JP6576386B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a heat-resistant photosensitive resin composition, and a partition wall or an insulating film of an organic EL display device using the composition.

  For example, in a display device such as an organic EL display, a partition wall material is used at an interval portion of a colored pattern in a display region or an edge of a peripheral portion of the display region in order to improve display characteristics. In the manufacture of the organic EL display device, in order to prevent the pixels of the organic material from coming into contact with each other, first, a partition is formed, and the pixel of the organic material is formed between the partitions. This partition is generally formed by photolithography using a photosensitive resin composition and has an insulating property. Specifically, the photosensitive resin composition is applied onto a substrate using a coating apparatus, and after removing volatile components by means of heating or the like, it is exposed through a mask. In the case of the positive type, development is performed by removing the exposed portion with a developer such as an alkaline aqueous solution, and the resulting pattern is heat-treated to form partition walls. Next, an organic material that emits light of three colors of red, green, and blue is formed between the partition walls by an inkjet method or the like to form a pixel of the organic EL display device.

  In this field, in recent years, display devices have been downsized and the contents to be displayed have been diversified, so that high performance or high definition of pixels has been demanded. For example, since a heat treatment process is performed when the partition walls are formed, it is required to have excellent heat resistance so as not to affect the peripheral members.

  For example, in Patent Document 1, a positive-type radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound is used as a radiation-sensitive resin composition that has high resolution and exhibits high light-shielding properties by heat treatment after exposure. A composition to which titanium black is added has been proposed.

JP 2001-281440 A

  Although the composition described in Patent Document 1 has sufficient sensitivity and light shielding properties, it is heated at high temperature in the air in order to enhance the light shielding properties, and the resin is oxidized and deteriorated. This increases the outgas due to the deterioration of the resin, so that the heat resistance is inferior, and it is not suitable for the manufacture and stable driving of the organic EL display device.

  This invention is made | formed based on such a situation, The objective is to provide the photosensitive resin composition excellent in heat resistance which can reduce generation | occurrence | production of outgas even if it passes through heat processing.

  As a result of intensive studies, the present inventors have found that a photosensitive resin composition containing an alkali-soluble resin and a quinonediazide compound, and having an alkali-soluble resin having a specific structure, generates outgas even after heat treatment. It has been found that it can be reduced.

（式中、Ｚは水素原子、塩素原子、カルボキシル基、シアノ基、炭素原子数１〜２０のアルキル基、炭素原子数８〜２０の１価の芳香族炭化水素基、炭素原子とヘテロ原子との合計原子数３〜２０の１価の複素環式基、−ＯＲ、−Ｎ（Ｒ)₂、−ＯＣ（＝Ｏ）Ｒ、−Ｃ（＝Ｏ）ＯＲ、−Ｃ（＝Ｏ）Ｎ（Ｒ)₂、−Ｐ（＝Ｏ）（ＯＲ)₂、−Ｐ（＝Ｏ)(Ｒ)₂から選ばれる少なくとも一種を示し、各Ｒは相互に独立に炭素原子数１〜１８のアルキル基、炭素原子数２〜１８のアルケニル基、炭素原子数６〜１８の１価の芳香族炭化水素基又は炭素原子とヘテロ原子との合計原子数３〜１８の１価の複素環式基を示し、＊は重合体との結合部を示す。）

（式中、Ｒ^aは電子求引基であり、Ｒ^b及びＲ^cは炭素原子数１〜５のアルキル基であり、＊は重合体との結合部である。） That is, the present invention includes the following aspects.
[Item 1]
(A) An alkali-soluble resin, and (B) a photosensitive resin composition containing a quinonediazide compound, wherein the (A) alkali-soluble resin is
At least one end of the molecular chain has a structure represented by the following formula (I), and at least one of the structures represented by the following formula (II) in the molecule and a structure represented by the following formula (III) A photosensitive resin composition comprising an alkali-soluble resin (a1) which is a polymer.

(In the formula, Z represents a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 8 to 20 carbon atoms, a carbon atom and a hetero atom, A monovalent heterocyclic group having 3 to 20 atoms in total, -OR, -N (R) ₂ , -OC (= O) R, -C (= O) OR, -C (= O) N ( R) ₂ , —P (═O) (OR) ₂ , —P (═O) (R) ₂ , wherein each R is independently an alkyl group having 1 to 18 carbon atoms, An alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a monovalent heterocyclic group having 3 to 18 total atoms of carbon atoms and heteroatoms, * Indicates a bond with the polymer.)

(In the formula, R ^a is an electron withdrawing group, R ^b and R ^c are alkyl groups having 1 to 5 carbon atoms, and * is a bond with a polymer.)

である、項目１に記載の感光性樹脂組成物。 [Item 2]
R ^a is —COOH, —CN, —COOCH ₃ , or

The photosensitive resin composition of item 1 which is.

（式中、Ｚは水素原子、塩素原子、カルボキシル基、シアノ基、炭素原子数１〜２０のアルキル基、炭素原子数８〜２０の１価の芳香族炭化水素基、炭素原子とヘテロ原子との合計原子数３〜２０の１価の複素環式基、−ＯＲ、−Ｎ（Ｒ)₂、−ＯＣ（＝Ｏ）Ｒ、−Ｃ（＝Ｏ）ＯＲ、−Ｃ（＝Ｏ）Ｎ（Ｒ)₂、−Ｐ（＝Ｏ）（ＯＲ)₂、−Ｐ（＝Ｏ)(Ｒ)₂から選ばれる少なくとも一種を示し、各Ｒは相互に独立に炭素原子数１〜１８のアルキル基、炭素原子数２〜１８のアルケニル基、炭素原子数６〜１８の１価の芳香族炭化水素基又は炭素原子とヘテロ原子との合計原子数３〜１８の１価の複素環式基を示し、Ｒ^b及びＲ^cは炭素原子数１〜５のアルキル基であり、Ｒ^dは炭素原子数１〜２０のアルキル基である。） [Item 3]
The structure represented by the formula (I) to the formula (III) is a structure derived from at least one compound selected from the group represented by the following formulas (IV-1) to (IV-8). Item 3. The photosensitive resin composition according to item 1 or 2.

(In the formula, Z represents a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 8 to 20 carbon atoms, a carbon atom and a hetero atom, A monovalent heterocyclic group having 3 to 20 atoms in total, -OR, -N (R) ₂ , -OC (= O) R, -C (= O) OR, -C (= O) N ( R) ₂ , —P (═O) (OR) ₂ , —P (═O) (R) ₂ , wherein each R is independently an alkyl group having 1 to 18 carbon atoms, An alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a monovalent heterocyclic group having 3 to 18 total atoms of carbon atoms and heteroatoms, R ^b and R ^c are alkyl groups having 1 to 5 carbon atoms, and R ^d is an alkyl group having 1 to 20 carbon atoms.)

[Item 4]
Item 4. The photosensitive resin composition according to any one of Items 1 to 3, wherein the alkali-soluble resin (a1) has a weight average molecular weight of 5,000 to 80,000.

[Item 5]
(C) The photosensitive resin composition as described in any one of the items 1-4 which further contains a black coloring agent.

[Item 6]
(A) The content of the quinonediazide compound is 10 to 100 parts by mass with respect to 100 parts by mass of the total amount of the alkali-soluble resin, and if present, the content of (C) the black colorant is 10 to 100 parts by mass. The photosensitive resin composition according to any one of Items 1 to 5, which is

[Item 7]
Item 7. The photosensitive resin composition according to any one of items 1 to 6, wherein the alkali-soluble resin (a1) is a copolymer of a polymerizable monomer having an alkali-soluble group and another polymerizable monomer. object.

[Item 8]
Item 8. The photosensitive resin composition according to Item 7, wherein the alkali-soluble group is at least one selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an acid anhydride group.

（式中、Ｒ¹は水素原子又は炭素原子数１〜５のアルキル基を表し、ｒは１〜５の整数を表す。）
で表されるモノマー単位を有する、項目７又は８に記載の感光性樹脂組成物。 [Item 9]
The alkali-soluble resin (a1) is represented by the following formula (V)

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and r represents an integer of 1 to 5)
The photosensitive resin composition of item 7 or 8 which has a monomer unit represented by these.

