JP5564589B2 - Photosensitive composition, pattern film, low refractive index film, optical device, and solid-state imaging device - Google Patents

Description

  The present invention relates to a pattern forming method, a pattern forming material, and a photosensitive film, a pattern film, a low refractive index film, an optical device, and a solid-state imaging device using the same.

  Low refractive index film is anti-reflection film, reflection film, semi-transmission semi-reflection film, visible light reflection infrared transmission film, infrared reflection visible light transmission film, blue reflection film, green reflection or red reflection film, bright line cut filter, color correction An optical functional film included in the film is formed on the optical member.

  Not only optical members with a flat surface shape, but also optical function members such as brightness enhancement lens films and diffusion films for liquid crystal backlights, Fresnel lenses, lenticular lenses, and microlenses used for video projection television screens are all made of resin. The desired geometrical optical performance is obtained because the material has a fine structure, but an optical functional film including a low refractive index film is also required on the surface of the fine structure.

  When a low refractive index film is used as an antireflection film, the low refractive index film having a single layer structure becomes an antireflection film as it is. As the refractive index of the antireflection film having a single layer structure, when the substrate is a transparent material such as a resin material, a low refractive index in the range of 1.2 to 1.35 is desired.

The typical material of the low refractive index film includes a fluorine polymer material having a refractive index of 1.35 to 1.4, and fine particles made of a polymer of a fluorine monomer having a refractive index of 1.37 to 1.46. Although there is a layer containing a porous material in which the material is fused (see, for example, Patent Document 1), a material having a refractive index of 1.3 or less has not been obtained.
Patent Documents 2 and 3 disclose a photocurable composition containing silica fine particles, but there is no description about forming a pattern by exposure and development.

  In addition to such reflectance characteristics, many problems such as complexity of the manufacturing process are desired to be solved. In Patent Documents 4 and 5, in order to eliminate the complexity of the manufacturing process, as a patterning method not using a photoresist, a silica-based material having photosensitivity is used, and the pattern is formed by exposing and developing itself. Although a method is described, the resolution in pattern formation is insufficient, and the low refractive index property of the resulting pattern is also insufficient.

Japanese Patent No. 3718031 International Publication No. 2007/060884 JP 2009-197155 A JP 2010-31222 A JP 2010-32996 A

This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives.
That is, the present invention provides a pattern forming method, a pattern forming material capable of forming a pattern having a low refractive index and a small amount of development residue with high resolution, a pattern forming material, and a photosensitive film, a pattern film, and a low refractive index using these. It aims at providing a film | membrane, an optical device, and a solid-state image sensor.

一般式（Ａ）中、Ｒ _１１ は、単結合若しくは２価の連結基、又は１価の置換基を表す。Ｒ _１１ が単結合若しくは２価の連結基である場合、該単結合若しくは２価の連結基は化合物（Ｃ’）が有する別の珪素原子と連結する。
Ｘ _１１ は、単結合又は２価の連結基を表す。
Ｒ _Ｐ は、重合性基を含む１価の基を表す。
〔３〕
前記一般式（Ａ）で表される構造単位を有する化合物が樹脂であり、樹脂の主鎖に珪素原子を含有する、上記〔２〕に記載の感光性組成物。
〔４〕
前記一般式（Ａ）において、Ｘ _１１ は、単結合、又は酸素原子、アルキレン基、アルケニレン基、アルキニレン基、アリーレン基、若しくはこれらの組み合わせを表す、上記〔２〕又は〔３〕に記載の感光性組成物。
〔５〕
前記一般式（Ａ）において、Ｒ _１１ は、アルキル基、アルケニル基、アルキニル基、アリール基又はアルコキシ基を表す、上記〔２〕〜〔４〕のいずれか１項に記載の感光性組成物。
〔６〕
前記重合性化合物が、分子量２０００以下の低分子化合物を含む、上記〔１〕に記載の感光性組成物。
〔７〕
前記重合性化合物が、重合性基を有する樹脂を含む、上記〔１〕に記載の感光性組成物。
〔８〕
前記樹脂が、ラジカル又はカチオン重合性繰り返し単位を有する、上記〔７〕に記載の感光性組成物。
〔９〕
前記ラジカル又はカチオン重合性繰り返し単位が、下記一般式（１）〜（３）のいずれかで表される繰り返し単位である、上記〔８〕に記載の感光性組成物。

一般式（１）〜（３）中、Ａ ^２１ 、Ａ ^２２ 及びＡ ^２３ は、各々独立に、酸素原子、硫黄原子又は−Ｎ（Ｒ ^４１ ）−を表し、Ｒ ^４１ は水素原子又はアルキル基を表す。
Ｇ ^２１ 、Ｇ ^２２ 及びＧ ^２３ は、各々独立に、２価の連結基を表す。
Ｘ ^２１ 及びＺ ^２１ は、各々独立に酸素原子、硫黄原子又は−Ｎ（Ｒ ^４２ ）−を表し、Ｒ ^４２ は水素原子又はアルキル基を表す。
Ｙ ^２１ は、単結合、酸素原子、硫黄原子、フェニレン基又は−Ｎ（Ｒ ^４３ ）−を表し、Ｒ ^４３ は水素原子又はアルキル基を表す。
Ｒ ^２１ 〜Ｒ ^４０ は、各々独立に水素原子又は１価の置換基を表す。
〔１０〕
前記重合性化合物が、分子量２０００以下の低分子化合物を含む、上記〔２〕〜〔５〕のいずれか１項に記載の感光性組成物。
〔１１〕
（Ａ）中空又は多孔質粒子、（Ｂ）活性光線又は放射線の照射により活性種を発生する化合物、及び（Ｃ’）不飽和価が５．３５ｍｍｏｌ／ｇ以上の重合性化合物を含有する感光性組成物であって、
前記化合物（Ｃ’）が、下記式（Ｃ−１３）〜（Ｃ−１８）、（Ｃ−２０）及び（Ｃ−２１）のいずれかで表される化合物である、感光性組成物。

〔１２〕
前記感光性組成物の全固形分に対する前記中空又は多孔質粒子（Ａ）の含有量が、７６質量％〜９５質量％である、上記〔２〕〜〔５〕、〔１０〕及び〔１１〕のいずれか１項に記載の感光性組成物。
〔１３〕
前記中空又は多孔質粒子の屈折率が１．１０〜１．４０である、上記〔１〕〜〔１２〕のいずれか１項に記載の感光性組成物。
〔１４〕
マイクロレンズの被覆用途に使用される上記〔１〕〜〔１３〕のいずれか１項に記載の感光性組成物。
〔１５〕
上記〔１〕〜〔１４〕のいずれか１項に記載の感光性組成物により得られるパターン膜。
〔１６〕
上記〔１５〕に記載のパターン膜である低屈折率膜。
〔１７〕
上記〔１６〕に記載の低屈折率膜を有する光学デバイス。
〔１８〕
上記〔１７〕に記載の光学デバイスを備えた固体撮像素子。
〔１９〕
（Ａ）中空又は多孔質粒子、（Ｂ）活性光線又は放射線の照射により活性種を発生する化合物、及び（Ｃ’）不飽和価が５．３５ｍｍｏｌ／ｇ以上の重合性化合物を含有する感光性組成物により得られるパターン膜。
〔２０〕
上記〔１９〕に記載のパターン膜である低屈折率膜。
〔２１〕
上記〔２０〕に記載の低屈折率膜を有する光学デバイス。
〔２２〕
上記〔２１〕に記載の光学デバイスを備えた固体撮像素子。
本発明は上記〔１〕〜〔２２〕の構成を有するものであるが、以下その他についても参考のため記載した。 The present invention has the following configuration, whereby the above object of the present invention is achieved.
[1]
Photosensitivity containing (A) hollow or porous particles, (B) a compound that generates active species upon irradiation with actinic rays or radiation, and (C ′) a polymerizable compound having an unsaturated value of 5.35 mmol / g or more. a composition,
The photosensitive composition whose content of the said hollow or porous particle (A) with respect to the total solid of the said photosensitive composition is 76 mass%-95 mass% .
[2]
Photosensitivity containing (A) hollow or porous particles, (B) a compound that generates active species upon irradiation with actinic rays or radiation, and (C ′) a polymerizable compound having an unsaturated value of 5.35 mmol / g or more. A composition comprising:
The photosensitive composition whose said compound (C ') is a compound which has a structural unit represented by the following general formula (A).

In General Formula (A), R ₁₁ represents a single bond, a divalent linking group, or a monovalent substituent. When R ₁₁ is a single bond or a divalent linking group, the single bond or divalent linking group is linked to another silicon atom of the compound (C ′).
X ₁₁ represents a single bond or a divalent linking group.
R _P represents a monovalent group containing a polymerizable group.
[3]
The photosensitive composition as described in [2] above, wherein the compound having the structural unit represented by the general formula (A) is a resin and contains a silicon atom in the main chain of the resin.
[4]
In the general formula (A), X ₁₁ represents a single bond or an oxygen atom, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, or a combination thereof. Sex composition.
[5]
In the general formula (A), R ₁₁ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or an alkoxy group, photosensitive composition according to any one of [2] to [4].
[6]
The photosensitive composition as described in [1] above, wherein the polymerizable compound contains a low molecular compound having a molecular weight of 2000 or less.
[7]
The photosensitive composition as described in [1] above, wherein the polymerizable compound contains a resin having a polymerizable group.
[8]
The photosensitive composition as described in [7] above, wherein the resin has a radical or cationic polymerizable repeating unit.
[9]
The photosensitive composition as described in [8] above, wherein the radical or cation polymerizable repeating unit is a repeating unit represented by any one of the following general formulas (1) to (3).

In the general formulas (1) to (3), A ²¹ , A ²² and A ²³ each independently represents an oxygen atom, a sulfur atom or —N (R ⁴¹ ) —, and R ⁴¹ represents a hydrogen atom or an alkyl group. Represent.
G ²¹ , G ²² and G ²³ each independently represent a divalent linking group.
X ²¹ and Z ²¹ each independently represent an oxygen atom, a sulfur atom or —N (R ⁴² ) —, and R ⁴² represents a hydrogen atom or an alkyl group.
Y ²¹ represents a single bond, an oxygen atom, a sulfur atom, a phenylene group, or —N (R ⁴³ ) —, and R ⁴³ represents a hydrogen atom or an alkyl group.
R ^{21 to} R ⁴⁰ each independently represent a hydrogen atom or a monovalent substituent.
[10]
The photosensitive composition according to any one of [2] to [5] above, wherein the polymerizable compound comprises a low molecular compound having a molecular weight of 2000 or less.
[11]
Photosensitivity containing (A) hollow or porous particles, (B) a compound that generates active species upon irradiation with actinic rays or radiation, and (C ′) a polymerizable compound having an unsaturated value of 5.35 mmol / g or more. A composition comprising:
The photosensitive composition whose said compound (C ') is a compound represented by either of following formula (C-13)-(C-18), (C-20), and (C-21).

