) ether, poly [[3-[(3-ethyl-3-oxetanyl) methoxy] propyl] silasesquioxane] derivatives, oxetanyl silicate, phenol novolac oxetane, 1,3-bis [(3-ethyloxetane-3 -Yl) methoxy] benzene and the like, but are not limited thereto. These may be used alone or in combination.

When the positive photosensitive resin composition of this embodiment contains (E) a compound having a glycidyl group or a compound having an oxetanyl group, the content thereof is (A) 100 parts by mass of the alkali-soluble resin. 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more. The content of the compound (E) having a glycidyl group or the compound having an oxetanyl group in the positive photosensitive resin composition is 25 parts by mass or less with respect to 100 parts by mass of the (A) alkali-soluble resin. Is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less.
When the positive photosensitive resin composition contains (E) a compound having a glycidyl group or a compound having an oxetanyl group, the content is 100 parts by mass as a whole of the solid content of the positive photosensitive resin composition. On the other hand, it is preferably 0.05 parts by mass or more, more preferably 0.3 parts by mass or more, and further preferably 0.5 parts by mass or more. In addition, the content of the compound (E) having a glycidyl group or a compound having an oxetanyl group is preferably 20 parts by mass or less with respect to 100 parts by mass as a whole of the solid content of the positive photosensitive resin composition. More preferably, it is more preferably 12 parts by mass or less.
(E) By adjusting the content of the compound having a glycidyl group or the compound having an oxetanyl group to such a range, the balance between the reactivity and the stability over time in the positive photosensitive resin composition is further improved. It becomes possible to improve effectively.

((F) polymerization initiator)
The positive photosensitive resin composition of this embodiment can contain (F) a polymerization initiator. Thereby, the polymerizability of (C) polyfunctional (meth) acrylate compound can be improved, and developability can be improved further.

(F) As a polymerization initiator, any one or more of an azo compound and an organic peroxide can be used. Any compound can be selected from known compounds among the compounds used as the polymerization initiator.
As the azo compound, for example, azobisisobutyronitrile (AIBN), 2,2-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate), 1,1 '-Azobis (cyclohexanecarbonitrile) (ABCN) can be used, and any one or more of these can be used.
Examples of organic peroxides include hydrogen peroxide, ditertiary butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). Any one or more of them can be used.

When the positive photosensitive resin composition of the present embodiment contains (F) a polymerization initiator, the content is 0.01 parts by mass or more with respect to 100 parts by mass of (A) the alkali-soluble resin. Preferably, it is 0.03 part by mass or more, and more preferably 0.05 part by mass or more. Moreover, it is preferable that content of (F) polymerization initiator in positive photosensitive resin composition is 5 mass parts or less with respect to 100 mass parts of (A) alkali-soluble resin, and is 3 mass parts or less. More preferably, it is more preferably 2 parts by mass or less.
Moreover, as a positive photosensitive resin composition, when (F) a polymerization initiator is contained, the content is 0.005 parts by mass or more with respect to 100 parts by mass as a whole of the solid content of the positive photosensitive resin composition. It is preferable that it is 0.01 mass part or more, and it is further more preferable that it is 0.02 mass part or more. Moreover, it is preferable that content of (F) polymerization initiator is 4 mass parts or less with respect to 100 mass parts of solid content whole of a positive photosensitive resin composition, and it is 2.5 mass parts or less. More preferably, it is 1.5 parts by mass or less.
(F) By adjusting the content of the polymerization initiator to such a range, the developability in the positive photosensitive resin composition can be improved more effectively.

((G) Surfactant)
The positive photosensitive resin composition of this embodiment may contain (G) a surfactant. The (G) surfactant includes, for example, a compound containing a fluorine group (for example, a fluorinated alkyl group) or a silanol group, or a compound having a siloxane bond as a main skeleton.
In this embodiment, it is more preferable to use a surfactant containing a fluorosurfactant or a silicone surfactant, and it is particularly preferable to use a fluorosurfactant. Examples of the surfactant include Megafac F-554, F-556, and F-557 manufactured by DIC Corporation, but are not limited thereto.