（式中、Ｒ²、Ｒ³は、それぞれ独立して水素原子、炭素原子数１〜３のアルキル基、完全若しくは部分的にフッ素化された炭素原子数１〜３のアルキル基、又はハロゲン原子を表し、Ｒ⁴は、水素原子、炭素原子数１〜６の直鎖あるいは環状アルキル基、フェニル基、又は、ヒドロキシ基、炭素原子数１〜６のアルキル基及び炭素原子数１〜６のアルコキシ基からなる群より選ばれた少なくとも一種で置換されたフェニル基を表す。）
で表されるモノマー単位を有する、項目７〜９のいずれか一項に記載の感光性樹脂組成物。 [Item 10]
The alkali-soluble resin (a1) is represented by the following formula (VI)

(Wherein R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fully or partially fluorinated alkyl group having 1 to 3 carbon atoms, or a halogen atom. R ⁴ represents a hydrogen atom, a linear or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy having 1 to 6 carbon atoms. Represents a phenyl group substituted with at least one selected from the group consisting of groups.)
The photosensitive resin composition as described in any one of the items 7-9 which has a monomer unit represented by these.

[Item 11]
(A) The photosensitive resin composition as described in any one of the items 1-10 in which alkali-soluble resin further contains alkali-soluble resin (a2) which has an epoxy group and a phenolic hydroxyl group.

[Item 12]
Polymerization in the presence of 0.01 to 10 parts by mass of a RAFT agent capable of imparting the structure of formula (I) or (II) and the structure of formula (III) to 100 parts by mass of the total amount of polymerizable monomers A step of polymerizing a polymerizable monomer and producing an alkali-soluble resin (A) containing an alkali-soluble resin (a1);
(A) The alkali-soluble resin, (B) a quinonediazide compound, and optionally (C) a step of mixing a black colorant to produce a resin composition, A method for producing a photosensitive resin composition.

[Item 13]
The partition or insulating film of the organic EL element which consists of a hardened | cured material of the photosensitive resin composition as described in any one of items 1-11.

[Item 14]
The organic EL element containing the hardened | cured material of the photosensitive resin composition as described in any one of items 1-11.

[Item 15]
(1) An application step in which the photosensitive resin composition according to any one of items 1 to 11 is dissolved in a solvent and applied to a substrate.
(2) A drying step for removing the solvent in the applied photosensitive resin composition,
(3) an exposure step of irradiating radiation through a photomask;
(4) A method for producing a radiation lithographic structure, comprising: a development step of forming a pattern by alkali development; and (5) a heat treatment step of heating at a temperature of 100 to 350 ° C.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition excellent in the heat resistance which can reduce outgas can be provided.

  The present invention is described in detail below.

(A) Alkali-soluble resin The (A) alkali-soluble resin of the present invention essentially comprises the following alkali-soluble resin (a1), but in addition, an alkali-soluble resin having an epoxy group and a phenolic hydroxyl group (a2) (“component ( a2) ”) and other alkali-soluble resins (a3) (also referred to as“ component (a3) ”). In the present invention, alkali-soluble means that it can be dissolved in an alkali solution, for example, a 2.38 mass% tetramethylammonium hydroxide aqueous solution.

（式中、Ｚは水素原子、塩素原子、カルボキシル基、シアノ基、炭素原子数１〜２０のアルキル基、炭素原子数８〜２０の１価の芳香族炭化水素基、炭素原子とヘテロ原子との合計原子数３〜２０の１価の複素環式基、−ＯＲ、−Ｎ（Ｒ)₂、−ＯＣ（＝Ｏ）Ｒ、−Ｃ（＝Ｏ）ＯＲ、−Ｃ（＝Ｏ）Ｎ（Ｒ)₂、−Ｐ（＝Ｏ）（ＯＲ)₂、−Ｐ（＝Ｏ)(Ｒ)₂から選ばれる少なくとも一種を示し、各Ｒは相互に独立に炭素原子数１〜１８のアルキル基、炭素原子数２〜１８のアルケニル基、炭素原子数６〜１８の１価の芳香族炭化水素基又は炭素原子とヘテロ原子との合計原子数３〜１８の１価の複素環式基を示し、＊は重合体との結合部を示す。）

（式中、Ｒ^aは電子求引基であり、Ｒ^b及びＲ^cは炭素原子数１〜５のアルキル基であり、＊は重合体との結合部である。） <Alkali-soluble resin (a1)>
As the alkali-soluble resin (a1), at least one of the structure represented by the following formula (I) at the end of the molecular chain and the structure represented by the following formula (II) in the molecule, and the following formula ( If it has a structure represented by III) and is an alkali-soluble polymer, it will not be restrict | limited. For example, those obtained by adding an alkali-soluble group to a resin that can be produced by radical polymerization, such as an acrylic resin and a styrene resin. These can be used alone or in combination of two or more kinds of resins.

(In the formula, Z represents a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 8 to 20 carbon atoms, a carbon atom and a hetero atom, A monovalent heterocyclic group having 3 to 20 atoms in total, -OR, -N (R) ₂ , -OC (= O) R, -C (= O) OR, -C (= O) N ( R) ₂ , —P (═O) (OR) ₂ , —P (═O) (R) ₂ , wherein each R is independently an alkyl group having 1 to 18 carbon atoms, An alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a monovalent heterocyclic group having 3 to 18 total atoms of carbon atoms and heteroatoms, * Indicates a bond with the polymer.)

(In the formula, R ^a is an electron withdrawing group, R ^b and R ^c are alkyl groups having 1 to 5 carbon atoms, and * is a bond with a polymer.)

  Here, the structures of the formulas (I) to (III) are polymerized with a radical polymerizable monomer (RAFT polymerization) in the presence of the following RAFT agent (Reversible Addition Fragmentation Transfer). Can be introduced into the polymer. That is, the structure of formula (I) to formula (III), which is a fragment of the RAFT agent shown below, is added to the polymer by RAFT polymerization. Alternatively, a group having a structure of formula (I) to formula (III) may be added to the polymer separately.

で表わされる群から選択される少なくとも１種などを使用することができる。中でも、

この構造のＲＡＦＴ剤はアウトガスの低減効果により優れるため好ましい。 Although it does not specifically limit as a RAFT agent (reversible addition cleavage chain transfer agent) which can provide the structure of said Formula (I)-Formula (III) to a polymer, For example,

At least one selected from the group represented by the following can be used. Above all,

The RAFT agent having this structure is preferable because it is excellent in the effect of reducing outgas.

Here, in the formula, Z is a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 8 to 20 carbon atoms, a carbon atom and a hetero atom. Monovalent heterocyclic group having 3 to 20 atoms in total, -OR, -N (R) ₂ , -OC (= O) R, -C (= O) OR, -C (= O) At least one selected from N (R) ₂ , —P (═O) (OR) ₂ , —P (═O) (R) ₂ , and each R is independently an alkyl having 1 to 18 carbon atoms. A alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a monovalent heterocyclic group having 3 to 18 total atoms of carbon atoms and heteroatoms. Show. R ^a is an electron withdrawing group, R ^b and R ^c are alkyl groups having 1 to 5 carbon atoms, and R ^d is an alkyl group having 1 to 20 carbon atoms.

  Examples of the alkyl group having 1 to 20 carbon atoms of Z in the formula include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, 1,1-dimethylpropyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1-dimethyl-3,3-dimethylbutyl group, Examples include n-nonyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, n-eicosyl group and the like. The number of carbon atoms more preferable as the alkyl group for Z is 1-15, and more preferably 1-10.

  Examples of the monovalent aromatic hydrocarbon group having 8 to 20 carbon atoms of Z include 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 9-anthracenyl group, α-methylbenzyl group, α, An α-dimethylbenzyl group, a phenethyl group, and the like can be given. 9-20 are preferable and, as for the carbon atom number in this monovalent | monohydric aromatic hydrocarbon group, it is more preferable that it is 10-20.

  In the monovalent heterocyclic group having 3 to 20 total atoms of carbon atoms and heteroatoms of Z, preferable heteroatoms are oxygen atoms and nitrogen atoms, and more preferably nitrogen atoms. Examples of the monovalent heterocyclic group having 3 to 20 total atoms of carbon atoms and hetero atoms of Z include an oxiranyl group, an aziridinyl group, a 2-furanyl group, a 3-furanyl group, a 2-tetrahydrofuranyl group, 3-tetrahydrofuranyl group, 1-pyrrole group, 2-pyrrole group, 3-pyrrole group, 1-pyrrolidinyl group, 2-pyrrolidinyl group, 3-pyrrolidinyl group, 1-pyrazole group, 2-pyrazole group, 3-pyrazole group 2-tetrahydropyranyl group, 3-tetrahydropyranyl group, 4-tetrahydropyranyl group, 2-thianyl group, 3-thianyl group, 4-thianyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl Group, 2-piperidinyl group, 3-piperidinyl group, 4-piperidinyl group, 2-morpholinyl group, 3-morpholinyl group and the like. That.