[ 12 ]
[ 2 ] to [5], [10] and [11] above, wherein the content of the hollow or porous particles (A) with respect to the total solid content of the photosensitive composition is 76% by mass to 95% by mass. The photosensitive composition of any one of these.
[ 13 ]
The photosensitive composition according to any one of [1] to [ 12 ] above, wherein the refractive index of the hollow or porous particles is 1.10 to 1.40 .
[14 ]
The photosensitive composition according to any one of [1] to [ 13 ], which is used for coating microlenses.
[ 15 ]
The pattern film obtained by the photosensitive composition of any one of said [1]-[ 14 ].
[ 16 ]
The low refractive index film | membrane which is a pattern film as described in said [ 15 ].
[ 17 ]
An optical device having the low refractive index film described in [ 16 ] above.
[ 18 ]
The solid-state image sensor provided with the optical device as described in said [ 17 ].
[19]
Photosensitivity containing (A) hollow or porous particles, (B) a compound that generates active species upon irradiation with actinic rays or radiation, and (C ′) a polymerizable compound having an unsaturated value of 5.35 mmol / g or more. Pattern film obtained by the composition.
[20]
A low refractive index film, which is the pattern film according to the above [19].
[21]
An optical device having the low refractive index film according to [20].
[22]
A solid-state imaging device comprising the optical device according to [21].
The present invention has the above-mentioned configurations [1] to [ 22 ], but the following are also described for reference.

一般式（１）〜（３）中、Ａ^２１、Ａ^２２及びＡ^２３は、各々独立に、酸素原子、硫黄原子又は−Ｎ（Ｒ^４１）−を表し、Ｒ^４１は水素原子又はアルキル基を表す。
Ｇ^２１、Ｇ^２２及びＧ^２３は、各々独立に、２価の連結基を表す。
Ｘ^２１及びＺ^２１は、各々独立に酸素原子、硫黄原子又は−Ｎ（Ｒ^４２）−を表し、Ｒ^４２は水素原子又はアルキル基を表す。
Ｙ^２１は、単結合、酸素原子、硫黄原子、フェニレン基又は−Ｎ（Ｒ^４３）−を表し、Ｒ^４３は水素原子又はアルキル基を表す。
Ｒ^２１〜Ｒ^４０は、各々独立に水素原子又は１価の置換基を表す。
［８］ 前記樹脂が、珪素原子又はフッ素原子を側鎖に含有する樹脂である、上記［５］〜［７］のいずれか１項に記載のパターン形成方法。
［９］ 前記樹脂が、下記一般式（４）又は（５）で表される繰り返し単位を含有する、上記［８］に記載のパターン形成方法。

一般式（４）中、Ｒ^１、Ｒ^２及びＲ^３はそれぞれ独立に、水素原子、アルキル基又はアリール基を表す。
Ｒ^４及びＲ^５はそれぞれ独立に、水素原子、アルキル基又はシロキシ基を表す。
Ｒ^６、Ｒ^７及びＲ^８はそれぞれ独立に、アルキル基、シロキシ基又はアルケニル基を表す。
Ｘ^１は２価の連結基を表す。
ｎ^１は０〜２０の整数を表す。
一般式（５）中、Ｒ^１、Ｒ^２及びＲ^３は、一般式（４）におけるＲ^１、Ｒ^２及びＲ^３と同義である。
Ｘ^２は２価の連結基を表す。
Ｒ^９はフッ素原子で置換されたアルキル基を表す。
［１０］ 前記一般式（４）又は（５）で表される繰り返し単位が、下記一般式（６）又は（７）で表される繰り返し単位である、上記［９］に記載のパターン形成方法。

一般式（６）中、Ｒ^１０は水素原子又はアルキル基を表す。
Ｒ^１１、Ｒ^１２及びＲ^１３はそれぞれ独立に、アルキル基、シロキシ基又はアルケニル基を表す。
Ａ^１１は酸素原子、硫黄原子又は−Ｎ（Ｒ^１５）−を表す。
Ｒ^１５は水素原子又はアルキル基を表す。
Ｙ^１１はアルキレン基、アルキレンオキシ基又はこれらの組み合わせを表す。
一般式（７）中、
Ａ^１２は酸素原子、硫黄原子又は−Ｎ（Ｒ^１５）−を表す。
Ｙ^１２はアルキレン基、アルキレンオキシ基又はこれらの組み合わせを表す。
Ｒ^１４はフッ素原子で置換されたアルキル基を表す。
Ｒ^１０及びＲ^１５は、一般式（６）におけるＲ^１０及びＲ^１５と同義である。
［１１］ 前記化合物（Ｃ）が、下記一般式（Ａ）で表される構造単位を有する化合物である、上記［３］に記載のパターン形成方法。

一般式（Ａ）中、Ｒ_１１は、単結合若しくは２価の連結基、又は１価の置換基を表す。Ｒ_１１が単結合若しくは２価の連結基である場合、該単結合若しくは２価の連結基は化合物（Ｃ）が有する別の珪素原子と連結する。
Ｘ_１１は、単結合又は２価の連結基を表す。
Ｒ_Ｐは、重合性基を含む１価の基を表す。
［１２］ 前記一般式（Ａ）で表される構造単位を有する化合物が樹脂であり、樹脂の主鎖に珪素原子を含有する、上記［１１］に記載のパターン形成方法。
［１３］ 前記一般式（Ａ）において、Ｘ_１１は、単結合、又は酸素原子、アルキレン基、アルケニレン基、アルキニレン基、アリーレン基、若しくはこれらの組み合わせを表す、上記［１１］又は［１２］に記載のパターン形成方法。
［１４］ 前記一般式（Ａ）において、Ｒ_１１は、１価の置換基を表す、上記［１１］〜［１３］のいずれか１項に記載のパターン形成方法。
［１５］ 前記一般式（Ａ）において、Ｒ_１１は、アルキル基、アルケニル基、アルキニル基、アリール基又はアルコキシ基を表す、上記［１４］に記載のパターン形成方法。
［１６］ 更に、（Ａ’）粒子分散剤を含有する、上記［１］〜［１５］のいずれか１項に記載のパターン形成方法。
［１７］ マイクロレンズの被覆用途に使用される上記［１］〜［１６］のいずれか１項に記載のパターン形成方法。
［１８］ （Ａ）中空又は多孔質粒子、（Ｂ）活性光線又は放射線の照射により活性種を発生する化合物、及び（Ｃ）前記活性種の作用により有機溶剤を含む現像液に対する溶解性が減少する化合物を含有する感光性組成物であるパターン形成材料。
［１９］ 上記［１８］に記載のパターン形成材料により形成される感光性膜。
［２０］ 上記［１］〜［１７］のいずれか１項に記載のパターン形成方法により得られるパターン膜。
［２１］ 上記［２０］に記載のパターン膜である低屈折率膜。
［２２］ 上記［２１］に記載の低屈折率膜を有する光学デバイス。
［２３］ 上記［２２］に記載の光学デバイスを備えた固体撮像素子。 [1] A pattern forming method including a step of forming a photosensitive film with a photosensitive composition, a step of exposing the photosensitive film, and a step of developing using a developer containing an organic solvent, wherein the photosensitive property The composition is soluble in a developer containing (A) hollow or porous particles, (B) a compound that generates active species upon irradiation with actinic rays or radiation, and (C) an organic solvent due to the action of the active species. The pattern formation method which is a photosensitive composition containing the compound to reduce.
[2] The pattern forming method according to the above [1], wherein the hollow or porous particles have a refractive index of 1.10 to 1.40.
[3] The pattern forming method according to the above [1] or [2], wherein the compound (C) is a polymerizable compound.
[4] The pattern forming method according to [3], wherein the polymerizable compound includes a low molecular compound having a molecular weight of 2000 or less.
[5] The pattern forming method according to [3], wherein the polymerizable compound includes a resin having a polymerizable group.
[6] The pattern forming method according to [5], wherein the resin has a radical or cationic polymerizable repeating unit.
[7] The pattern forming method according to [6], wherein the radical or cation polymerizable repeating unit is a repeating unit represented by any one of the following general formulas (1) to (3).

In the general formulas (1) to (3), A ²¹ , A ²² and A ²³ each independently represents an oxygen atom, a sulfur atom or —N (R ⁴¹ ) —, and R ⁴¹ represents a hydrogen atom or an alkyl group. Represent.
G ²¹ , G ²² and G ²³ each independently represent a divalent linking group.
X ²¹ and Z ²¹ each independently represent an oxygen atom, a sulfur atom or —N (R ⁴² ) —, and R ⁴² represents a hydrogen atom or an alkyl group.
Y ²¹ represents a single bond, an oxygen atom, a sulfur atom, a phenylene group, or —N (R ⁴³ ) —, and R ⁴³ represents a hydrogen atom or an alkyl group.
R ^{21 to} R ⁴⁰ each independently represent a hydrogen atom or a monovalent substituent.
[8] The pattern forming method according to any one of [5] to [7], wherein the resin is a resin containing a silicon atom or a fluorine atom in a side chain.
[9] The pattern forming method according to [8], wherein the resin contains a repeating unit represented by the following general formula (4) or (5).

In general formula (4), R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group or an aryl group.
R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group or a siloxy group.
R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group, a siloxy group or an alkenyl group.
X ¹ represents a divalent linking group.
n ¹ represents an integer of 0 to 20.
In the general formula ^(5), R 1, ^{R 2} and ^{R 3} have the same meaning as ^R 1, ^{R 2} and ^{R 3} in the general formula (4).
X ² represents a divalent linking group.
R ⁹ represents an alkyl group substituted with a fluorine atom.
[10] The pattern forming method according to [9], wherein the repeating unit represented by the general formula (4) or (5) is a repeating unit represented by the following general formula (6) or (7). .

In general formula (6), R ¹⁰ represents a hydrogen atom or an alkyl group.
R ¹¹ , R ¹² and R ¹³ each independently represents an alkyl group, a siloxy group or an alkenyl group.
A ¹¹ represents an oxygen atom, a sulfur atom, or —N (R ¹⁵ ) —.
R ¹⁵ represents a hydrogen atom or an alkyl group.
Y ¹¹ represents an alkylene group, an alkyleneoxy group, or a combination thereof.
In general formula (7),
A ¹² represents an oxygen atom, a sulfur atom, or —N (R ¹⁵ ) —.
Y ¹² represents an alkylene group, an alkyleneoxy group, or a combination thereof.
R ¹⁴ represents an alkyl group substituted with a fluorine atom.
R ¹⁰ and ^{R 15} have the same meanings as ^{R 10} and ^{R 15} in the general formula (6).
[11] The pattern forming method according to [3], wherein the compound (C) is a compound having a structural unit represented by the following general formula (A).