In the positive photosensitive resin composition of the present embodiment, when (G) a surfactant is contained, the content thereof is 0.005 parts by mass or more with respect to 100 parts by mass of (A) the alkali-soluble resin. Preferably, it is 0.007 parts by mass or more, and more preferably 0.01 parts by mass or more. Further, the content of the surfactant (G) in the positive photosensitive resin composition is preferably 2 parts by mass or less with respect to 100 parts by mass of the (A) alkali-soluble resin, and is 1 part by mass or less. More preferably, it is more preferably 0.5 parts by mass or less.
Moreover, when (G) surfactant is contained as positive photosensitive resin composition, the content is 0.003 mass part or more with respect to 100 mass parts of the whole solid content of positive photosensitive resin composition. It is preferable that it is 0.005 mass part or more, and it is further more preferable that it is 0.008 mass part or more. Further, the content of the (G) surfactant is preferably 1.5 parts by mass or less, more preferably 0.8 parts by mass or less, based on the total solid content of the positive photosensitive resin composition. Preferably, it is 0.4 parts by mass or less.
(G) By adjusting the content of the surfactant to such a range, the flatness when obtaining a cured film from the positive photosensitive resin composition can be effectively improved. In addition, it is possible to prevent the occurrence of radial striations on the coating film during spin coating.

(Other ingredients)
In addition, you may add additives, such as antioxidant, a coloring agent, a filler, and a sensitizer, in the photosensitive resin composition as needed. The antioxidant can include, for example, one or more selected from the group of phenolic antioxidants, phosphorus antioxidants, and thioether antioxidants. Although it does not specifically limit as a coloring agent, For example, C.I. I. PR254, C.I. I. PR177 and C.I. I. A red pigment exemplified by PR224 and the like; I. PG7 and C.I. I. Green pigments exemplified by PG36 and the like, C.I. I. PB15: 6 and C.I. I. A blue pigment exemplified by PB60 and the like; I. PY138, C.I. I. PY139, C.I. I. PY150, C.I. I. PY128 and C.I. I. Organic pigments such as yellow pigments exemplified by PY185, carbon, titanium carbon, iron oxide, titanium white, silica, talc, magnesium carbonate, calcium carbonate, mica, aluminum hydroxide, precipitated barium carbonate, chromium oxide, manganese oxide , And one or more selected from inorganic pigments such as titanium oxide. The filler can contain 1 type, or 2 or more types selected from inorganic fillers, such as a silica, for example. The sensitizer is selected from the group of, for example, anthracene, xanthone, anthraquinone, phenanthrene, chrysene, benzpyrene, fluoracene, rubrene, pyrene, indanthrine and thioxanthen-9-ones 1 type, or 2 or more types can be included.

((S) solvent)
The positive photosensitive resin composition of this embodiment may contain a solvent. In this case, the positive photosensitive resin composition is varnished. Examples of the solvent include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), gamma butyrolactone (GBL), N-methylpyrrolidone (NMP), methyl n-amyl ketone. One or more of (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol methyl ethyl ether, and benzyl alcohol can be included.

The content of the (S) solvent in the positive photosensitive resin composition of the present embodiment is not particularly limited, but is (A) 100 parts by mass or more with respect to 100 parts by mass of the alkali-soluble resin. Is more preferable, and 150 parts by mass or more is more preferable.
Further, the content of the (S) solvent in the positive photosensitive resin composition of the present embodiment is preferably 1000 parts by mass or less, and 800 parts by mass or less with respect to 100 parts by mass of the (A) alkali-soluble resin. It is more preferable that (S) When content of a solvent exists in the said range, moderate handling property can be brought about.

(Electronic device)
Next, the electronic device according to the present embodiment will be described.
FIG. 1 is a cross-sectional view illustrating an example of the electronic device 100.
FIG. 1 illustrates the case where the electronic device 100 is a liquid crystal display device and the insulating film 20 is used as a planarization film. An electronic device 100 illustrated in FIG. 1 is provided on, for example, a substrate 10, a transistor 30 provided on the substrate 10, an insulating film 20 provided on the substrate 10 so as to cover the transistor 30, and the insulating film 20. Wiring 40.
This insulating film 20 can be constituted by a cured film made of a cured product of the positive photosensitive resin composition of the present embodiment.

  The substrate 10 is, for example, a glass substrate. The transistor 30 is a thin film transistor that constitutes a switching element of a liquid crystal display device, for example. On the substrate 10, for example, a plurality of transistors 30 are arranged in an array. The transistor 30 shown in FIG. 1 includes, for example, a gate electrode 31, a source electrode 32, a drain electrode 33, a gate insulating film 34, and a semiconductor layer 35. The gate electrode 31 is provided on the substrate 10, for example. The gate insulating film 34 is provided on the substrate 10 so as to cover the gate electrode 31. The semiconductor layer 35 is provided on the gate insulating film 34. The semiconductor layer 35 is, for example, a silicon layer. The source electrode 32 is provided on the substrate 10 so that a part thereof is in contact with the semiconductor layer 35. The drain electrode 33 is provided on the substrate 10 so as to be separated from the source electrode 32 and partially in contact with the semiconductor layer 35.