-OR of Z, -N (R) ₂ , -OC (= O) R, -C (= O) OR, -C (= O) N (R) ₂ , -P (= O) (OR) ₂ And P (═O) (R) ₂ , an alkyl group having 1 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a total number of carbon atoms and heteroatoms of 3 As the monovalent heterocyclic group of ˜18, for example, an alkyl group having 1 to 20 carbon atoms exemplified for Z, or a monovalent heterocyclic group having 3 to 20 total atoms of carbon atoms and heteroatoms Among the groups, there can be mentioned groups having 18 or less carbon atoms, and examples of the monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms include a phenyl group, a 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 9-anthracenyl group, benzyl group, α-methylbenzyl group, α , Α-dimethylbenzyl group, phenethyl group and the like. Of these, a phenyl group, a benzyl group, and a methylbenzyl group are preferable, and a phenyl group is more preferable.

  Examples of the alkenyl group having 2 to 18 carbon atoms of R include a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2 -Pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group and the like can be mentioned. Of these, a vinyl group, a 1-propenyl group, and a 2-propenyl group are preferable, and a vinyl group is more preferable.

−ＮＯ_２、−Ｂｒ、−Ｃｌ、−Ｉ、−Ｆ等を挙げることができる。中でも、アウトガスの低減効果を考慮した場合、−ＣＯＯＨ、−ＣＮ、−ＣＯＯＣＨ_３、又は

が好ましい。 The electron withdrawing group for R ^{a in} the formula is not limited to the following, but includes, for example, —COOH, —CN, —CHO, —COOR ^x (R ^x is an alkyl group, preferably 1 to 3 carbon atoms). Alkyl group),

-NO _2, mention may be made of -Br, -Cl, -I, and -F, and the like. Among them, when considering the effect of reducing outgassing, -COOH, -CN, -COOCH _3, or

Is preferred.

R ^b and R ^c in the formula are not particularly limited as long as they are alkyl groups having 1 to 5 carbon atoms, and R ^d is an alkyl group having 1 to 20 carbon atoms. Examples of the alkyl group include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, 1, 1-dimethylpropyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1-dimethyl-3,3-dimethylbutyl group, n-nonyl group, n-decyl group, n- dodecyl group, n- tetradecyl, n- hexadecyl group, n- octadecyl group, and a n- eicosyl group and the like, can be in accordance with the number of carbon atoms, selects a R ^b, R ^c and R ^d . Among them, in consideration of the outgassing reduction effect, R ^b and R ^c are preferably methyl groups, and R ^d is preferably an alkyl group having 4 or more, 8 or more, or 10 or more carbon atoms, An n-dodecyl group is preferred.

<Partial structure of alkali-soluble resin (a1)>
The alkali-soluble resin (a1) of the present invention can be obtained by radical polymerization (in particular, RAFT polymerization in this case) of a polymerizable monomer using the RAFT agent exemplified above as a chain transfer agent. The alkali-soluble group may be introduced by copolymerization with a polymerizable monomer having an alkali-soluble group (for example, a carboxyl group), or may be introduced after the polymerization.

As for alkali-soluble resin (a1), the structure derived from the RAFT agent illustrated below is introduce | transduced into the frame | skeleton by said RAFT polymerization.

（式中、Ｒ^a〜Ｒ^ｄは前述と同じである。）
を用いてラジカル重合を行うと、生成する重合体には以下のような反応により

（II）及び（III）の構造が導入される（構造式（ア））。ただし、Ｐ_ｍ、Ｐ_ｎは重合体、Ｐ_ｍ・、Ｐ_ｎ・等は生成重合体ラジカルを示す。なお、ＲＡＦＴ重合により構造式（ア）で示される重合体の他、構造式（イ）及び（ウ）で示される重合体等も生成するが、生成物が取り得る全ての構造式を示すのは非実際的である。ＲＡＦＴ剤として（IV−５）〜（IV−８）を用いれば、上記スキームと同様にして（I）の構造も重合体に導入される。 For example, as a RAFT agent

(Wherein, R ^a to R ^d are the same as above.)
When radical polymerization is performed using

The structures of (II) and (III) are introduced (Structural Formula (A)). However, _Pm , _Pn represents a polymer, and _Pm ·, _Pn ·, etc. represent generated polymer radicals. In addition to the polymer represented by the structural formula (a) by RAFT polymerization, the polymers represented by the structural formulas (a) and (c) are also produced, but all structural formulas that the product can take are shown. Is impractical. When (IV-5) to (IV-8) are used as RAFT agents, the structure of (I) is also introduced into the polymer in the same manner as in the above scheme.

  When the present inventors heated the photosensitive resin composition by employing the alkali-soluble resin (a1) (also referred to as “component (a1)”) as the alkali-soluble resin (A) of the photosensitive resin composition. It has been found that the outgas generated can be reduced. The use of the component (a1) of the present invention is considered to be effective for reducing the outgas other than the residual monomer in addition to the effect of reducing the outgas based on the residual monomer. This is because, in the case of an alkali-soluble resin that does not contain the component (a1), outgassing occurs even if the resin is reprecipitated to remove residual monomers, whereas in the case of an alkali-soluble resin that contains the component (a1) This is because after the reprecipitation treatment, the generation of outgas is reduced as compared with the alkali-soluble resin not containing the component (a1). This reduction effect of outgas is not limited by any theory, but the structure derived from the above-mentioned RAFT agent, that is, the structure of the above formula (I) or formula (II) and the structure of formula (III) This is thought to be due to the fact that it was formed in the polymer skeleton. In the photosensitive resin composition of the present invention, the weight reduction rate in the heating test described in the following examples can be 5% or less.

<Manufacture of alkali-soluble resin (a1)>
The alkali-soluble resin (a1) can be produced by radical polymerization of a polymerizable monomer having an alkali-soluble group and another polymerizable monomer using a RAFT agent (chain transfer agent). Examples of the alkali-soluble group include a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, and an acid anhydride group. Alternatively, an alkali-soluble group may be added after synthesizing a copolymer by RAFT polymerization. Examples of the polymerizable group that the polymerizable monomer has include a radical polymerizable carbon-carbon unsaturated group. _{Specifically, CH 2 = CH-, CH 2} = C (CH 3) -, CH 2 = CHCO-, CH 2 = C (CH 3) CO -, - OC-CH = CH-CO- illustrate like it can. Examples of the polymerizable monomer having an alkali-soluble group include 4-hydroxystyrene, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth). Acrylic acid, β-styryl (meth) acrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, Examples include 4-hydroxyphenyl methacrylate, 3,5-dimethyl-4-hydroxybenzylacrylamide, 4-hydroxyphenylacrylamide, 4-hydroxyphenylmaleimide, 3-maleimidopropionic acid, 4-maleimidobutyric acid, and 6-maleimidohexanoic acid. .

  Examples of other polymerizable monomers include polymerizable styrene derivatives such as styrene, vinyl toluene, α-methyl styrene, p-methyl styrene, and p-ethyl styrene, acrylamide, acrylonitrile, vinyl n-butyl ether, and the like. Vinyl alcohol ethers, (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester (Meth) acrylic acid ester such as 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, isobornyl (meth) acrylate, maleic anhydride, Feni Maleimides include N- substituted maleimide and cyclohexyl maleimide. Here, “(meth) acryl” means “acryl” and “methacryl”. Among them, from the viewpoint of heat resistance and the like, the component (a1) has one or more kinds of cyclic structures such as an alicyclic structure, an aromatic structure, a polycyclic structure, an inorganic cyclic structure, and a heterocyclic structure. It is preferable to have.

（式中、Ｒ¹は水素原子又は炭素原子数１〜５のアルキル基を表し、ｒは１〜５の整数を表す。）で表されるモノマー単位を形成し得るものが好ましい。該モノマー単位を形成し得るアルカリ可溶性基を有する重合性単量体としては、４−ヒドロキシフェニルメタクリレートが特に好ましい。 Furthermore, as the polymerizable monomer having an alkali-soluble group, the following formula (V)

(Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and r represents an integer of 1 to 5). As the polymerizable monomer having an alkali-soluble group capable of forming the monomer unit, 4-hydroxyphenyl methacrylate is particularly preferable.

（式中、Ｒ²及びＲ³は、それぞれ独立して水素原子、炭素原子数１〜３のアルキル基、完全若しくは部分的にフッ素化された炭素原子数１〜３のアルキル基、又はハロゲン原子を表し、Ｒ⁴は、水素原子、炭素原子数１〜６の直鎖若しくは環状アルキル基、フェニル基、又はヒドロキシ基、炭素原子数１〜６のアルキル基及び炭素原子数１〜６のアルコキシ基からなる群より選ばれた少なくとも一種で置換されたフェニル基を表す。）で表されるモノマー単位を形成し得るものが好ましい。該モノマー単位を形成し得るその他の重合性単量体としては、フェニルマレイミド及びシクロヘキシルマレイミドが特に好ましい。 Other polymerizable monomers are represented by the following formula (VI)

(Wherein R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fully or partially fluorinated alkyl group having 1 to 3 carbon atoms, or a halogen atom. R ⁴ represents a hydrogen atom, a linear or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. Represents a phenyl group substituted with at least one selected from the group consisting of: a monomer unit represented by As other polymerizable monomers capable of forming the monomer unit, phenylmaleimide and cyclohexylmaleimide are particularly preferable.