In General Formula (A), R ₁₁ represents a single bond, a divalent linking group, or a monovalent substituent. When R ₁₁ is a single bond or a divalent linking group, the single bond or divalent linking group is linked to another silicon atom of the compound (C).
X ₁₁ represents a single bond or a divalent linking group.
R _P represents a monovalent group containing a polymerizable group.
[12] The pattern forming method according to the above [11], wherein the compound having the structural unit represented by the general formula (A) is a resin, and contains a silicon atom in the main chain of the resin.
[13] In the above general formula (A), X ₁₁ represents a single bond or an oxygen atom, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, or a combination thereof, in the above [11] or [12] The pattern formation method as described.
[14] The pattern forming method according to any one of [11] to [13], wherein in the general formula (A), R ₁₁ represents a monovalent substituent.
[15] The pattern forming method according to [14], wherein in the general formula (A), R ₁₁ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or an alkoxy group.
[16] The pattern forming method according to any one of the above [1] to [15], further comprising (A ′) a particle dispersant.
[17] The pattern forming method according to any one of [1] to [16], which is used for coating microlenses.
[18] (A) Hollow or porous particles, (B) a compound that generates active species upon irradiation with actinic rays or radiation, and (C) the solubility in a developer containing an organic solvent is reduced by the action of the active species. The pattern formation material which is a photosensitive composition containing the compound to do.
[19] A photosensitive film formed of the pattern forming material according to [18].
[20] A pattern film obtained by the pattern forming method according to any one of [1] to [17].
[21] A low refractive index film, which is the pattern film according to [20].
[22] An optical device having the low refractive index film according to [21].
[23] A solid-state imaging device including the optical device according to [22].

The present invention preferably further has the following configuration.
[24] The pattern forming method according to any one of [1] to [17], wherein the compound (B) is a photopolymerization initiator.
[25] The pattern forming method according to any one of [1] to [17] and [24], wherein the hollow or porous particles (A) are hollow particles.
[26] The pattern forming method according to any one of [1] to [17] and [25], wherein the hollow or porous particles (A) are silica particles.

  According to the present invention, a pattern forming method, a pattern forming material, and a photosensitive film, a pattern film, and a low refractive index that can form a pattern having a low refractive index and a small amount of development residue with high resolution. A film, an optical device, and a solid-state imaging device can be provided.

The present invention will be described in detail below.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, “active light” or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.

  The pattern forming method of the present invention is a pattern forming method including a step of forming a photosensitive film with a photosensitive composition, a step of exposing the photosensitive film, and a step of developing using a developer containing an organic solvent. The photosensitive composition contains (A) hollow or porous particles, (B) a compound that generates active species upon irradiation with actinic rays or radiation, and (C) a development containing an organic solvent by the action of the active species. It is a pattern formation method which is a photosensitive composition containing the compound which the solubility with respect to a liquid reduces.

The reason why the effects of the present invention can be obtained by using the pattern forming method of the present invention is not clear, but by using hollow or porous particles (A), the refractive index of the obtained pattern can be sufficiently reduced. In addition, it is considered that the use of the compound (B) and the compound (C) in combination greatly contributes to obtaining a pattern with high resolution.
Further, although its action is unknown, it is presumed that the use of the hollow or porous particles (A) and the compound (C) in combination contributes to the suppression of the development residue for some reason. Is done.

The photosensitive composition used in the pattern forming method according to the present invention is typically a negative composition (a composition that forms a negative pattern).
The present invention also relates to (A) hollow or porous particles, (B) a compound that generates active species upon irradiation with actinic rays or radiation, and (C) dissolution in a developer containing an organic solvent by the action of the active species. The present invention also relates to a pattern forming material which is a photosensitive composition containing a compound with reduced properties.
Furthermore, this invention relates also to the photosensitive film | membrane formed with the said pattern formation material.

  Hereinafter, each component of the photosensitive composition will be described in detail.

[1] (A) Hollow or porous particle The hollow particle has a structure having a cavity inside and refers to a particle having a cavity surrounded by an outer shell, and the porous particle is a porous substance having a large number of cavities. Refers to particles.
The hollow or porous particles are preferably porous particles from the viewpoint of obtaining better dry etching resistance.
The porosity of such particles is preferably 10-80% by volume, more preferably 20-60% by volume, and most preferably 30-60% by volume. The porosity of the hollow or porous particles is preferably in the above range from the viewpoint of reducing the refractive index and maintaining the durability of the particles.
The hollow or porous particles are more preferably hollow particles from the viewpoint of easily reducing the refractive index. For example, when the hollow particles are made of silica, the hollow silica particles have air with a low refractive index (refractive index = 1.0), and therefore the refractive index is normal silica (refractive index = Compared with 1.46), it is significantly lower.

  A method for producing hollow particles is described in, for example, JP-A-2001-233611. Moreover, the manufacturing method of porous particle | grains is described in each gazette, such as Unexamined-Japanese-Patent No. 2003-327424, 2003-335515, 2003-226516, 2003-238140, etc., for example.

The hollow or porous particles preferably have an average particle size of 1 to 200 nm, more preferably 10 to 100 nm.
The average particle diameter of the hollow or porous particles can be determined from a photograph obtained by observing the dispersed particles with a transmission electron microscope. The projected area of the particles is obtained, and the equivalent circle diameter is obtained therefrom to obtain the average particle size (usually, 300 or more particles are measured in order to obtain the average particle size).

The refractive index of the hollow or porous particles is preferably 1.10 to 1.40, more preferably 1.15 to 1.35, and most preferably 1.15 to 1.30. .
The refractive index here represents the refractive index of the entire particle, and when the particle is a hollow particle, it does not represent the refractive index of only the outer shell forming the hollow particle. When the particles are porous particles, the refractive index of the porous particles can be measured with an Abbe refractometer (manufactured by Atago Co., Ltd.).

The hollow or porous particles are preferably hollow or porous inorganic particles from the viewpoint of lowering the refractive index. Examples of the inorganic low refractive index particles include magnesium fluoride and silica particles, and silica particles are more preferable from the viewpoint of low refractive index properties, dispersion stability, and cost.
The primary particle diameter of these inorganic particles is preferably 1 to 100 nm, and more preferably 1 to 60 nm.
The inorganic particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical shape, but may be a bead shape, a shape having a major axis / minor axis ratio of 1 or more, or an indefinite shape.

The specific surface area of the inorganic particles is preferably 10~2000m ² / g, more preferably from 20~1800m ² / g, and most preferably 50~1500m ² / g.

Inorganic particles are used in a dispersion or coating solution to stabilize the dispersion, or to increase the affinity and binding properties with the binder component, such as a physical surface such as plasma discharge treatment or corona discharge treatment. Chemical surface treatment with a treatment, a surfactant, a coupling agent, or the like may be performed. The use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Of these, silane coupling treatment is particularly effective.
That is, when the inorganic particles are silica particles and the coupling agent is a silane compound, the organosilyl group (monoorganosilyl, diorganosilyl, triorganosilyl group) becomes silica particles by the reaction of the silane compound and the silanol group. It binds to the surface. Examples of the organic group that the surface-treated silica particles have on the surface include saturated or unsaturated hydrocarbon groups having 1 to 18 carbon atoms and halogenated hydrocarbon groups having 1 to 18 carbon atoms.
The above-mentioned coupling agent may be used as a surface treatment agent for inorganic particles in order to perform surface treatment in advance before the preparation of the coating solution for low refractive index film, or may be further added as an additive during the preparation of the coating solution.
The inorganic particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.

Commercially available silica particles can be used.
For example, Julia Catalysts Co., Ltd. through rear series (isopropanol (IPA) dispersion, 4-methyl-2-pentanone (MIBK) dispersion, etc.), OSCAL series, Nissan Chemical Co., Ltd. Snowtex series (IPA dispersion, ethylene glycol) Dispersion, methyl ethyl ketone (MEK) dispersion, dimethylacetamide dispersion, MIBK dispersion, propylene glycol monomethyl acetate dispersion, propylene glycol monomethyl ether dispersion, methanol dispersion, ethyl acetate dispersion, butyl acetate dispersion, xylene-n-butanol dispersion, toluene dispersion, etc.) Sirenax manufactured by Nippon Steel Mining Co., Ltd., PL series manufactured by Fuso Chemical Industry Co., Ltd. (IPA dispersion, toluene dispersion, propylene glycol monomethyl ether dispersion, methyl ethyl ketone dispersion, etc.), manufactured by EVONIK Erotic Jill series (propylene glycol acetate dispersion, ethylene glycol dispersion, MIBK dispersion, etc.), it is possible to use silica particles, such as EVONIK Co. AERODISP series.

  When silica particles are added to the photosensitive composition as a dispersion containing silica particles and a particle dispersant (details of the particle dispersant will be described later), the content of silica particles in the silica dispersion is 10 % By mass to 50% by mass is preferable, 15% by mass to 40% by mass is more preferable, and 15% by mass to 30% by mass is still more preferable.

  Hollow or porous particles may be used alone or in combination of two or more. When using 2 or more types together, you may use a hollow particle and a porous particle together, for example.

  The content of the hollow or porous particles with respect to the total solid content of the photosensitive composition is preferably 76% by mass to 95% by mass.

When forming a film by using the photosensitive composition, coating amount of the hollow or porous particles is ^{preferably 1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , further preferably from ^{10mg / m 2 ~60mg / m 2} . When it is 1 mg / m ² or more, the effect of lowering the refractive index and the effect of improving scratch resistance can be reliably obtained, and when it is 100 mg / m ² or less, fine irregularities are formed on the surface of the film. It is possible to suppress deterioration of the integrated reflectance.

[2] (A ′) Particle Dispersant From the viewpoint of improving the dispersibility of hollow or porous particles, the photosensitive composition is further
(A ′) It is preferable to contain a particle dispersant.

Particle dispersants include polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylic copolymers, naphthalene sulfone. Examples thereof include dispersion resins such as acid formalin condensates and compounds such as polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, and alkanol amines, and resins are preferable (hereinafter referred to as “dispersion resins”). ").
Dispersing resins can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.

  The dispersion resin is adsorbed on the surface of the particles and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures.

The weight average molecular weight of the dispersing resin (measured in terms of polystyrene by GPC method), more preferably from preferably from 1,000-2 × 10 ^5, a ^{2000~1 × 10 5, 5000~5 × 10} 4 It is particularly preferred that

  The dispersion resin is also available as a commercial product. As such a specific example, “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group) manufactured by BYK Chemie. ), 111, 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), “BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), EFKA Corporation “EFKA 4047, 4050-4010-4165 (polyurethane)”, EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (Fatty acid polyester), 6745 (phthalosy Nin derivative), 6750 (azo pigment derivative) "," Ajisper PB821, PB822 "manufactured by Ajinomoto Fan Techno Co.," Floren TG-710 (urethane oligomer) "manufactured by Kyoeisha Chemical Co.," Polyflow No. 50E, No. 300 (acrylic). Copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, manufactured by Enomoto Kasei Co., Ltd. “DA-725”, “Demol RN, N (naphthalene sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer) Polycarboxylic acid) "," Emulgen 920, 930, 935, 985 (polyoxyethylene nonyl sulfonate) Nil ether) ”,“ acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (functional part at the terminal part) manufactured by Lubrizol. 24000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Nikko Chemical Co., Ltd., "EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450" manufactured by Morishita Sangyo Co., Ltd. Examples thereof include dispersion resins such as “Id 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100”.