The insulating film 20 functions as a planarization film for eliminating a step due to the transistor 30 and the like and forming a flat surface on the substrate 10. Moreover, the insulating film 20 is comprised with the hardened | cured material of the above-mentioned positive type photosensitive resin composition. The insulating film 20 is provided with an opening 22 that penetrates the insulating film 20 so as to be connected to the drain electrode 33.
A wiring 40 connected to the drain electrode 33 is formed on the insulating film 20 and in the opening 22. The wiring 40 functions as a pixel electrode that constitutes a pixel together with the liquid crystal.
An alignment film 90 is provided on the insulating film 20 so as to cover the wiring 40.

A counter substrate 12 is disposed above one surface of the substrate 10 where the transistor 30 is provided so as to face the substrate 10. A wiring 42 is provided on one surface of the counter substrate 12 facing the substrate 10. The wiring 42 is provided at a position facing the wiring 40. An alignment film 92 is provided on the one surface of the counter substrate 12 so as to cover the wiring 42.
The liquid crystal constituting the liquid crystal layer 14 is filled between the substrate 10 and the counter substrate 12.

The electronic device 100 shown in FIG. 1 can be formed as follows, for example.
First, the transistor 30 is formed over the substrate 10. Next, the positive photosensitive resin composition is applied to one surface of the substrate 10 on which the transistor 30 is provided by a printing method or a spin coating method to form the insulating film 20 that covers the transistor 30. Next, lithography processing is performed on the insulating film 20 to pattern the insulating film 20. Thereby, an opening 22 is formed in a part of the insulating film 20. Next, the insulating film 20 is heated and cured. As a result, the insulating film 20 that is a planarizing film is formed on the substrate 10.
Next, a wiring 40 connected to the drain electrode 33 is formed in the opening 22 of the insulating film 20. Thereafter, the counter substrate 12 is disposed on the insulating film 20, and liquid crystal is filled between the counter substrate 12 and the insulating film 20 to form the liquid crystal layer 14.
As a result, the electronic device 100 shown in FIG. 1 is formed.

  It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.

  Next, examples of the present invention will be described.

(Synthesis of monomer 1)
In a reaction vessel equipped with a stirrer and a cooler, 700.0 g of dicyclopentadiene and 100.0 g of liquid paraffin are added, and the decomposition product obtained by heating at 160 to 170 ° C. is converted into a cooler (cooling water The mixture was cooled at a temperature of 5 ° C. to obtain cyclopentadiene. Next, 283.2 g of oxetane acrylic (OXE-10, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was placed in another reaction vessel, and 100 g of the cyclopentadiene obtained above was obtained over 3 hours at 20 ° C. Was added successively, followed by stirring for 16 hours at 30 ° C to 35 ° C. Subsequently, the reaction product obtained thereby was fractionally purified by a vacuum distillation apparatus using a Vigreux column to obtain a monomer 1 represented by the following formula (13).

^{The 1} H-NMR spectrum and ¹³ C-NMR spectrum were analyzed, and it was confirmed that the obtained monomer 1 had a structure represented by the above formula. Moreover, the obtained monomer 1 was a structural isomer mixture of endo / exo = 78/22. In addition, the measured NMR spectrum data were as follows.

¹ H-NMR (400 MHz, CDCl ₃ ): 0.91 (t, endo-3H), 0.92 (t, exo-3H), 1.29 (d, endo-1H), 1.37-1. 47 (m, 2H), 1.52 (d, exo-1H), 1.73-1.80 (m, 2H), 1.90-1.97 (m, 1H), 2.26-2. 30 (m, exo-1H), 2.92 (brs, 1H), 2.98-3.03 (m, endo-1H), 3.05 (brs, exo-1H), 3.23 ( s, endo-1H), 4.16 (dd, endo-2H), 4.23 (dd, exo-2H), 4.40 (d, endo-2H), 4.41 (d, exo-2H) 4.46 (d, endo-2H), 4.49 (dd, exo-2H), 5.92 (dd, endo-1H), 6 11-6.16 (m, exo-2H), 6.21 (dd, endo-1H).
¹³ C-NMR (100 MHz, CDCl ₃ ): 8.0, 26.9, 29.1, 30.3, 41.6, 42.4, 42.6, 42.6, 43.1, 43.3 , 45.7, 46.3, 46.6, 49.6, 65.9, 66.2, 77.8, 77.9, 132.1, 135.6, 137.9, 138.0, 174 .7, 176.2 ppm.