  As a polymerization initiator in producing a copolymer of a polymerizable monomer having an alkali-soluble group and another polymerizable monomer by radical polymerization, 2,2′-azobisisobutyronitrile, 2′-azobis (2-methylbutyronitrile), dimethyl 2,2′-azobis (2-methylpropionate), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis ( Azo polymerization initiators such as 2,4-dimethylvaleronitrile) (AVN), dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylcumyl peroxide, 10-hour half-life temperature of di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, etc. A peroxide polymerization initiator at 100 to 170 ° C., or a peroxide polymerization initiator such as benzoyl peroxide, lauroyl peroxide, 1,1′-di (t-butylperoxy) cyclohexane, t-butylperoxypivalate, etc. Can be used. The amount of the polymerization initiator used is generally 0.01 parts by mass or more, 0.05 parts by mass or more, 0.5 parts by mass or more, 40 parts by mass or less, and 100 parts by mass with respect to 100 parts by mass of the polymerizable monomer mixture. It is preferable that it is less than or equal to 15 parts by mass.

  The RAFT agent can be used in the range of 0.005 to 20 parts by mass with respect to 100 parts by mass of the total amount of polymerizable monomers, and can be used in the range of 0.01 to 10 parts by mass. preferable.

  The weight average molecular weight (Mw) of the alkali-soluble resin (a1) of the photosensitive resin composition of the present invention is 5,000 to 80,000, preferably 6,000 to 70,000, and 7,000. More preferably, it is ˜60,000. The number average molecular weight (Mn) is in the range of 1000 to 30000, preferably 3000 to 25,000, and more preferably 5,000 to 20,000. The polydispersity (Mw / Mn) is 1.0 to 3.0, preferably 1.1 to 2.8, and more preferably 1.2 to 2.5. When the weight average molecular weight, number average molecular weight, and polydispersity are in this range, the alkali solubility and developability are excellent.

  By using a polymer obtained by radical polymerization of these polymerizable monomers, it is possible to improve shape maintenance and developability and contribute to reduction of outgas.

  Although there is no restriction | limiting in particular in the reaction temperature and reaction time in manufacture of the alkali-soluble resin (a1) of the photosensitive resin composition of this invention, 50-150 degreeC of polymerization temperature is preferable, More preferably, it is 60-130 degreeC, More preferably, it is 70-120 degreeC. The polymerization time is preferably 2 to 24 hours, more preferably 3 to 12 hours, and further preferably 4 to 8 hours. Further, a nitrogen gas atmosphere is preferable during production.

  In addition to the component (a1) described above, the alkali-soluble resin (A) of the present invention includes (a2) an alkali-soluble resin having an epoxy group and a phenolic hydroxyl group (also referred to as “component (a2)”) and other alkali-soluble resins. Resin (a3) (also referred to as “component (a3)”) can be included.

(A2) Alkali-soluble resin having epoxy group and phenolic hydroxyl group The alkali-soluble resin of component (a2) is, for example, a compound having at least two epoxy groups in one molecule (hereinafter referred to as “epoxy compound”). And the epoxy group of hydroxybenzoic acid can be reacted with each other. However, the reaction rate is adjusted so that the epoxy group remains. In the photosensitive resin composition of the present invention, since the alkali-soluble resin (a2) has an epoxy group, there is an advantage that chemical resistance, heat resistance and the like are improved by reacting with a phenolic hydroxyl group during heating and crosslinking. In addition, having a phenolic hydroxyl group has an advantage of being soluble in an alkaline aqueous solution.

  An example of a reaction in which one of the epoxy groups of the epoxy compound reacts with a carboxyl group of hydroxybenzoic acid to form a compound having a phenolic hydroxyl group is shown in the following reaction formula 1.

Examples of the compound having at least two epoxy groups in one molecule include phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol type epoxy resins, biphenol type epoxy resins, naphthalene skeleton-containing epoxy resins, and heterocyclic epoxy resins. Etc. These epoxy compounds only need to have two or more epoxy groups in one molecule and can be used alone, but may be used in combination of two or more. In addition, since these compounds are a thermosetting type, it cannot be uniquely described from the difference in the presence or absence of an epoxy group, the kind of functional group, a polymerization degree, etc. as common knowledge of those skilled in the art. An example of the structure of the novolac type epoxy resin is shown in Formula (1). Incidentally, ^{R 5} in the formula (1) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 50.

  Examples of the phenol novolac type epoxy resin include EPICLON (registered trademark) N-770 (manufactured by DIC Corporation), jER (registered trademark) -152 (manufactured by Mitsubishi Chemical Corporation), and the like.

  Examples of the cresol novolac type epoxy resin include EPICLON (registered trademark) N-695 (manufactured by DIC Corporation), EOCN (registered trademark) -102S (manufactured by Nippon Kayaku Co., Ltd.), and the like.

  Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resins such as jER (registered trademark) 828, jER (registered trademark) 1001 (manufactured by Mitsubishi Chemical Corporation), and YD-128 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.). Bisphenol F type epoxy resins such as JER (registered trademark) 806 (manufactured by Mitsubishi Chemical Corporation), YDF-170 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), and the like.

  Examples of the biphenol type epoxy resin include jER (registered trademark) YX-4000, jER (registered trademark) YL-6121H (manufactured by Mitsubishi Chemical Corporation), and the like.

  Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (trade name, manufactured by Nippon Kayaku Co., Ltd.), EXA-4750 (trade name, manufactured by DIC Corporation), and the like.

  Examples of the alicyclic epoxy resin include EHPE (registered trademark) -3150 (manufactured by Daicel Chemical Industries, Ltd.).

  Examples of the heterocyclic epoxy resin include TEPIC (registered trademark), TEPIC-L, TEPIC-H, and TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.).

  “Hydroxybenzoic acid” refers to a compound in which at least one of positions 2 to 6 of benzoic acid is substituted with a hydroxyl group. For example, salicylic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4 -Dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2-hydroxy-5-nitrobenzoic acid, 3-hydroxy Examples include -4-nitrobenzoic acid and 4-hydroxy-3-nitrobenzoic acid, and dihydroxybenzoic acids are preferable in terms of enhancing alkali developability. These hydroxybenzoic acids can be used alone or in combination of two or more.

  The method for obtaining a compound having an alkali-soluble phenolic hydroxyl group from the epoxy compound and hydroxybenzoic acid is preferably 0.20 to 0.90 equivalent of hydroxybenzoic acid with respect to 1 equivalent of epoxy group of the epoxy compound. Preferably, 0.25 to 0.85 equivalent, more preferably 0.30 to 0.80 equivalent is used. If hydroxybenzoic acid is 0.2 equivalent or more, sufficient alkali solubility is expressed, and if it is 0.9 equivalent or less, increase in molecular weight due to side reaction can be suppressed.

  A catalyst may be used to accelerate the reaction. The amount of the catalyst used is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the reaction raw material mixture composed of an epoxy compound and hydroxybenzoic acids. The reaction temperature is preferably 60 to 150 ° C., and the reaction time is preferably 3 to 30 hours. Examples of the catalyst used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, chromium octoate, and zirconium octoate.

  The number average molecular weight of the alkali-soluble resin (a2) having an epoxy group and a phenolic hydroxyl group is preferably in the range of 500 to 8000, more preferably in the range of 1000 to 6000, and more preferably in the range of 1500 to 4000. Further preferred. If the molecular weight is 500 or more, the solubility in an alkaline aqueous solution is appropriate, so that the resin of the photosensitive material is good. If the molecular weight is 8000 or less, the coatability and developability are good.

(A3) Other alkali-soluble resins Examples of other alkali-soluble resins (a3) include polyalkenylphenol resins. The polyalkenyl phenol resin is obtained by converting a hydroxyl group of a known phenol resin into an alkenyl ether, and further rearranging the alkenyl ether group into Claisen. The polyalkenylphenol resin preferably has the structure of the formula (2). By containing such a resin, it is possible to improve the development characteristics of the resulting photosensitive resin composition and to contribute to the reduction of outgas.