The dispersion resin is selected from the structural units represented by any one of the general formulas (21) to (23) described later in the compound (C) in which the solubility in the developer containing the organic solvent is reduced by the action of the active species. You may have at least one.
Further, the dispersion resin may be a resin obtained by using a compound represented by the general formula (E-1) described later in the compound (C) as a copolymer.

  As the particle dispersant, nonionic, anionic, and cationic sea surface active agents can be used. These surfactants are also available as commercial products, such as phthalocyanine derivatives (commercial products EFKA-745 (manufactured by Efka)), Solsperse 5000 (manufactured by Nippon Lubrizol Corporation); organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.) Manufactured by Co., Ltd.), (meth) acrylic acid-based (co) polymer polyflow No. 75, no. 90, no. 95 (above, manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene Nonionic surfactants such as octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; anions such as W004, W005, W017 (above, Yusho Co., Ltd.) Surfactants: Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, and other various Solsperse dispersants (manufactured by Nippon Lubrizol Co., Ltd.); Capulonic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (above, manufactured by ADEKA Corporation), and Isonet S-20 (manufactured by Sanyo Chemical Co., Ltd.) can be mentioned. In addition, amphoteric dispersants such as Hinoact T-8000E manufactured by Kawaken Fine Chemical Co., Ltd. are also included.

Moreover, ELEBASE BA-100, BA-200, BCP-2, BUB-3, BUB-4, CP-800K, EDP-475, HEB-5, Finesurf 270, 7045, 7085, Braunon DSP-12.5, DT-03, L-205, LPE-1007, O-205, S-202, S-204, S-207, S-205T (Aoki Yushi Kogyo), EMULGEN A-500, PP-290, Amate 102, 105 , 302, 320, Aminone PK-02S, Emanon CH-25, Emulgen 104P, 108, 404, 408, A-60, A-90, B-66, LS-106, LS-114, Rheodor 430V, 440V, 460V , TW-S106, TW-S120V, Rheodor Super TW-L120 (Kao), Examples include Neukargen 3000S, Fu S-3PG, FE-7PG, Pionein D-6414 (Takemoto Yushi), DYNOL604, Orphine PD-002W, Surfynol 2502, 440, 465, 485, 61 (Nisshin Chemical Industry). it can.
Also, Phosphanol ML-200, Emar 20T, E-27, Neopelex GS, Perex NBL, SS-H, SS-L, Poise 532A, Ramtel ASK, E-118B, E-150 (Kao Corporation) , EMULSOGEN COL-020, 070, 080 (Clariant), Prisurf A208B, A210B, A210G, A219B, AL, Labelin FC-45 (Daiichi Kogyo Seiyaku), Pionein A-24-EA, A-28-B, A -29-M, A-44-B, A-44TW (Takemoto Yushi), AKYPO RLM100NV, RLM45, RLM45NV, ECT-3, ECT-3NEX, ECT-7, Phosten HLP, HLP-1, HLP-TEA (Japan) Surfactant Industry).
These particle dispersants may be used alone or in combination of two or more.

The content of the particle dispersant in the photosensitive composition is preferably 1 to 100% by mass, more preferably 5 to 80% by mass, and 10 to 60% by mass with respect to the hollow or porous particles. Further preferred.
Specifically, when the particle dispersant is a dispersion resin, the amount used is preferably 5 to 100% by mass and more preferably 10 to 80% by mass with respect to the hollow or porous particles. preferable.

[3] (B) Compound that generates active species upon irradiation with actinic rays or radiation The photosensitive composition contains (B) a compound that generates active species upon irradiation with actinic rays or radiation.
The photosensitive composition of the present invention imparted with photosensitivity by containing the compound (B) can be suitably used for a photoresist, a color resist, an optical coating material, and the like.
As a compound (B), a photoinitiator can be mentioned suitably. Preferred examples of the active species include radicals, cationic species, or anionic species (more preferably, radicals or cationic species).
Hereinafter, the photopolymerization initiator will be described in detail.

The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferred and photoexcited. It may be an activator that produces some action with a sensitizer and generates active radicals, or an initiator that initiates cationic polymerization according to the type of monomer.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 200 to 800 nm (more preferably 300 to 450 nm).

  Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferred.

(Photo radical polymerization initiator)
Examples of the radical photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), hexaarylbiimidazole compounds, lophine dimers, benzoins, ketals. , 2,3-dialkyldione compounds, organic peroxides, thio compounds, disulfide compounds, azo compounds, borates, inorganic complexes, coumarins, ketone compounds (benzophenones, thioxanthones, thiochromones, anthraquinones) ), Aromatic onium salts, fluoroamine compounds, ketoxime ethers, acetophenones (aminoacetophenone compounds, hydroxyacetophenone compounds), acylphosphine compounds such as acylphosphine oxides, oximes such as oxime derivatives Compounds, and the like.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromomethyl-5-styryl-1,3,4 Oxadiazole, etc.).

  Examples of benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. It is.

  Examples of borates include, for example, Japanese Patent Nos. 2764769 and 2002-116539, and “Rad Tech'98. Proceeding April” by Kunz, Martin et al., Pages 19-22 (1998, Chicago). ) And the like described in the organic borate. Examples thereof include compounds described in paragraph numbers [0022] to [0027] of JP-A-2002-116539. Examples of other organic boron compounds include JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014. Specific examples include organoboron transition metal coordination complexes and the like, and specific examples include ion complexes with cationic dyes.

  In addition, as radical polymerization initiators other than the above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine (for example, Carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-n-propoxycoumarin), 3,3′- Rubonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3 -(3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, etc.), acylphosphine oxides (for example, bis (2,4 , 6-Trimethylbenzoyl) -phenylphos Fin oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl) -Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.) And compounds described in JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, and US Pat. No. 3,615,455.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, In propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

  The radical polymerization initiator is more preferably a compound selected from the group consisting of aminoacetophenone compounds, hydroxyacetophenone compounds, acylphosphine compounds, and oxime compounds. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969, an acylphosphine oxide initiator described in Japanese Patent No. 4225898, an oxime initiator, and an oxime initiator. As the agent, compounds described in JP-A No. 2001-233842 can also be used.

  As the aminoacetophenone initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Japan Ltd.) can be used. Further, as the acylphosphine-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF Japan Ltd.) can be used.

  The hydroxyacetophenone compound is preferably a compound represented by the following formula (V).

In the formula (V), Rv ¹ is a hydrogen atom, an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms), or a divalent organic compound. Represents a group. When Rv ¹ is a divalent organic group, two photoactive hydroxyacetophenone structures (that is, a structure in which the substituent Rv ¹ is excluded from the compound represented by the general formula (V)) are formed via Rv ¹ Represents a dimer formed by linking. Rv ² and Rv ³ each independently represent a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms). Rv ² and Rv ³ may combine to form a ring (preferably a ring having 4 to 8 carbon atoms).
Alkyl and alkoxy groups as the Rv ^1, the alkyl group as Rv ² and Rv ^3, and, ring and Rv ² and Rv ³ is formed by bonding, it may further have a substituent.

Examples of the hydroxyacetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCURE 1173), 2-hydroxy-2-methyl-1-phenylbutan-1-one, and 1- (4 -Methylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-isopropylphenyl) -2-methylpropan-1-one, 1- (4-butylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 2-hydroxy-2-methyl-1- (4-octylphenyl) propan-1-one, 1- (4-dodecylphenyl) -2-methylpropan-1-one, 1- (4-methoxyphenyl) -2-methylpropan-1-one, 1- (4-methylthiophenyl) -2-methylpropan-1-one, 1 -(4-Chlorophenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-bromophenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-1- (4 -Hydroxyphenyl) -2-methylpropan-1-one, 1- (4-dimethylaminophenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-carboethoxyphenyl) -2-hydroxy 2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1- ON (IRGACURE 2959).
In addition, as commercially available α-hydroxyacetophenone compounds, Irgacure 184 (IRGACURE 184), Darocur 1173 (DAROCURE 1173), Irgacure 127 (IRGACURE 127), Irgacure 2959 (IRGACURE 2959), Irgacure 1800 (IRGAC URE) from BASF Japan Polymerization initiators available under the trade names Irgacure 1870 (IRGACURE 1870) and DAROCURE 4265 can also be used.

  As the acylphosphine-based initiator, commercially available products IRGACURE-819, IRGACURE-819DW, DAROCUR-TPO (trade names: all manufactured by BASF Japan Ltd.) can be used. A phosphine initiator described in JP-A-2009-134098 can also be applied.

  Examples of oxime compounds such as oxime derivatives that are preferably used as a photopolymerization initiator in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, and 3-propionyloxyimino. Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4 -Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

Examples of oxime compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
IRGACURE-OXE01 (manufactured by BASF Japan), IRGACURE-OXE02 (manufactured by BASF Japan), CGI-124 (manufactured by BASF Japan), and CGI-242 (manufactured by BASF Japan) are also suitably used as commercial products.
Furthermore, the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A can also be suitably used.
Most preferably, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-267979 and the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061 are mentioned.
Specifically, the oxime compound is preferably a compound represented by the following formula (I). The NO bond of the oxime bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. Good.

(In formula (I), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.)
The monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group. , Dodecyl group, okdadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1- Naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2- Methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, and , 3 Nitorofenashiru group can be exemplified.

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, specifically, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a 9-anthryl group. 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, Xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, tarnaphthalenyl group, quarternaphthalenyl group, heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, ASEAN Trirenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, ter Nthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, specifically, an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2 -Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, and And 4-methoxybenzoyl group.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, specifically, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, or a hexyloxy group. Examples thereof include a carbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  Specific examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanyl. Phenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxy Carbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl , 4-fluorophenyl oxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and a 4-methoxy phenyloxy carbonyl group can be exemplified.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
Specifically, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiyl Nyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl Group Midinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolidinyl group Examples include a group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, and thioxanthryl group.

  Specific examples of the alkylthiocarbonyl group which may have a substituent include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, and an octadecylthiocarbonyl group. Examples thereof include a group and a trifluoromethylthiocarbonyl group.

  Specific examples of the arylthiocarbonyl group which may have a substituent include a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonyl group, and a 4-phenylsulfanylphenylthiocarbonyl group. 4-dimethylaminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3 -Chlorophenylthiocarbonyl group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenyl Two thiocarbonyl group, and a and a 4-methoxyphenylthiocarbonyl group.