(Synthesis of alkali-soluble resin (A-1))
In a sealable reaction vessel, monomer 1 (10.8 g, 45.8 mmol) obtained by the above synthesis example, norbornene carboxylic acid (11.92 g, 91.7 mmol), methyl glycidyl ether norbornene (57.6 g, 320 mmol) ), Maleimide (28.88 g, 297.7 mmol), and cyclohexylmaleimide (16.32 g, 91.2 mmol). Furthermore, 58.4 g of propylene glycol monomethyl ether (PGME) in which azo polymerization initiator V-601 (8.4 g, 36.5 mmol) was dissolved was added to the reaction vessel and stirred and dissolved. Next, after the dissolved oxygen in the system was removed by nitrogen bubbling, the container was sealed and reacted at 70 ° C. for 16 hours. The reaction mixture was then cooled to room temperature and diluted with 226 g of tetrahydrofuran (THF). The diluted solution was poured into a large amount of methanol to precipitate an alkali-soluble resin (A-1). Next, the polymer was collected by filtration, further washed with methanol, and then vacuum-dried at 30 ° C. for 16 hours. The yield of alkali-soluble resin (A-1) was 64.6 g, and the yield was 51%. The alkali-soluble resin (A-1) was dissolved in propylene glycol methyl ether acetate to prepare a solution having a solid concentration of 30%. Further, the alkali-soluble resin (A-1) had a weight average molecular weight Mw of 13,500 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.71.
The obtained alkali-soluble resin (A-1) had a structure represented by the following formula (10).

In addition, the polystyrene conversion value calculated | required from the calibration curve of the standard polystyrene (PS) obtained by GPC measurement was used for the weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained alkali-soluble resin. The measurement conditions are as follows.
Tosoh Corporation Gel Permeation Chromatography Equipment HLC-8320GPC
Column: Tosoh Corporation TSK-GEL Supermultipore HZ-M
Detector: RI detector for liquid chromatogram Measurement temperature: 40 ° C
Solvent: THF
Sample concentration: 2.0 mg / milliliter In addition, the measurement conditions of a weight average molecular weight (Mw) and a number average molecular weight (Mn) are the same also in the synthesis | combination of alkali-soluble resin (A-2)-(A-4) mentioned later. It is.

(Synthesis of alkali-soluble resin (A-2))
In a reaction vessel equipped with a stirrer and a condenser tube, monomer 1 (1.18 g, 5 mmol), maleimide (2.18 g, 22.5 mmol) obtained by the above synthesis example, N-cyclohexylmaleimide (4.92 g, 27.5 mmol), norbornene carboxylic acid (2.60 g, 20.0 mmol), methyl glycidyl ether norbornene (3.6 g, 20.0 mmol), and dibutyl fumaric acid (1.14 g, 5 mmol) were weighed. Further, 8.9 g of propylene glycol monomethyl ether acetate in which azo polymerization initiator V-601 (0.92 g, 4.0 mmol) was dissolved was added to the reaction vessel, and stirred and dissolved. Next, after removing dissolved oxygen in the system by nitrogen bubbling, the reaction was held at 70 ° C. in a nitrogen atmosphere for 5 hours. The reaction mixture was then cooled to room temperature and diluted by adding 30 g of methyl ethyl ketone (MEK). The diluted solution was poured into a large amount of hexane to precipitate an alkali-soluble resin (A-2). Next, the alkali-soluble resin (A-2) was collected by filtration, further washed with hexane, and then vacuum-dried at 30 ° C. for 16 hours.
The yield of alkali-soluble resin (A-2) was 13.4 g, and the yield was 86%. The alkali-soluble resin (A-2) was dissolved in propylene glycol methyl ether acetate to prepare a solution having a solid content of 30%. The polymer had a weight average molecular weight Mw of 8,800 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 2.19.
The obtained alkali-soluble resin (A-2) had a structure represented by the following formula (11).