(In Formula (2), R < ⁶ >, R < ⁷ > and R <^8> are respectively independently a hydrogen atom, a C1-C5 alkyl group, Formula (3)

(In Formula (3), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or a carbon atom. Represents an aryl group having 6 to 12 atoms, * in formula (3) represents an linking group with a carbon atom constituting an aromatic ring), and an alkoxy group having 1 to 2 carbon atoms Alternatively, it represents a hydroxyl group, and at least one of R ⁶ , R ⁷ and R ⁸ is an alkenyl group represented by the formula (3). Q is an alkylene group represented by the formula —CR ⁹ R ¹⁰ —, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, or R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a cyclohexane having 5 to 10 carbon atoms. An alkyl group or an aryl group having 6 to 12 carbon atoms is represented. When two or more structures of the formula (2) are present in one molecule, the structures of the formula (2) may be the same or different.

  In addition, when a component (a1) corresponds also to alkali-soluble resin (a2) which has an epoxy group and a phenolic hydroxyl group, it shall handle as a component (a1). When the component (a2) corresponds to other alkali-soluble resin (a3) such as polyalkenylphenol resin, it is handled as the component (a2). That is, the alkali-soluble resin (a2) having an epoxy group and a phenolic hydroxyl group and the other alkali-soluble resin (a3) exclude those corresponding to the component (a1).

  As the alkali-soluble resin (A), one type of resin may be used alone, or two or more types of resins may be used in combination. In 100 parts by mass of the alkali-soluble resin (A), the total amount of at least one selected from the group represented by the component (a2) and the component (a3) is preferably 0 to 80% by mass, more preferably 10 It is -75 mass%, More preferably, it is 20-70 mass%. When component (a2) and component (a3) are contained within this range, the heat resistance of the photosensitive resin composition is good.

(B) Quinonediazide compound The photosensitive resin composition of this invention contains a quinonediazide compound as a radiation sensitive compound. Examples of the quinonediazide compound include those in which a quinonediazide compound having a sulfo group is bonded to a polyhydroxy compound with an ester. From the viewpoint of the contrast between the exposed area and the unexposed area, it is preferable that 50 mol% or more and 20 mol% or more of the functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide. By using such a quinonediazide compound, it is possible to obtain a positive photosensitive resin composition that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp that is a general ultraviolet ray. it can.

  Polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC , DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR -PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.) 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A , Bisphenol E, methylene bisphenol, BisP-AP (quotient Name, but include the Honshu Chemical Industry Co., Ltd.), and the like, but is not limited to these.

  Specific examples of the quinonediazide compound include 1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester of the polyhydroxy compound.

  It is known that a quinonediazide compound generates a carboxyl group through a reaction shown in the following reaction formula 2 when exposed to ultraviolet light or the like. Generation | occurrence | production of a carboxyl group enables it to melt | dissolve the exposed part (film | membrane) with respect to an alkaline solution, and alkali developability expresses.

  Although content of the quinonediazide compound (B) in the photosensitive resin composition in this invention changes with quinonediazide compounds to be used, 10-100 mass parts is preferable on the basis of 100 mass parts of alkali-soluble resin (A), and more. Preferably it is 15-90 mass parts, More preferably, it is 20-80 mass parts. Alkali developability is favorable in it being 10 mass parts or more on the basis of 100 mass parts of alkali-soluble resin (A). If it is 100 parts by mass or less, the rate of decrease in heating at 300 ° C. or more is difficult to increase.

(Optional component)
The photosensitive resin composition of this invention can add a black coloring agent, a dispersing agent, another coloring agent, a thermosetting agent, surfactant, a solvent, etc. as an arbitrary component. The optional component is defined as not applicable to either (A) or (B).

(C) Black colorant The photosensitive resin composition of the present invention can further contain, as an optional component, for example, a black colorant in order to impart light shielding properties to the partition material. As such a black colorant, for example, a black dye (c1) defined by the color index (CI) of Solvent Black 27 to 47 can be used. The black dye is preferably C.I. of Solvent Black 27, 29 or 34. I. It is stipulated in. Solvent Black 27-47 C.I. I. When at least one of the dyes defined in the above is used as a black dye, the optical density (OD value) per 1 μm thickness of the film of the photosensitive resin composition after baking is set to 0.1 to 3.0. Can maintain a color closer to black. The optical density (OD value) per 1 μm of film thickness can be measured using a transmission densitometer and a film thickness measuring device. From this advantage, when the photosensitive resin composition of the present invention is used as a partition material for a display device such as an organic EL display, the visibility of the display device can be improved.

  As for content of the black coloring agent (C) in the photosensitive resin composition in this invention, 10-100 mass parts is preferable on the basis of 100 mass parts of alkali-soluble resin (A), More preferably, it is 20-90 mass parts. More preferably, it is 30-80 mass parts. The content of the black dye (c1) can also be in the same range as the content of the black colorant (C). When the content of the black dye (c1) is 10 parts by mass or more, the OD value per 1 μm thickness of the cured film after baking can be in the range of 0.1 to 3.0, and even when heated Black color can be retained. When it is 100 parts by mass or less, the remaining film ratio, heat resistance, sensitivity, and the like are good.

  A black pigment (c2) can also be used as the black colorant of the present invention. Examples of the black pigment include black pigments such as carbon black, carbon nanotube, acetylene black, graphite, iron black, aniline black, and titanium black. These may be used alone or in combination of two or more. The black pigment can be used in the form of a dispersion. The black pigment is preferably titanium black or carbon black, and more preferably titanium black.

  The titanium black used in the present invention is not limited to the following, but a method of heating and reducing a mixture of titanium dioxide and titanium metal in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), A method of reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (special feature) JP-A-60-65069, JP-A-61-201610), a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia (JP-A-61-201610), etc. Can be used. Examples of commercially available titanium black include Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13-MT, 16M, UF-8 manufactured by Mitsubishi Materials Corporation, and Tilac D manufactured by Ako Kasei Co., Ltd. Can be mentioned. These titanium blacks may be used alone or in combination of two or more.

  Titanium black is preferably 3 to 30 parts by mass, more preferably 5 to 20 parts by mass, and still more preferably 8 to 15 parts by mass based on 100 parts by mass of the alkali-soluble resin (A). If the content of titanium black is 3 to 30 parts by mass based on 100 parts by mass of the alkali-soluble resin (A), the desired OD value (optical density) can be obtained.

  The average particle diameter D50 (volume basis) of titanium black in the dispersion is preferably 5 to 100 nm. When the average particle diameter D50 is 5 to 100 nm, high light shielding properties can be obtained. The average particle size D50 can be measured using a laser diffraction / scattering particle size distribution measuring device Microtrac wave (Nikkiso Co., Ltd.).

  As the black colorant (C), when a black dye or titanium black specified by the color index (CI) of Solvent Black 27 to 47 is adopted, the heat resistance is particularly excellent, so that a high temperature treatment of 200 ° C. or higher is performed. Even later, the photosensitive resin composition containing the black colorant can maintain a high light-shielding property while maintaining a black color.

(D) Dispersant A dispersant may be used to disperse a pigment such as titanium black. Examples of the dispersant include trade names DISPERBYK-110, DISPERBYK-111 (manufactured by Big Chemie Japan Co., Ltd.), trade names DISPARON (registered trademark) PW-36, DISPARON (registered trademark) DA-375 (Enomoto Kasei Co., Ltd.). Manufactured phosphoric acid esters, polyphosphoric acid esters, phosphoric acid polyesters, polyether phosphoric acid esters, etc., trade names Floren G-700, Floren G-900, Floren GW-1500 (Kyoeisha) Carboxy group-containing polymer dispersants such as Chemicals Co., Ltd., and higher fatty acid ester dispersants such as trade names Ajisper (registered trademark) PN411 and Azisper (registered trademark) PA111 (manufactured by Ajinomoto Fine Techno Co., Ltd.). Among them, a dispersant having no graft chain in the skeleton, for example, trade names DISPERBYK-110, DISPERBYK-111 (manufactured by Big Chemie Japan Co., Ltd.) and the like are preferably used.

  It is preferable that 1-40 mass parts is contained with respect to 100 mass parts of black pigments (c2), More preferably, it is 2-30 mass parts, More preferably, it is 3-20 mass parts. If a dispersing agent is 1-40 mass parts with respect to 100 mass parts of black pigment (c2), particle | grains can be disperse | distributed favorably.

(E) Other colorants The photosensitive resin composition of the present invention may further contain other colorants as optional components. Examples of such a colorant include dyes, organic pigments, and inorganic pigments, which can be used according to the purpose.

  Specific examples of dyes include azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, croconium dyes, merocyanine dyes, stilbene dyes, diphenylmethane dyes, triphenylmethane dyes, fluorane dyes, spiropyran dyes, phthalocyanine dyes, Examples include indigo dyes, fulgide dyes, nickel complex dyes, and azulene dyes.