  The monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Of these, the structures shown below are particularly preferred.
In the following structure, Y, X, and n have the same meanings as Y, X, and n in formula (II) described later, and preferred examples are also the same.

Examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cyclohexylene group having 6 to 12 carbon atoms, and an alkynylene group having 2 to 12 carbon atoms. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, A is an alkylene substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. Group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) An alkylene group substituted with

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent. Examples of the substituent include the same substituents as those introduced into the substituted aryl group mentioned above as specific examples of the aryl group which may have a substituent.
Among these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  In the formula (I), it is preferable in terms of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure. Me represents a methyl group, and Et represents an ethyl group.

  The oxime compound is preferably a compound represented by the following formula (II).

(In formula (II), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents 0-5. (It is an integer.)
R, A, and Ar in formula (II) have the same meanings as R, A, and Ar in formula (I), and preferred examples are also the same.

  Examples of the monovalent substituent represented by X include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a heterocyclic group, and a halogen atom. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Among these, X is preferably an alkyl group from the viewpoints of solvent solubility and improvement in absorption efficiency in the long wavelength region.
Moreover, n in Formula (2) represents the integer of 0-5, and the integer of 0-2 is preferable.

  Examples of the divalent organic group represented by Y include the structures shown below. In the groups shown below, “*” represents a bonding position between Y and an adjacent carbon atom in the formula (II).

  Among these, from the viewpoint of increasing sensitivity, the following structures are preferable.

  Furthermore, the oxime compound is preferably a compound represented by the following formula (III).

(In formula (III), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 0 to 5.)
R, X, A, Ar, and n in the formula (III) are respectively synonymous with R, X, A, Ar, and n in the formula (II), and preferred examples are also the same.

  Specific examples (B-1) to (B-10) of oxime compounds that can be suitably used are shown below, but the present invention is not limited thereto.

  The oxime compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 405 nm.

The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 3,000 to 300,000, more preferably 5,000 to 300,000, and more preferably 10,000 to 200,000 from the viewpoint of sensitivity. It is particularly preferred that
A known method can be used for the molar extinction coefficient of the compound. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Varian Inc., Carry-5 spctrophotometer) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.

(Photocationic polymerization initiator)
The cationic photopolymerization initiator may be any compound that generates a substance that initiates cationic photopolymerization by receiving energy rays such as ultraviolet rays, preferably an onium salt, more preferably an aromatic onium salt, and an arylsulfonium. Further preferred are salts and aryliodonium salts.

Specific examples of the onium salt include diphenyliodonium, 4-methoxydiphenyliodonium, bis (4-methylphenyl) iodonium, bis (4-tert-butylphenyl) iodonium, bis (dodecylphenyl) iodonium, triphenylsulfonium, diphenyl- 4-thiophenoxyphenylsulfonium, bis [4- (diphenylsulfonio) -phenyl] sulfide, bis [4- (di (4- (2-hydroxyethyl) phenyl) sulfonio) -phenyl] sulfide, η5-2,4 -(Cyclopentadienyl) [1,2,3,4,5,6-η]-(methylethyl) -benzene] -iron (1+) and the like. Specific examples of anions include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarsenate (AsF ₆ ⁻ ), hexachloroantimonate (SbCl). ₆ ^-), perchlorate ion (ClO ₄ ^-), trifluoromethanesulfonate ion _(CF 3 SO ₃ ^-), fluorosulfonic acid ion (FSO ₃ ^-), toluenesulfonate ion, trinitrobenzene sulfonate anion, trinitrotoluene Examples include sulfonate anions.

  In particular, specific examples of the aromatic onium salt include aromatic halonium salts described in JP-A-50-151996, JP-A-50-158680, JP-A-50-151997, JP Group VIA aromatic onium salts described in JP-A-52-30899, JP-A-56-55420, JP-A-55-125105, etc., Group VA-aromatics described in JP-A-50-158698, etc. Onium salts, oxosulfoxonium salts described in JP-A-56-8428, JP-A-56-149402, JP-A-57-192429, etc., described in JP-A-49-17040, etc. Aromatic diazonium salts, thiobililium salts, iron / allene complexes, aluminum complexes / photolytic silicon compound systems described in US Pat. No. 4,139,655 Agents, halides that photogenerate a hydrogen halide, o- nitrobenzyl ester compounds, imide sulfonate compound, bissulfonyldiazomethane compounds, mention may be made of an oxime sulfonate compound.

  As the photocationic polymerization initiator that can be used in the present invention, for example, a chemical amplification type photoresist or a compound used for photocationic polymerization can be widely used (edited by Organic Electronics Materials Research Group, “Organization for Imaging”). Materials, "Bunshin Publishing (1993), pages 187-192). These compounds are described in THE CHEMICAL SOCIETY OF JAPAN Voi. 71 no. 11, 1998, as well as the photocationic polymerization initiator described in “Organic Materials for Imaging”, edited by Organic Electronics Materials Study Group, Bunshin Publishing (1993), can be easily synthesized by known methods. .

  Commercially available photocationic polymerization initiators include UVI-6950, UVI-6970, UVI-6974, UVI-6990, UVI-6992 (above, Union Carbide), Adekaoptomer SP-150, SP-151. , SP-170, SP-171, SP-172 (above, manufactured by ADEKA Corporation), Irgacure 261, IRGACURE OXE01, IRGACURE CGI-1397, CGI-1325, CGI-1380, CGI-1311, CGI-263, CGI -268, CGI-1397, CGI-1325, CGI-1380, CGI-1311 (above, manufactured by BASF Japan), CI-2481, CI-2624, CI-2639, CI-2064 (above, Nippon Soda Co., Ltd.) Manufactured), CD-1010, CD-10 11, CD-1012 (above, manufactured by Sartomer), DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103, MPI-103, BBI-103 (above, Midori Chemical ( ), PCI-061T, PCI-062T, PCI-020T, PCI-022T (Nippon Kayaku Co., Ltd.), PHOTOINITIATOR 2074 (Rhodia), UR-1104, UR-1105, UR- 1106, UR-1107, UR-1113, UR-1114, UR-1115, UR-1118, UR-1200, UR-1201, UR-1202, UR-1203, UR-1204, UR-1205, UR-1207, UR-1401, UR-1402, UR-1403, UR-M1010, U -M1011, UR-M10112, UR-SAIT01, UR-SAIT02, UR-SAIT03, UR-SAIT04, UR-SAIT05, UR-SAIT06, UR-SAIT07, UR-SAIT08, UR-SAIT09, UR-SAIT10, UR-SAIT11 UR-SAIT12, UR-SAIT13, UR-SAIT14, UR-SAIT15, UR-SAIT16, UR-SAIT22, UR-SAIT30 (above, manufactured by URAY). Among these, UVI-6970, UVI-6974, Adekaoptomer SP-170, SP-171, SP-172, CD-1012 and MPI-103 have higher photocuring sensitivity due to the composition containing them. Can be expressed. Said photocationic polymerization initiator can be used individually by 1 type or in combination of 2 or more types.

  A radical photopolymerization initiator or a cationic photopolymerization initiator may be used alone, or two or more kinds may be freely combined.

  The content of the compound (B) with respect to the total solid content of the photosensitive composition is preferably 0.1 to 50% by mass, preferably 0.5 to 20% by mass, and 1 to 5% by mass. More preferably it is.

[4] (C) Compound whose solubility in a developer containing an organic solvent is reduced by the action of an active species The photosensitive composition is reduced in solubility in a developer containing an organic solvent by the action of (C) an active species. Contains compounds.

  Hereinafter, the compound whose solubility in the developer containing the organic solvent is reduced by the action of the active species will be described in detail.

  As the compound whose solubility in a developer containing an organic solvent is reduced by the action of the active species, a polymerizable compound can be preferably exemplified.

  The polymerizable compound may be a low molecular compound or a resin having a polymerizable group, but from the viewpoint of easily dispersing hollow or porous particles in the film, the polymerizable compound has a polymerizable group. The polymerizable compound preferably includes a low molecular weight compound and a resin having a polymerizable group, from the viewpoint of easy adjustment of sensitivity and strength.

First, the low molecular weight compound as the polymerizable compound will be described.
Examples of such a polymerizable compound include an addition polymerizable compound having at least one ethylenically unsaturated double bond. Specifically, it is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. The polymerizable compound is preferably a low molecular compound having a molecular weight of 2000 or less, more preferably a low molecular compound having a molecular weight of 1500 or less, and still more preferably a low molecular compound having a molecular weight of 900 or less. Here, the low molecular weight compound in the present invention refers to a compound having an unsaturated bond (so-called polymerizable monomer) by cleaving the unsaturated bond using an initiator and growing the bond in a chain manner. It is not a so-called polymer or oligomer obtained, but a compound having a constant molecular weight of 2000 or less (more preferably 1500 or less, more preferably 900 or less) (a compound having substantially no molecular weight distribution). The molecular weight is usually 100 or more.

Examples of the polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, etc. These are esters of saturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.
As these specific compounds, the compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane, and their EO-modified product, PO-modified products thereof.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (E) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (E)
(However, R ⁴ and R ⁵ each independently represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a curable composition having a very high photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers, can also be used.

  In the present invention, from the viewpoint of curing sensitivity, it preferably contains two or more ethylenically unsaturated bonds, and more preferably contains three or more ethylenically unsaturated bonds. Especially, it is preferable to contain 2 or more (meth) acrylic acid ester structures, it is more preferable to contain 3 or more, and it is most preferable to contain 4 or more. Furthermore, it is preferable to contain an EO modified body from the viewpoint of curing sensitivity and developability of the unexposed area. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.

  From the above viewpoint, bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified product, etc. are mentioned as preferable ones. Also, as commercially available products, urethane oligomer UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.) Made), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (made by Kyoeisha).

  Among them, bisphenol A diacrylate EO modified, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified, di Examples of commercially available modified products such as pentaerythritol hexaacrylate EO include DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 ( Kyoeisha) is more preferable.

  In addition, ethylenically unsaturated compounds having an acid group are also suitable. Examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate. Some TO-1382 and the like can be mentioned.

  The polymerizable compound is also preferably a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as anurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane acrylates as described in JP-B-37193, polyester acrylates and epoxy resins described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490 Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products with (meth) acrylic acid, and mixtures thereof.

  In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the said general formula, n is 0-14 and m is 1-8. A plurality of R and T present in one molecule may be the same or different.
However, in each of the radical polymerizable monomers represented by the general formulas (MO-1) to (MO-5), at least one of the plurality of Rs is —OC (═O) CH═CH ₂ , or a group represented by _{-OC (= O) C (CH} 3) = CH 2.