(Synthesis of alkali-soluble resin (A-3))
A flask equipped with a condenser and a stirrer was charged with azo polymerization initiator V-601 (7 g, 0.03 mol) and 150 g of propylene glycol methyl ether acetate. Subsequently, styrene (8.23 g, 0.08 mol), methacrylic acid (11.34 g, 0.13 mol), glycidyl methacrylate (37.45 g, 0.26 mol), norbornane lactone methacrylate represented by the following formula (12) ( (11.66 g, 0.05 mol) and 1.5 g of α-methylstyrene dimer were charged, and then gently stirred while replacing with nitrogen, the temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours. To obtain a solution of the alkali-soluble resin (A-3). The concentration of this solution was adjusted using propylene glycol methyl ether acetate to prepare a 30% solid content concentration solution.
Mw of the obtained alkali-soluble resin (A-3) was 25,000, and Mw / Mn was 2.4.

(Synthesis of alkali-soluble resin (A-4))
A flask equipped with a condenser and a stirrer was charged with azo polymerization initiator V-601 (7 g, 0.03 mol) and 220 g of propylene glycol methyl ether acetate. Subsequently, styrene (8.23 g, 0.08 mol), methacrylic acid (11.34 g, 0.13 mol), glycidyl methacrylate (37.45 g, 0.26 mol), (3-ethyl-3-oxetanemethyl) methacrylate ( 4.85 g, 0.03 mol), and norbornane lactone methacrylate (5.83 g, 0.03 mol) shown in the above formula (12) and 1.5 g of α-methylstyrene dimer were charged, and then slowly replaced with nitrogen. Stirring was started, the temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours for polymerization to obtain an alkali-soluble resin (A-4) solution. The concentration of this solution was adjusted using propylene glycol methyl ether acetate to prepare a 30% solid content concentration solution.
Mw of the obtained alkali-soluble resin (A-4) was 25,000, and Mw / Mn was 2.4.

(Preparation of photosensitive resin composition)
Using 20 g of the alkali-soluble resin solution (solid content 30% solution) obtained above, for each of Examples 1 to 9 and Comparative Examples 1 to 3, a varnish-like photosensitive resin composition was prepared as follows. Prepared. First, each component blended according to Table 1 was dissolved in a mixed solvent of propylene glycol methyl ether acetate: diethylene glycol methyl ethyl ether = 70: 30 so as to have a solid content of 20%. Subsequently, the mixed solution obtained by this was filtered with the 0.2-micrometer PTFE filter, and the photosensitive resin composition was prepared. The details of each component other than the alkali-soluble resin in Table 1 are as follows.

(B) Photosensitizer Photosensitizer (B-1): PA-28, manufactured by Daitokemix Co., Ltd. Photosensitizer (B-2): PA-3, manufactured by Daitokemix Co., Ltd. PA-28 and PA-3 are 4,4 ′-(1- {4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene) bisphenol and 1,2-naphthoquinonediazide-5 represented by the following formulas An esterified product with sulfonyl chloride.

(C) Polyfunctional (meth) acrylate compound compound (C-1): Glycerin dimethacrylate compound (C-2): Tetramethylol triacrylate compound (C′-3): Neopentyl glycol dimethacrylate compound (C′-4) ): Ethylene glycol dimethacrylate All the above compounds were manufactured by Shin-Nakamura Chemical Co., Ltd.

(D) Adhesion aid Adhesion aid (D-1): 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Silicone Co., Ltd.)

(E) Compound compound having glycidyl group (E-1): Alicyclic epoxy compound (Celoxide 2081, manufactured by Daicel Corporation)

(F) Polymerization initiator Polymerization initiator (F-1): 2,2-azobis (2,4-dimethylvaleronitrile)

(G) Surfactant Surfactant (G-1): Fluorosurfactant (F-557, manufactured by DIC Corporation)

  The photosensitive resin composition obtained as described above was evaluated according to the following items.