  Examples of the pigment include C.I. I. Pigment Yellow 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Pigment orange 36, 43, 51, 55, 59, 61, C.I. I. Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Pigment violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment Blue 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Pigment green 7, C.I. I. And CI pigment brown 23, 25, 26.

(F) Thermosetting agent It is preferable to contain a thermosetting agent in the photosensitive resin composition of the present invention because the composition can be cured by heating. As the thermosetting agent, a thermal radical generator can be used. Preferable thermal radical generators include organic peroxides, specifically dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butyl. Organic peroxides such as cumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, etc. having a 10-hour half-life temperature of 100 to 170 ° C. Can be mentioned. As for content of a thermosetting agent, 5 mass parts or less are preferable with respect to 100 mass parts of alkali-soluble resin (A), More preferably, it is 4 mass parts or less, More preferably, it is 3 mass parts or less.

(G) Surfactant The photosensitive resin composition of the present invention can further contain, as an optional component, for example, a surfactant in order to improve applicability or developability of the coating film. . Examples of such surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether Polyoxyethylene aryl ethers such as polyoxyethylene dilaurate, nonoxy surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene distearate; Megafac® F-251, F-281, F-430, F-444, R-40, F-553, F-554, F-555, F-556, F-557, F-558, F-559 ( Above, product name, manufactured by DIC Corporation), -Fluorine (registered trademark) S-242, S-243, S-385, S-386, S-420, S-611 (above, trade names, manufactured by ACG Seimi Chemical Co., Ltd.) Surfactant: Organosiloxane polymers KP323, KP326, KP341 (above, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. These may be used alone or in combination of two or more. Such a surfactant is preferably blended in an amount of 2 parts by mass or less, more preferably 1 part by mass or less, and still more preferably 0.5 parts by mass or less based on 100 parts by mass of the alkali-soluble resin (A). The

(H) Solvent The photosensitive resin composition of the present invention is preferably dissolved in a solvent and used in the form of a solution from the viewpoint of applicability to a substrate. The photosensitive resin composition of the present invention can be adjusted to a viscosity suitable for various coating methods depending on the amount of solvent. Although an appropriate solid content concentration can be adopted depending on the purpose of use, for example, the solid content concentration can be 1 to 60% by mass, preferably 3 to 50% by mass, and more preferably 5 to 40% by mass.

  Examples of the solvent include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, diethylene glycol monomethyl ether, Diethylene glycols such as diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, etc. Glycol alkyl ether acetates, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, cyclohexanone, ethyl 2-hydroxypropionate, Methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, 3-methoxy Esters such as ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, N-methyl-2-pyrrolidone, N, N -Amides such as dimethylformamide and N, N-dimethylacetamide can be used. These solvents may be used alone or in combination of two or more.

[Method for Preparing Photosensitive Resin Composition]
The photosensitive resin composition of the present invention can be prepared by dissolving or dispersing the alkali-soluble resin (A), the quinonediazide compound (B), and, if necessary, the optional components in the solvent. it can. Depending on the purpose of use, an appropriate solid content concentration can be adopted, and for example, the solid content concentration can be 10 to 60% by mass. The prepared solution of the composition is usually filtered before use. Examples of the filtering means include a membrane filter having a pore diameter of 0.05 to 1.0 μm. The photosensitive resin composition of the present invention thus prepared is also excellent in long-term storage stability.

[Method for producing pigment dispersion]
When mixing the pigment, it is preferable to disperse the pigment in a solvent before mixing with the alkali-soluble resin (A) and the quinonediazide compound (B). The pigment dispersion can be produced by mixing a pigment, a solvent, and, if necessary, a dispersant. For example, when titanium black is used, a dispersion can be obtained by mixing titanium black, γ-butyrolactone, and DISPERBYK-111 (manufactured by Big Chemie Japan Co., Ltd.). There are no particular restrictions on the disperser used to disintegrate or disperse the pigments. Ball types such as ball mills, sand mills, bead mills, paint shakers, rocking mills, blades such as kneaders, paddle mixers, planetary mixers, Henschel mixers, etc. Examples thereof include a roll type such as a mold and a three-roll mixer, and other examples include a crushing machine, a colloid mill, an ultrasonic wave, a homogenizer, and a rotation / revolution mixer. Among these, a ball type that can stably and finely disperse in a short time is preferable. Examples of the material of the ball used in the ball mold include glass, silicon nitride, alumina, zircon, zirconia, and steel. As the bead diameter, a general shape having a diameter of 0.03 to 25 mm can be used, but a small diameter of 5 mm or less is preferable from the viewpoint of miniaturization.

  The order of addition when preparing a dispersion using a bead mill is not particularly limited, but the following order is desirable to obtain a good dispersion.

  First, a dispersing agent is uniformly dispersed in a solvent. In the case where the dispersant is not uniformly dispersed in the solvent in advance, an area having a high concentration of the dispersant is partially generated, which tends to cause problems such as particle aggregation. The required amount of pigment is then placed in the previously prepared solution and finally the beads. When aggregation is observed in the pigment, preliminary dispersion may be performed. A binder resin or other resin component may be used for the purpose of compatibility with the resin and suppression of reaggregation of the pigment.

  The order of mixing the pigment dispersion with the alkali-soluble resin, the quinonediazide compound, and optional components is not particularly limited. For example, the alkali-soluble resin is dissolved in a solvent, and the quinonediazide compound, the pigment dispersion, Accordingly, a photosensitive resin composition in a solution state can be prepared by mixing additives such as a thermosetting agent and a surfactant at a predetermined ratio.

  The stirrer used when mixing the pigment dispersion with the alkali-soluble resin, the quinonediazide compound, and the optional components is not particularly limited. Ball types such as ball mill, sand mill, bead mill, paint shaker, rocking mill, kneader, paddle Examples include a blade type such as a mixer, a planetary mixer, a Henschel mixer, a roll type such as a three-roll mixer, and a crushing machine, a colloid mill, an ultrasonic wave, a homogenizer, a rotation / revolution mixer, and a mechanical stirrer. When used at a laboratory level, a mechanical stirrer is preferable because it can be stably mixed in a short time. The stirring blade used at the time of stirring can be appropriately selected from a fan, a propeller, a cross, a turbine, a dragonfly type, and the like. A resin composition can be obtained by mixing a pigment dispersion or an alkali-soluble resin solution and stirring at room temperature for 1 to 10 minutes at a rotation speed of 10 to 1000 rpm. It is preferable to filter the prepared composition liquid before use. Examples of the filtering means include a membrane filter having a pore diameter of 0.05 to 1.0 μm. The photosensitive resin composition of the present invention thus prepared is also excellent in long-term storage stability.

[Pattern formation and curing method]
When the photosensitive resin composition of the present invention is used for radiation lithography, first, the photosensitive resin composition of the present invention is applied to the substrate surface, and the solvent is removed by means such as heating to form a coating film. be able to. The method for applying the photosensitive resin composition to the substrate surface is not particularly limited, and various methods such as a spray method, a roll coating method, a slit method, and a spin coating method can be employed.

  After applying the photosensitive resin composition of the present invention to the substrate surface, the solvent is usually dried by heating (pre-baking) to form a coating film. The heating conditions vary depending on the type of each component, the blending ratio, etc., but it is usually applied by heating at 70 to 130 ° C. for a predetermined time, for example, 1 to 20 minutes on a hot plate, or 3 to 60 minutes in an oven. A membrane can be obtained.

  Next, the pre-baked coating film is irradiated with radiation (eg, visible light, ultraviolet light, far ultraviolet light, etc.) through a mask having a predetermined pattern (exposure process), and then developed with a developer to remove unnecessary portions. To form a predetermined patterned coating film (development process). When naphthoquinone diazide sulfonic acid ester is used as a positive photosensitive compound, preferable radiation is ultraviolet to visible light having a wavelength of 250 to 450 nm.

  Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; Secondary amines such as n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline Quaternary ammonium salts such as pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonane, and other cyclic amines Using an aqueous solution of an alkali such as Kill. Although there is no restriction | limiting in particular in a density | concentration, 0.5-5.0 mass% is preferable. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like to the alkaline aqueous solution can also be used as a developer. The development time is usually 30 to 180 seconds, and the development method may be any of a liquid piling method, a shower method, a dipping method, and the like. After the development, washing with running water is performed for 30 to 90 seconds, unnecessary portions are removed, and the pattern is formed by air drying with compressed air or compressed nitrogen. Thereafter, the coating film can be obtained by heating the pattern at a predetermined temperature, for example, 120 to 350 ° C. for 20 to 200 minutes using a heating device such as a hot plate or an oven. (Heat treatment process).