  Specific examples of the radical polymerizable monomer represented by the above general formulas (MO-1) to (MO-5) include compounds described in paragraph numbers 0248 to 0251 of JP2007-26979A. Can also be suitably used in the present invention.

  About these polymeric compounds, the details of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of the photosensitive composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Also, from the viewpoint of increasing the strength of the film, those having three or more functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic ester, methacrylic ester, styrene compound, vinyl ether compound) are used in combination. Thus, a method of adjusting both sensitivity and intensity is also effective. In addition, the compatibility and dispersibility with other components (for example, photopolymerization initiators) that can be contained in the photosensitive composition are also important factors in selecting and using the polymerizable compound, for example, The compatibility may be improved by using a low-purity compound or by using two or more kinds in combination. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a support.

Next, a resin having a polymerizable group (hereinafter also referred to as a developable binder resin) as the polymerizable compound will be described.
The developing binder resin is not particularly limited as long as it is a resin whose solubility in a developer containing an organic solvent is reduced by the action of active species, but is selected from the viewpoints of heat resistance, developability, curability, availability, and the like. It is preferable that

It is preferable that the main chain having the longest chain length in the resin is composed of only carbon atoms or has a structure connected by oxygen atoms or nitrogen atoms.
Resin polymerization is classified according to the reaction point, such as chain polymerization, sequential polymerization, and living polymerization. From the classification of reaction mechanism, addition polymerization, polycondensation, polyaddition, addition condensation, etc. Polymerization, anionic polymerization, coordination polymerization, ring-opening polymerization and the like are known, and generally known ones can be applied.
When the resin forms a copolymer, random copolymerization, alternating copolymerization, block copolymerization, graft copolymerization, and the like can be arbitrarily selected.

  The polymerizable group is not particularly limited, but is preferably a radical, a cation, or a group having a bond that undergoes a polymerization reaction by heating, and includes an unsaturated group (such as a carbon-carbon unsaturated double bond), an epoxy group, or an oxetane group. It is preferably an unsaturated group.

  Examples of the unsaturated group include a (meth) acryloyl group, a (meth) acrylamide group, a thio (meth) acryloyl group, a (meth) acryloyl group, a (meth) acrylamide group, and a carbon-carbon group other than a thio (meth) acryloyl group. A saturated group is mentioned.

The carbon-carbon unsaturated group other than the (meth) acryloyl group, (meth) acrylamide group and thio (meth) acryloyl group is preferably a radical polymerizable group, a cationic polymerizable group or a group having a bond that reacts by heating. . Examples of such carbon-carbon unsaturated groups include vinyl group, allyl group, propargyl group, cyclopentenyl group, cyclohexenyl group, styryl group, vinyl ether group, vinyl ester group, allyl ether group, allyl ester group, propargyl ether group. , Propargyl ester group and dicyclopentenyl group are preferable, vinyl group, allyl group, allyl ester group, propargyl ester group and dicyclopentenyl group are particularly preferable, and vinyl group is most preferable.
The polymerizable group in the present invention is preferably a (meth) acryloyl group, a (meth) acrylamide group, a thio (meth) acryloyl group or a vinyl group, more preferably a (meth) acryloyl group, a (meth) acrylamide group or a vinyl group. .

  Moreover, in order to introduce a polymerizable group into a resin, for example, by using a monomer that can impart a polymerizable group after polymerization, the resin is polymerized, and after polymerization, a treatment for imparting a polymerizable group is performed. It can be carried out.

  The resin having a polymerizable group is preferably a radical or cationic polymerizable repeating unit. The radical or cation polymerizable repeating unit is cross-linked between polymer molecules by the action of acid or radical, and gels, thereby contributing to a decrease in solubility in a developer containing an organic solvent.

The radical polymerizable repeating unit is preferably introduced into the resin by reacting the compound having the radical polymerizable group with the resin capable of binding with the compound having the radical polymerizable group.
Examples of the resin having a radical polymerizable repeating unit include a carboxyl group-containing resin, a glycidyl group-containing unsaturated compound such as glycidyl (meth) acrylate and allyl glycidyl ether, allyl alcohol, 2-hydroxy acrylate, and 2-hydroxy methacrylate. Resin obtained by reacting an unsaturated alcohol such as a resin, a resin having a hydroxyl group, a free isocyanate group-containing unsaturated compound, a resin obtained by reacting an unsaturated acid anhydride, an addition reaction product of an epoxy resin and an unsaturated carboxylic acid, Resins in which polybasic acid anhydrides are reacted, addition reaction products of conjugated diene copolymers and unsaturated dicarboxylic acid anhydrides, resins in which hydroxyl group-containing polymerizable monomers are reacted, and elimination reactions are caused by base treatment. A resin having a specific functional group that gives an unsaturated group is synthesized and subjected to base treatment. Resin or the like to produce an unsaturated group can be cited as typical resin between.

  Among them, a resin obtained by reacting a carboxyl group-containing resin with a glycidyl group-containing unsaturated compound such as glycidyl (meth) acrylate or allyl glycidyl ether, or a resin obtained by polymerizing a hydroxyl group-containing (meth) acrylic acid ester compound ( ) Resin obtained by reacting (meth) acrylic acid ester having a free isocyanate group such as acrylic acid-2-isocyanatoethyl, resin having a repeating unit represented by the following general formulas (1) to (3), base treatment A resin having a specific functional group that gives rise to an unsaturated group by elimination reaction is synthesized, and a resin or the like that generates an unsaturated group while maintaining an alkali-soluble group by subjecting the resin to a base treatment. More preferred.

  The resin having a cationically polymerizable repeating unit may have a cationically polymerizable group in the side chain. For example, a polymer containing an epoxy group, an oxetane group or the like in the side chain is also useful.

  In order to obtain a resin having a cationically polymerizable repeating unit, for example, a monomer having an epoxy group (hereinafter sometimes referred to as “monomer for introducing an epoxy group”) is polymerized as a monomer component. That's fine. Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. These monomers for introducing an epoxy group may be only one type or two or more types. When the monomer component in obtaining the resin having a cationic polymerizable repeating unit contains a monomer for introducing the epoxy group, the content ratio is not particularly limited, It should be 70% by mass, preferably 10 to 60% by mass.

  The radical or cationic polymerizable repeating unit is preferably a repeating unit represented by any one of the following general formulas (1) to (3).

In the general formulas (1) to (3), A ²¹ , A ²² and A ²³ each independently represents an oxygen atom, a sulfur atom or —N (R ⁴¹ ) —, and R ⁴¹ represents a hydrogen atom or an alkyl group. Represents.
G ²¹ , G ²² and G ²³ each independently represent a divalent linking group.
X ²¹ and Z ²¹ each independently represent an oxygen atom, a sulfur atom or —N (R ⁴² ) —, and R ⁴² represents a hydrogen atom or an alkyl group.
Y ²¹ represents a single bond, an oxygen atom, a sulfur atom, a phenylene group, or —N (R ⁴³ ) —, and R ⁴³ represents a hydrogen atom or an alkyl group.
R ^{21 to} R ⁴⁰ each independently represent a hydrogen atom or a monovalent substituent.

In the general formula (1), R ^{21 to} R ²³ each independently represents a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent represented by R ^{21 to} R ²³ include an alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) which may have a substituent. Examples of the substituent that the alkyl group may have include a hydroxyl group and a halogen atom. Among these, R ²¹ and R ²² are preferably hydrogen atoms, and R ²³ is preferably a hydrogen atom or a methyl group.
R ^{24 to} R ²⁶ each independently represents a hydrogen atom or a monovalent substituent. Examples of R ²⁴ include a hydrogen atom or an alkyl group which may have a substituent (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms). Examples of the preferable substituent include a hydroxyl group and a halogen atom. Among them, R ²⁴ is preferably a hydrogen atom, a methyl group, or an ethyl group. R ²⁵ and R ²⁶ may each independently have a hydrogen atom, a halogen atom, an alkoxycarbonyl group (preferably 2 to 15 carbon atoms), a sulfo group, a nitro group, a cyano group, or a substituent. A good alkyl group (preferably having 1 to 20 carbon atoms), an aryl group which may have a substituent (preferably 6 to 20 carbon atoms), an alkoxy group which may have a substituent (preferably having a carbon number) 1 to 15), an aryloxy group which may have a substituent (preferably 6 to 20 carbon atoms), an alkylsulfonyl group which may have a substituent (preferably 1 to 20 carbon atoms), substituted And arylsulfonyl group (preferably having 6 to 20 carbon atoms) which may have a group. Among them, a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may have a substituent, and a substituent may be mentioned. An aryl group are preferred even though, more preferably alkyl group which may have a hydrogen atom or a substituent, more preferably a hydrogen atom or a methyl group. Here, examples of the substituent that can be introduced include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, a methyl group, an ethyl group, and a phenyl group.

A ²¹ represents an oxygen atom, a sulfur atom, or —N (R ⁴¹ ) —, and X ²¹ represents an oxygen atom, a sulfur atom, or —N (R ⁴² ) —. Here, R ⁴¹ and R ⁴² each independently represent a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms). A ²¹ and X ²¹ are preferably oxygen atoms.
G ²¹ represents a divalent linking group. Examples of the divalent linking group represented by G ²¹ include an alkylene group that may have a substituent, a cycloalkylene group that may have a substituent, and a divalent that may have a substituent. Aromatic group, —OC (O) —, —C (O) O—, —N (R ⁴⁴ ) — and a linking group formed by combining these (total carbon number is preferably 1-20, It is more preferable that the number is 1 to 15, and it is more preferable that the number of carbon atoms is 2 to 10. R ⁴⁴ represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms). More preferred as G ^21, alkylene group which may have a substituent having 1 to 20 carbon atoms, the substituents may cycloalkylene group which may have a 3 to 20 carbon atoms, 6 to 20 carbon atoms A divalent aromatic group which may have a substituent, —OC (O) —, —C (O) O—, —N (R ⁴⁴ ) — and a linking group formed by combining these; Among them, a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, a cycloalkylene group which may have a substituent having 3 to 10 carbon atoms, or a 6 to 12 carbon atom. The divalent aromatic group which may have a substituent, —OC (O) —, —C (O) O—, —N (R ⁴⁴ ) — and a linking group formed by combining these have strength, development It is preferable in terms of performance such as property.

Here, the substituent in G ²¹ is preferably a group in which a hydrogen atom is bonded to a hetero atom except a hydroxyl group, for example, a group not containing an amino group, a thiol group, or a carboxyl group, and preferably a hydroxyl group.