<Sensitivity>
About each Example and each comparative example, the patterning exposure sensitivity of the photosensitive resin composition obtained as follows was measured. First, the photosensitive resin composition is spin-coated on a 4-inch silicon wafer substrate (rotation number: 500-2500 rpm), and prebaked at 90 ° C. for 120 seconds using a hot plate, so that the thickness is about 2.5 μm. A resin film 1 was obtained. Next, using a quartz chromium mask, exposure was performed with a PLA-501F (extra-high pressure mercury lamp) manufactured by Canon Inc. Thereafter, the exposed substrate was developed with a 0.7% tetramethylammonium hydroxide aqueous solution by a dipping method at 23 ° C. for 45 seconds.
Thereafter, the substrate was rinsed with pure water for 60 seconds, and spin drying was performed using a spin coater to produce the patterning resin film 2.
The exposure amount from which the 10 μm mask pattern becomes a 10 μm resist pattern was obtained from this substrate using a Nikon optical microscope, and this value was measured as the exposure sensitivity. In Table 1, this exposure amount is shown in units of “mJ / cm ² ”.

<Remaining film ratio after development>
The thickness was calculated by the following formula from the film thickness 1 of the pre-baked resin film 1 and the film thickness 2 of the patterning resin film 2 produced by the same method as the sensitivity measurement method.
Residual film ratio after development (%) = film thickness 2 / film thickness 1 * 100

<Adhesion evaluation>
Using the patterning resin film 2 produced by the same method as the sensitivity measurement method, evaluation was performed using a pattern in which 5 * 5 = 25 4 μm pillar patterns are arranged.
All 25 sticks are in close contact with each other; ◎
24 to 20 sticking things; ○
19 to 10 in close contact; △
10 or less; ×

  As shown in Table 1, in each example, it was possible to achieve both sensitivity and adhesion by including a (meth) acrylate compound having a specific substituent in the resin composition.

  The positive photosensitive resin composition of the present invention has an excellent balance between developability and adhesiveness, and can be applied to various processes including the formation of a planarization film of a display device.

10 substrate 12 counter substrate 14 liquid crystal layer 20 insulating film 22 opening 30 transistor 31 gate electrode 32 source electrode 33 drain electrode 34 gate insulating film 35 semiconductor layers 40 and 42 wiring 90 and 92 alignment film 100 electronic device

Claims (12)

A positive photosensitive resin composition comprising the following components (A), (B), and (C).
(A) Alkali-soluble resin (B) Photosensitizer (C) Polyfunctional (meth) acrylate compound having a hydroxyl group and 2 or more and 4 or less (meth) acryl groups in the molecule The positive photosensitive resin composition according to claim 1,
The (A) alkali-soluble resin is a positive photosensitive resin composition containing a carboxyl group in its structure. The positive photosensitive resin composition according to claim 1, wherein
The (A) alkali-soluble resin is a positive photosensitive resin composition containing a norbornene skeleton in its structure. The positive photosensitive resin composition according to any one of claims 1 to 3,
0.01 mass of a polyfunctional (meth) acrylate compound having a hydroxyl group and 2 or more and 4 or less (meth) acryl groups in the molecule (C) with respect to 100 mass parts of the (A) alkali-soluble resin. A positive photosensitive resin composition comprising 10 parts by mass or more and 10 parts by mass or less. The positive photosensitive resin composition according to any one of claims 1 to 4,
The (C) polyfunctional (meth) acrylate compound having a hydroxyl group and 2 to 4 (meth) acrylic groups in the molecule is glycerin diacrylate, glycerin dimethacrylate, tetramethylol triacrylate, tetramethylol trimethacrylate. A positive photosensitive resin composition, which is one or more compounds selected from the group consisting of: A positive photosensitive resin composition according to any one of claims 1 to 5,
Further, (D) a positive photosensitive resin composition containing an adhesion assistant. The positive photosensitive resin composition according to claim 6,
A positive photosensitive resin composition comprising 0.1 to 30 parts by mass of the (D) adhesion assistant with respect to 100 parts by mass of the (A) alkali-soluble resin. The positive photosensitive resin composition according to claim 6 or 7,
The ratio of the content of the polyfunctional (meth) acrylate compound having a hydroxyl group and 2 to 4 (meth) acrylic groups in the molecule (C) relative to the content of the (D) adhesion assistant, A positive photosensitive resin composition having a value of 0.0001 or more and 10 or less. The positive photosensitive resin composition according to any one of claims 1 to 8,
Further, (E) a positive photosensitive resin composition containing a compound having a glycidyl group or a compound having an oxetanyl group. A positive photosensitive resin composition according to any one of claims 1 to 9,
Further, (F) a positive photosensitive resin composition containing a polymerization initiator.   The cured film comprised with the hardened | cured material of the positive photosensitive resin composition of any one of Claims 1 thru | or 10.   An electronic device comprising the cured film according to claim 11.

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