  The present invention includes (1) a coating process in which the photosensitive resin composition is dissolved in a solvent and applied to a substrate; (2) a drying process in which the solvent in the coated photosensitive resin composition is removed; 3) An exposure process of irradiating radiation through a photomask; (4) a development process of forming a pattern by alkali development; and (5) a heat treatment process of heating at a temperature of 100 to 350 ° C. Can be adopted. This method can be used, for example, for forming partition walls and insulating films of organic EL elements.

  In the present invention, a partition wall of an organic EL device comprising a cured product of the photosensitive resin composition can be obtained.

  In the present invention, an insulating film of an organic EL device comprising a cured product of the photosensitive resin composition can be obtained.

  The present invention can provide an organic EL device containing a cured product of the photosensitive resin composition.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example and a comparative example, this invention is not limited to this Example.

(1) Component (a): Production and evaluation of alkali-soluble resin solution [Production Example 1]
In a 300 mL three-necked flask, 170 g of propylene glycol monomethyl ether acetate as a solvent was added and heated to 85 ° C. under a nitrogen gas atmosphere. As a polymerizable monomer having an alkali-soluble group, 4-hydroxyphenyl methacrylate ( Showa Denko "PQMA" 73g, other polymerizable monomer N-cyclohexylmaleimide (Nippon Shokubai Co., Ltd.) 27g, polymerization initiator dimethyl azobisisobutyrate (Wako Pure Chemical Industries "V-" 601 ") 1.7 g, and a solution obtained by completely dissolving 1.8 g of a compound represented by the following formula (r1) as a RAFT agent (" 723010 "manufactured by Sigma-Aldrich) in 170 g of propylene glycol monomethyl ether acetate is added dropwise over 2 hours. And further reacted at 85 ° C. for 4 hours. The reaction solution cooled to room temperature was dropped into 2000 g of toluene to precipitate a polymer. The precipitated polymer was collected by filtration and vacuum dried at 90 ° C. for 10 hours to collect milky white powder. This was dissolved in γ-butyrolactone to obtain a resin liquid having a solid content of 20% by mass (resin liquid A1-1). This polymer had a number average molecular weight of 12,400 and a weight average molecular weight of 21,100.

[Production Examples 2 to 9 and Comparative Production Examples 1 to 3]
It manufactured according to the composition shown in Table 1 by the method similar to manufacture example 1. In addition, the unit of the numerical value of each component of the manufacture example described in Table 1 and a comparative manufacture example is "g". The structure of the RAFT agent used in Production Examples 1 to 9 is as shown in the following formulas (r2) to (r5). The resin liquids prepared in Production Examples 2 to 9 were designated as resin liquids A2 to A9, respectively, and the resin liquids prepared in Comparative Production Examples 1 to 3 were designated as resin liquids X1 to X3, respectively. The number average molecular weight and the weight average molecular weight of the polymers obtained in Production Examples 2 to 9 and Comparative Production Examples 1 to 3 were as shown in Table 1, respectively.

  About the resin liquid prepared by each manufacture example and each comparative manufacture example, the weight reduction rate (outgas) was evaluated. The results are shown in Table 1. The evaluation method is as follows.

[Weight average molecular weight and number average molecular weight]
Under the following measurement conditions, the number average molecular weight and the weight average molecular weight were calculated using a calibration curve prepared using a polystyrene standard.
Device name: Shodex (registered trademark) GPC-101
Column: Shodex (registered trademark) LF-804
Mobile phase: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: Shodex (registered trademark) RI-71
Temperature: 40 ° C

[Weight reduction rate]
The resin liquids of Production Examples 1 to 9 and Comparative Production Examples 1 to 3 were heated at 250 ° C. for 60 minutes in a nitrogen gas atmosphere to dry the solvent. Science) was used to measure the weight reduction rate of the resin component when heated at 300 ° C. for 90 minutes in a nitrogen gas atmosphere. Evaluation was made with a weight reduction rate of less than 5% as “good” and a weight reduction rate of 5% or more as “bad”.

  From Production Examples 1 to 9 in Table 1, the polymer having at least one of the structures represented by the above formulas (I) and (II) and the structure represented by the formula (III) has a weight loss rate of 5%. Less than low, it was excellent in the effect of reducing outgas. On the other hand, from Comparative Production Examples 1 to 3, the polymer not containing at least one of the structures represented by the formulas (I) and (II) and the structure represented by the formula (III) has a weight loss rate exceeding 5%. It was found that outgassing was remarkably generated and it was difficult to apply to partition materials with high temperature treatment.

(2) Component (a2): Production of alkali-soluble resin solution having epoxy group and phenolic hydroxyl group [Production of resin liquid A2-1]
170 g of propylene glycol monomethyl ether acetate (manufactured by Daicel Corporation) as a solvent in a 300 mL three-necked flask as a compound having EPICLON (registered trademark) N-695 (manufactured by DIC Corporation) as a compound having at least two epoxy groups in one molecule 43 g of cresol novolac type epoxy resin, epoxy equivalent 215) was charged and dissolved at 60 ° C. in a nitrogen atmosphere. There, 20 g of 3,5-dihydroxybenzoic acid (manufactured by Wako Pure Chemical Industries, Ltd.) as hydroxybenzoic acid (0.7 equivalent with respect to 1 equivalent of epoxy group of epoxy compound) and triphenylphosphine (Hokuko Chemical) as a reaction catalyst 0.2 g of Kogyo Co., Ltd.) was added and reacted at 110 ° C. for 12 hours. The reaction solution was returned to room temperature, and a solution diluted with γ-butyrolactone to a solid content of 20% by mass was collected by filtration (resin liquid A2-1). The number average molecular weight of the obtained reaction product was 3200, and the weight average molecular weight was 7000. The measuring method of molecular weight is the same as that of the resin liquid A1-1.

[Production of Resin Liquid A2-2]
170 g of propylene glycol monomethyl ether acetate (manufactured by Daicel Corporation) as a solvent in a 300 mL three-necked flask as a compound having EPICLON (registered trademark) N-695 (manufactured by DIC Corporation) as a compound having at least two epoxy groups in one molecule 43 g of cresol novolac type epoxy resin, epoxy equivalent 215) was charged and dissolved at 60 ° C. in a nitrogen gas atmosphere. There, 15 g of 3,5-dihydroxybenzoic acid (manufactured by Wako Pure Chemical Industries, Ltd.) as hydroxybenzoic acid (0.53 equivalent to 1 equivalent of epoxy group of epoxy compound) and triphenylphosphine (Hokuko Chemical) as a reaction catalyst 0.2 g of Kogyo Co., Ltd.) was added and reacted at 110 ° C. for 12 hours. The reaction solution was returned to room temperature, and a solution diluted with γ-butyrolactone to a solid content of 20% by mass was collected by filtration (resin liquid A2-2). The number average molecular weight of the obtained reaction product was 2,800, and the weight average molecular weight was 6,200.

(3) Preparation and evaluation of photosensitive resin composition [Example 1]
(B) TS-100G (Toyo Gosei Co., Ltd., α, α, α-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene 1,2-naphthoquinonediazide-5-sulfone as a quinonediazide compound Acid ester) was dissolved in γ-butyrolactone to obtain a resin liquid having a solid content of 20% by mass (resin liquid B). VALIFAST (registered trademark) BLACK 3804 (manufactured by Orient Chemical Co., Ltd.), which is a mixture of solvent black 34 and amines, was dissolved in γ-butyrolactone as a black dye to obtain a resin liquid having a solid content of 10% by mass (resin liquid) C). Surflon S-386 (manufactured by AGC Seimi Chemical) as a leveling agent was dissolved in γ-butyrolactone to obtain a resin liquid having a solid content of 1% by mass (resin liquid D).

  50 g of the resin liquid A1-1 obtained in Production Example 1, 100 g of the resin liquid A1-2, 200 g of the resin liquid A2-1, 150 g of the resin liquid B (Note that the resin solid content of A1-1 + A2-1) Resin solid content of B + 100 wt parts of resin solid content), 430 g of resin liquid C and 22 g of resin liquid D were mixed and dissolved. After confirming dissolution visually, it was filtered through a membrane filter having a pore diameter of 0.22 μm to prepare a photosensitive resin composition.

[Examples 2-4, Comparative Examples 1-2]
In the same manner as in Example 1, the compounds were blended according to the blending composition shown in Table 2. In addition, the unit of the number of each component of the Examples described in Table 2 is “g”, and the value in parentheses is the mass part of solid content.

  About the photosensitive resin composition prepared in each Example, alkali developability, pattern formation property, pattern linearity, shape maintenance property, optical density, and weight reduction rate were evaluated. The results are shown in Table 2. The evaluation method is as follows.