In the general formula (2), R ^{27 to} R ²⁹ each independently represent a hydrogen atom or a monovalent substituent. A preferred range of R ²⁷ to R ²⁹ are the same as the preferred ranges of the above ^R 21 ^{to R 23.}
R ^{30 to} R ³² each independently represent a hydrogen atom or a monovalent substituent. Specific examples of R ^{30 to} R ³² include a hydrogen atom, a halogen atom, a dialkylamino group (preferably having 2 to 20 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 15 carbon atoms), a sulfo group, and a nitro group. A group, a cyano group, an optionally substituted alkyl group (preferably having 1 to 20 carbon atoms), an optionally substituted aryl group (preferably having 6 to 20 carbon atoms), and a substituent group. An optionally substituted alkoxy group (preferably having a carbon number of 1 to 15), an optionally substituted aryloxy group (preferably having a carbon number of 6 to 20), and an optionally substituted alkyl Examples include a sulfonyl group (preferably having a carbon number of 1 to 20), an arylsulfonyl group optionally having a substituent (preferably having a carbon number of 6 to 20), etc. Among them, a hydrogen atom, an alkoxycarbonyl group, Alkyl group which may have a substituent, aryl group which may have a substituent is preferable.
Examples of the substituent that may be introduced include the same manner as mentioned general formula (1) as a substituent which may be introduced into R ²¹ to R ^23.

A < ²² > represents an oxygen atom, a sulfur atom, or -N (R < ⁴¹ >)-each independently. Here, R ⁴¹ represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms).
G ²² represents a divalent linking group. Specific examples and preferred ranges of the divalent linking group represented by G ²² are the same as the specific examples and preferred ranges of the divalent linking group represented by G ²¹ described above.
Y ²¹ represents a single bond, an oxygen atom, a sulfur atom, —N (R ⁴³ ) — or a phenylene group. Here, R ⁴³ represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) which may have a substituent. The phenylene group represented by Y ²¹ may have a substituent, and examples of the substituent include an alkyl group and a halogen atom.

In the general formula (3), R ^{33 to} R ³⁵ each independently represents a hydrogen atom or a monovalent substituent. The preferred range of R ^{33 to} R ^{35 is the same as} the preferred range of R ^{21 to} R ²³ described above.
R ^{36 to} R ⁴⁰ each independently represent a hydrogen atom or a monovalent substituent. Specific examples and preferred ranges of R ^{36 to} R ⁴⁰ are the same as the specific examples and preferred ranges of R ^{30 to} R ³² .
A ²³ represents an oxygen atom, a sulfur atom, or —N (R ⁴¹ ) —, and Z ²¹ represents an oxygen atom, a sulfur atom, or —N (R ⁴² ) —. The R ⁴¹ and ^{R 42,} are the same as those for ^{R 41} and ^{R 42} in the general formula (1).

G ²³ represents a divalent linking group. Specific examples and preferred ranges of the divalent linking group represented by G ²³ are the same as the specific examples and preferred ranges of the divalent linking group represented by G ²² described above.

  The synthesis of the polymer having the repeating units represented by the general formulas (1) to (3) is performed based on the synthesis method described in paragraph numbers [0027] to [0057] of JP-A No. 2003-262958. Can do. Among these, it is preferable to use the synthesis method 1) in the publication.

  The content of the radically or cationically polymerizable repeating unit in the developable binder resin is 1 mol% to 70 mol with respect to all repeating units in the developable binder resin in order to increase sensitivity and suppress chipping of the cured pattern. %, More preferably 5 mol% to 60 mol%, and most preferably 10 mol% to 60 mol%.

  One preferred embodiment of the developable binder resin is a resin containing a silicon atom or a fluorine atom in the side chain. According to this embodiment, a resin having a silicon atom or a fluorine atom has a low polarizability, and when such a resin is used, the refractive index of the photosensitive composition can be lowered. As a result, the photosensitive composition The refractive index of the pattern obtained from the object is further reduced. In particular, when the developable binder resin contains silicon atoms in the side chain, the presence of silicon atoms, which are inorganic materials, is considered to contribute to the improvement of weather resistance.

The resin containing a fluorine atom in the side chain is preferably a resin containing a repeating unit having a fluorine atom in the side chain.
The resin containing a repeating unit having a fluorine atom in the side chain is preferably a resin obtained using a fluorine-containing monomer for reducing the refractive index.
In order to realize a low refractive index, it is preferable to use a homopolymer or copolymer of a fluorine-containing monomer, or a copolymer of a fluorine-containing monomer and a non-fluorine monomer.

  The following are mentioned as a fluorine-containing monomer.

  In the above formula, n represents an integer.

  Although the polymer structure obtained from the said fluorine monomer is shown below, this invention is not limited to this.

(Where l + m + n is 1 to 6, l is an integer from 0 to 5, m is an integer from 1 to 4, n is an integer from 0 to 1, and R is F or CF ₃ . is there.)

(However, R ₁ and R ₂ are each independently F or CF _3. )

  The resin containing a silicon atom in the side chain is preferably a resin containing a repeating unit having a silicon atom in the side chain.

  The repeating unit containing a silicon atom or a fluorine atom in the side chain, which may be contained in the developable binder resin, is preferably a repeating unit represented by the following general formula (4) or (5).

In general formula (4), R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group or an aryl group.
R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group or a siloxy group.
R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group, a siloxy group or an alkenyl group.
X ¹ represents a divalent linking group.
n ¹ represents an integer of 0 to 20.
In the general formula ^(5), R 1, ^{R 2} and ^{R 3} have the same meaning as ^R 1, ^{R 2} and ^{R 3} in the general formula (4).
X ² represents a divalent linking group.
R ⁹ represents an alkyl group substituted with a fluorine atom.

The alkyl group represented by R ¹ , R ² and R ³ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group.
The aryl group represented by R ¹ , R ² and R ³ is preferably an aryl group having 5 to 30 carbon atoms, and more preferably an aryl group having 6 to 8 carbon atoms.
These alkyl groups and aryl groups may have a substituent such as a hydroxyl group, a halogen atom, or a carboxyl group.
Most preferred is when R ¹ and R ² represent a hydrogen atom and R ³ is a hydrogen atom or an alkyl group.

R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group or a siloxy group. The siloxy group is a monovalent substituent in which a silicon atom of a silyl group having an arbitrary substituent is bonded through an oxygen atom.
The alkyl group represented by R ⁴ and R ⁵ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group.
The siloxy group represented by R ⁴ and R ⁵ is a structure represented by —OSi (R ⁵¹ ) (R ⁵² ) (R ⁵³ ), and R ⁵¹ , R ⁵² and R ⁵³ are each independently an alkyl group or Represents an alkenyl group. The alkyl group represented by R ⁵¹ , R ⁵² and R ⁵³ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. The alkenyl group represented by R ⁵¹ , R ⁵² and R ⁵³ is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 4 carbon atoms, and most preferably a vinyl group.

R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group, a siloxy group or an alkenyl group. The alkyl group represented by R ⁶ , R ⁷ and R ⁸ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group.
The siloxy group represented by R ⁶ , R ⁷ and R ⁸ is a structure represented by —OSi (R ⁵¹ ) (R ⁵² ) (R ⁵³ ), and the definition and preferred range thereof are the aforementioned R ⁴ and R This is the same as the siloxy group represented by ⁵ .
The alkenyl group represented by R ⁶ , R ⁷ and R ⁸ is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 4 carbon atoms, and most preferably a vinyl group.

X ¹ and X ² represent a divalent linking group. Examples of the divalent linking group represented by X ¹ and X ² include an oxygen atom, a sulfur atom, an alkylene group, a cycloalkylene group, a phenylene group, —OC (O) —, —C (O) O—, —C (O) N (R ¹⁵ ) — and a linking group formed by a combination thereof (total carbon number is preferably 1 to 20, more preferably 1 to 15 carbon atoms, more preferably 2 to 10 is more preferable). R ¹⁵ represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms), and is preferably a hydrogen atom.
The divalent linking group represented by X ¹ and X ² is preferably an alkylene group, a —COO—Rt— group, an —O—Rt— group, or a group formed by combining two or more thereof.
Rt represents an alkylene group or a cycloalkylene group, preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group, — (CH ₂ ) ₂ — group, or — (CH ₂ ) ₃ — group.
The alkylene group contained in the divalent linking group as X ¹ and X ² may be substituted with a hydroxyl group or a trialkylsilyl group (preferably a trimethylsilyl group).

n ¹ represents an integer of 0 to 20, preferably an integer of 0, more preferably an integer of 0 to 5.

R ⁹ represents an alkyl group substituted with a fluorine atom, preferably an alkyl group substituted with a fluorine atom having 1 to 20 carbon atoms, and is an alkyl group substituted with a fluorine atom having 1 to 10 carbon atoms. It is more preferable. The number of fluorine atoms in the alkyl group substituted with the fluorine atom represented by R ⁹ is preferably 3 to 20, and more preferably 3 to 15.

  Furthermore, the repeating unit represented by the general formula (4) and the repeating unit represented by the general formula (5) are respectively represented by the repeating unit represented by the following general formula (6) and the general formula (7). A repeating unit is preferred from the viewpoint of the ease of synthesis.

In general formula (6), R ¹⁰ represents a hydrogen atom or an alkyl group.
R ¹¹ , R ¹² and R ¹³ each independently represents an alkyl group, a siloxy group or an alkenyl group.
A ¹¹ represents an oxygen atom, a sulfur atom, or —N (R ¹⁵ ) —.
R ¹⁵ represents a hydrogen atom or an alkyl group.
Y ¹¹ represents an alkylene group, an alkyleneoxy group, or a combination thereof.
In general formula (7),
A ¹² represents an oxygen atom, a sulfur atom, or —N (R ¹⁵ ) —.
Y ¹² represents an alkylene group, an alkyleneoxy group, or a combination thereof.
R ¹⁴ represents an alkyl group substituted with a fluorine atom.
R ¹⁰ and ^{R 15} have the same meanings as ^{R 10} and ^{R 15} in the general formula (6).

In general formula (6), R ¹⁰ represents a hydrogen atom or an alkyl group. The alkyl group represented by R ¹⁰ may have a substituent such as a hydroxyl group, a halogen atom, or a carboxyl group. The alkyl group represented by R ¹⁰ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group, an ethyl group, or a propyl group. And most preferably a methyl group.

R ¹¹ , R ¹² and R ¹³ each independently represents an alkyl group, a siloxy group or an alkenyl group. The preferred range of the alkyl group, siloxy group and alkenyl group represented by R ¹¹ , R ¹² and R ¹³ is preferably the alkyl group, siloxy group and alkenyl group represented by the aforementioned R ⁶ , R ⁷ and R ^8. Similar to range.

A ¹¹ represents an oxygen atom, a sulfur atom, or —N (R ¹⁵ ) —. R ¹⁵ represents a hydrogen atom or an alkyl group, and a preferred range is the same as described above. A ¹¹ is preferably an oxygen atom or —N (R ¹⁵ ) —, and more preferably an oxygen atom.

Y ¹¹ represents an alkylene group, an alkyleneoxy group, or a combination thereof. Y ¹¹ is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 5 carbon atoms. Specific examples include a methylene group, an ethylene group, and a propylene group. The alkylene group contained in Y ¹¹ may be substituted by a hydroxyl group.