[Alkali developability, pattern formability, pattern linearity]
A glass substrate (size 70 mm × 70 mm × 0.7 mm) was bar-coated with the photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 2 so that the dry film thickness was about 2 μm, and was 80 ° C. at 120 ° C. Second solvent was dried. Furthermore, 100 mJ / cm < ² > exposure was performed through the photomask made from quartz with the exposure apparatus (Brand name Multilight ML-251A / B, Ushio Electric Co., Ltd. product) incorporating the ultra high pressure mercury lamp. The amount of exposure was measured using an ultraviolet integrated light meter (trade name: UIT-150 light receiving unit UVD-S365, manufactured by USHIO INC.). The exposed coating film was subjected to alkali development with a 2.38 mass% tetramethylammonium hydroxide aqueous solution using a spin developing device (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.), and evaluated for alkali developability. In observation using an optical microscope (VH-Z250, manufactured by Keyence Corporation), the case where there was no residue after alkali development was judged as “good”, and the case where there was a residue was judged as “bad”.

  The pattern forming property was evaluated by measuring the line width of the pattern after alkali development. Using an optical microscope (VH-Z250, manufactured by Keyence Co., Ltd.), this was performed by confirming the locations where the line width of the photomask line & space pattern was 10 μm. If the line width of the line & space pattern of the pattern after alkali development is 1: 1, the line width of the line portion is within ± 10%, and other than “good” is “good”, it The pattern forming property was evaluated as “impossible”.

  In the evaluation of the linearity of the pattern, “good” is given when the pattern is almost linear, “good” is given when the pattern is slightly wavy, and “impossible” is given otherwise.

[Shape maintenance]
After forming the pattern in the same manner as described above, the glass substrate was placed on a hot plate heated to 150 ° C., and after 30 minutes, the change in pattern shape and line width was measured with a stylus step meter (SURFCOM 130A, manufactured by Tokyo Seimitsu Co., Ltd.) Was used to evaluate. Those that did not change due to heating were judged as “good”, those with a round pattern shape were judged as “good”, and others were judged as “impossible”.

[Optical density]
A glass substrate (size 70 mm × 70 mm × 0.7 mm) was bar-coated with the photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 2 so that the dry film thickness was about 1 μm, and was 80 ° C. at 120 ° C. Dried for 2 seconds. Further, after being heated at 60 ° C. for 30 minutes in a nitrogen gas atmosphere, it was cured by heating at 250 ° C. for 60 minutes in a nitrogen gas atmosphere. Using the coating film, the film thickness was measured with a film thickness measuring device (F20-NIR, manufactured by Filmetrics Co., Ltd.), and the optical density was measured with a transmission densitometer (BMT-1, manufactured by Sakata Inx Engineering Co., Ltd.). Table 2 shows the optical density value (OD value) per 1 μm thickness of the coating film.
[Weight reduction rate]
After the photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were heated at 250 ° C. for 60 minutes in a nitrogen gas atmosphere to dry the solvent, a differential thermothermal gravimetric simultaneous measurement apparatus (TG / DTA7200, Inc. Hitachi High-Tech Science) measured the weight reduction rate of the resin component when heated at 300 ° C. for 90 minutes in a nitrogen gas atmosphere. Evaluation was made with a weight reduction rate of less than 7.5% as “good” and a weight reduction rate of 7.5% or more as “bad”.

  From Examples 1 to 4 in Table 2, the photosensitive resin composition of the present invention is well-balanced in all aspects of alkali developability, pattern formability, pattern linearity, shape maintenance, optical density, and outgas reduction effect. I found it excellent. On the other hand, it turned out that the comparative examples 1-2 are difficult to apply to the partition material etc. accompanying a high temperature process from the point of outgas.

  Since the photosensitive resin composition of the present invention can reduce the generation of outgas, it can be suitably used for forming partition walls, insulating films and the like of organic EL elements that are subjected to positive radiation lithography and heat treatment.

Claims (14)

A photosensitive resin composition containing (A) an alkali-soluble resin, ( B) a quinonediazide compound , and (C) a black colorant , wherein (A) the alkali-soluble resin is
At least one end of the molecular chain has a structure represented by the following formula (I), and at least one of the structures represented by the following formula (II) in the molecule and a structure represented by the following formula (III) A photosensitive resin composition comprising an alkali-soluble resin (a1) which is a polymer.

(In the formula, Z represents a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 8 to 20 carbon atoms, a carbon atom and a hetero atom, A monovalent heterocyclic group having 3 to 20 atoms in total, -OR, -N (R) ₂ , -OC (= O) R, -C (= O) OR, -C (= O) N ( R) ₂ , —P (═O) (OR) ₂ , —P (═O) (R) _{2 is} selected, and each R is independently an alkyl group having 1 to 18 carbon atoms, An alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a monovalent heterocyclic group having 3 to 18 total atoms of carbon atoms and heteroatoms, * Indicates a bond with the polymer.)

(In the formula, R ^a is an electron withdrawing group, R ^b and R ^c are alkyl groups having 1 to 5 carbon atoms, and * is a bond with a polymer.) R ^a is —COOH, —CN, —COOCH ₃ , or

The photosensitive resin composition according to claim 1, wherein The structure represented by the formula (I) to the formula (III) is a structure derived from at least one compound selected from the group represented by the following formulas (IV-1) to (IV-8). The photosensitive resin composition of Claim 1 or 2.

(In the formula, Z represents a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 8 to 20 carbon atoms, a carbon atom and a hetero atom, A monovalent heterocyclic group having 3 to 20 atoms in total, -OR, -N (R) ₂ , -OC (= O) R, -C (= O) OR, -C (= O) N ( R) ₂ , —P (═O) (OR) ₂ , —P (═O) (R) ₂ , wherein each R is independently an alkyl group having 1 to 18 carbon atoms, An alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a monovalent heterocyclic group having 3 to 18 total atoms of carbon atoms and heteroatoms, R ^b and R ^c are alkyl groups having 1 to 5 carbon atoms, and R ^d is an alkyl group having 1 to 20 carbon atoms.)   The photosensitive resin composition as described in any one of Claims 1-3 whose weight average molecular weights of the said alkali-soluble resin (a1) are 5,000-80,000. (A) The content of the quinonediazide compound is 10 to 100 parts by mass, and the content of the ( C) black colorant is 10 to 100 parts by mass with respect to 100 parts by mass of the total amount of the alkali-soluble resin. Item 5. The photosensitive resin composition according to any one of Items 1 to 4 . The photosensitive resin according to any one of claims 1 to 5 , wherein the alkali-soluble resin (a1) is a copolymer of a polymerizable monomer having an alkali-soluble group and another polymerizable monomer. Composition. The photosensitive resin composition according to claim 6 , wherein the alkali-soluble group is at least one selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an acid anhydride group. The alkali-soluble resin (a1) is represented by the following formula (V)

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and r represents an integer of 1 to 5)
The photosensitive resin composition of Claim 6 or 7 which has a monomer unit represented by these. The alkali-soluble resin (a1) is represented by the following formula (VI)

(Wherein R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fully or partially fluorinated alkyl group having 1 to 3 carbon atoms, or a halogen atom. R ⁴ represents a hydrogen atom, a linear or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. Represents a phenyl group substituted with at least one selected from the group consisting of
In having represented by monomer units, a photosensitive resin composition according to any one of claims 6-8. (A) an alkali-soluble resin further contains an alkali-soluble resin (a2) having an epoxy group and a phenolic hydroxyl group, a photosensitive resin composition according to any one of claims 1-9. Polymerization in the presence of 0.01 to 10 parts by mass of a RAFT agent capable of imparting the structure of formula (I) or (II) and the structure of formula (III) to 100 parts by mass of the total amount of polymerizable monomers A step of producing an alkali-soluble resin (A) containing an alkali-soluble resin (a1) obtained by polymerizing a functional monomer;
The method of manufacturing a resin composition by mixing the (A) alkali-soluble resin, (B) a quinonediazide compound, and ( C) a black colorant, according to any one of claims 1 to 10 . A method for producing a photosensitive resin composition. Partition wall or an insulating film of an organic EL device comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 1 0. The organic EL device comprising the cured product of the photosensitive resin composition according to any one of claims 1 to 1 0. (1) An application step in which the photosensitive resin composition according to any one of claims 1 to 10 is dissolved in a solvent and applied to a substrate.
(2) A drying step for removing the solvent in the applied photosensitive resin composition,
(3) an exposure step of irradiating radiation through a photomask;
(4) A method for producing a radiation lithographic structure, comprising: a development step of forming a pattern by alkali development; and (5) a heat treatment step of heating at a temperature of 100 to 350 ° C.