In the general formula ^{(7), A 12} represents an oxygen atom, a sulfur atom or -N ^{(R 15)} - represents a. A ¹² is preferably an oxygen atom or —N (R ¹⁵ ) —, and more preferably an oxygen atom.
Y ¹² represents an alkylene group, an alkyleneoxy group, or a combination thereof. Y ¹² is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms. Specific examples include a methylene group, an ethylene group, and a propylene group. The alkylene group contained in Y ¹² may be substituted with an alkyl group (preferably a trifluoromethyl group) substituted with a fluorine atom.
R ¹⁴ represents an alkyl group substituted with a fluorine atom. The preferred range of the alkyl group substituted with a fluorine atom represented by R ¹⁴ is the same as the alkyl group substituted with the fluorine atom represented by R ⁹ described above.
R ¹⁰ and ^{R 15} are synonymous with ^{R 10} and ^{R 15} in the general formula (6), and preferred ranges are also the same.

  Specific examples of the repeating unit represented by the general formula (4) include the following repeating units.

  Specific examples of the repeating unit represented by the general formula (5) include the following repeating units.

  The developable binder resin preferably has the radical or cation polymerizable repeating unit and at least one repeating unit represented by any one of the general formulas (4) to (7). Sensitive curability and alkali developability with few residues can be achieved more reliably.

  At least one repeating unit represented by any one of the general formulas (4) to (7) contributes to lowering the refractive index of the developing binder resin. Further, from the viewpoint of weather resistance, it is more preferable that the developing binder resin contains a silicon atom in the side chain, that is, contains a repeating unit represented by the general formula (4) or (6).

  The content of the repeating unit containing a silicon atom or a fluorine atom in the side chain in the developable binder resin is preferably 1 mol% to 90 mol% with respect to all repeating units in the developable binder resin. % To 70 mol% is more preferable, and 20 mol% to 60 mol% is most preferable.

  The developable binder resin may have a cyano group, and specifically may have a repeating unit containing a cyano group. In this case, the developable binder resin preferably has a repeating unit containing a cyano group represented by the following general formula (III).

In general formula (III):
R _c31 represents a hydrogen atom, an alkyl group, a cyano group, or a —CH ₂ —O—Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group.
R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, or a cycloalkenyl group. These groups may be substituted with a cyano group.
However, at least one of R _c31 and R _c32 contains a cyano group.
L _c3 represents a single bond or a divalent linking group.

In general formula (III), the alkyl group represented by R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
R _c32 is preferably an unsubstituted alkyl group.
The divalent linking group of L _c3 is preferably an alkylene group (preferably having a carbon number of 1 to 5), an oxy group, or an ester bond (a group represented by —COO—).

  The repeating unit represented by the general formula (III) is preferably a repeating unit represented by the following general formula (CIII-1).

In general formula (CIII-1), R ₅ represents a hydrocarbon group. R _{c 31} has the same meaning as _{R c 31} of the general formula (III). However, at least one of R _c31 and R ₅ contains a cyano group.

Examples of the hydrocarbon group for R ₅ include a chain or cyclic structure. Specific examples in the case of having a cyclic structure include a monocyclic or polycyclic cycloalkyl group (preferably having 3 to 12 carbon atoms, more preferably 3 to 7 carbon atoms), a monocyclic or polycyclic cycloalkenyl group (carbon number). 3 to 12 are preferable), more preferably 6 to 12 carbon atoms, and an aralkyl group (preferably 7 to 20 carbon atoms, more preferably 7 to 12 carbon atoms).

The cycloalkyl group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. The bridged cyclic hydrocarbon ring includes a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, and a tetracyclic hydrocarbon ring. Etc. The bridged cyclic hydrocarbon ring also includes, for example, a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed.
Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 ^2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

  These hydrocarbon groups may have a substituent, and preferred substituents include bromine atom, chlorine atom, alkyl group, hydroxyl group substituted with hydrogen atom, amino group substituted with hydrogen atom, cyano Groups. Preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The above alkyl group may further have a substituent, and the substituent that may further have a bromine atom, a chlorine atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, or a hydrogen atom substituted An amino group formed can be mentioned.

  Examples of the substituent for the hydrogen atom include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group. Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms, preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl groups, and preferred substituted ethyl groups. 1-ethoxyethyl, 1-methyl-1-methoxyethyl, preferred acyl groups include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl groups, etc., aliphatic acyl groups having 1 to 6 carbon atoms, alkoxycarbonyl Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.

Specific examples of the repeating unit containing a cyano group represented by the general formula (III) are shown below, but are not limited thereto (in the specific examples, Ra is a hydrogen atom, an alkyl group, cyano A group or —CH ₂ —O—Rac ₂ group, wherein Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group.

  The content of the repeating unit containing a cyano group is preferably from 10 to 80 mol%, more preferably from 10 to 60 mol%, based on all repeating units of the developing binder resin.

  The developable binder resin may be a resin obtained by using a compound represented by the following general formula (E-1) (hereinafter sometimes referred to as “ether dimer”) as a copolymer. .

In formula (E-1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group. The hydrocarbon group as R ¹ and R ² is preferably a hydrocarbon group having 1 to 15 carbon atoms, and may further have a substituent.

The photosensitive composition contains a resin obtained by using the compound represented by the general formula (E-1) as a copolymer, whereby the heat resistance of a cured coating film formed using the composition is increased. And transparency are further improved.
In the general formula (E-1) representing the ether dimer, the hydrocarbon group represented by R ¹ and R ² is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and isopropyl. A linear or branched alkyl group such as a group, n-butyl group, isobutyl group, t-butyl group, t-amyl group, stearyl group, lauryl group, 2-ethylhexyl group; an aryl group such as a phenyl group; An alicyclic group such as a cyclohexyl group, t-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, 2-methyl-2-adamantyl group; 1-methoxyethyl group, An alkyl group substituted with alkoxy such as 1-ethoxyethyl group; an alkyl group substituted with aryl group such as benzyl; and the like.
Among these, a group containing a primary or secondary carbon which is difficult to be removed by an acid or heat, such as a methyl group, an ethyl group, a cyclohexyl group, or a benzyl group, is particularly preferable in terms of heat resistance.
Note that R ¹ and R ² may be the same type of substituents or different substituents.

  Specific examples of the ether dimer include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2 ′-[oxybis (methylene)] bis-2-propeno , Di (stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2 -Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1- Ethoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis ( Methylene)] bis-2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t- Tilcyclohexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 Examples include '-[oxybis (methylene)] bis-2-propenoate and di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate. Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be only one kind or two or more kinds.

  The content of the repeating unit corresponding to the compound represented by the general formula (E-1) is preferably 20 to 90 mol%, and preferably 30 to 60 mol% with respect to all the repeating units of the developing binder resin. More preferably.

The developable binder resin may contain a repeating unit other than the repeating units described above (hereinafter also referred to as other repeating units).
Examples of other repeating units include repeating units having an alkali-soluble group.

Examples of the alkali-soluble group include an acid group, an alcoholic hydroxyl group, a pyrrolidone group, and an alkylene oxide group, and an acid group is more preferable.
The acid group is not particularly limited, and examples thereof include a carboxyl group, an active methylene group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, and a carboxylic acid anhydride group. A carboxyl group and an active methylene group are preferable, and An acid group is more preferable. Note The active methylene group is preferably a group represented by _{-NH-C (O) -CH 2} -C (O) -R M, R M represents an alkyl group or an alkoxy group, these groups You may have substituents, such as a fluorine atom. R _M is preferably an alkyl group or alkoxy group having 1 to 6 carbon atoms, more preferably a methyl group, a trifluoromethyl group or a methoxy group. These acid groups may be used alone or in combination of two or more. In order to introduce an acid group into the binder resin, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as “monomer for introducing an acid group”). ) As a monomer component.

In addition, when introducing an acid group using a monomer capable of imparting an acid group after polymerization as a monomer component, for example, a treatment for imparting an acid group as described later is required after the polymerization.
Examples of the monomer having an acid group include a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid, a monomer having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, maleic anhydride, and itaconic anhydride. Although the monomer etc. which have a carboxylic anhydride group are mentioned, Especially, (meth) acrylic acid is preferable among these.

Examples of the monomer capable of imparting an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate. These monomers for introducing an acid group may be only one type or two or more types.
In the case of using a monomer capable of imparting an acid group after polymerization, the treatment for imparting the acid group after polymerization includes a treatment of modifying a part of the polar group of the polymer side chain by a polymer reaction.

  The developable binder resin may or may not contain a repeating unit having an alkali-soluble group, but if it is contained, the content of the repeating unit having an alkali-soluble group in the developable binder resin is 1 mol% to 50 mol% is preferable, 1 mol% to 40 mol% is more preferable, and 1 mol% to 30 mol% is most preferable.

  Examples of the monomer corresponding to the other repeating unit include the following compounds (1) to (12).

  (1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as

  (2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

  (3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, methacryl Acid hexyl, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl methyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, Alkyl methacrylates such as allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate;

  (4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

  (5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.

  (6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.

  (7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.

  (8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

  (9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

  (10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.

  (11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.

  (12) Methacrylic acid monomers having a hetero atom bonded to the α-position, for example, compounds described in JP-A No. 2002-309057, JP-A No. 2002-311569 and the like can be mentioned.

  In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. Urethane binder polymers containing acid groups described in No. 271741, JP-A-11-352691 and the like, and urethane binder polymers having acid groups and double bonds in side chains as described in JP-A No. 2002-107918 are It is preferable because of its excellent strength.

The developable binder resin can be obtained by radical polymerization or cationic polymerization of a polymerizable monomer corresponding to each repeating unit by a conventionally known method.
Examples of the solvent used in the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, 2-methoxyethyl acetate, Diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water, etc. Is mentioned.
These solvents are used alone or in combination of two or more.

The radical polymerization initiator used for synthesizing the binder resin includes benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, diisopropyl peroxycarbonate, di-t-butyl peroxide, and t-butyl peroxide. Examples thereof include organic peroxides such as oxybenzoate and azo compounds such as 2,2′-azobisisobutyronitrile.
These radical polymerization initiators are preferably used in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the monomer.

  Further, as one of the preferred embodiments of the compound (C) in which the solubility in a developer containing an organic solvent is reduced by the action of the active species, a compound having a structural unit represented by the following general formula (A) is exemplified. Can do. According to this embodiment, the compound having a silicon atom has a low polarizability, and when such a compound is used, the refractive index of the photosensitive composition can be lowered, and as a result, the compound obtained from the photosensitive composition can be obtained. The refractive index of the resulting pattern is also reduced. In addition, the presence of silicon atoms, which are inorganic materials, is considered to contribute to the improvement of weather resistance.

In General Formula (A), R ₁₁ represents a single bond, a divalent linking group, or a monovalent substituent. When R ₁₁ is a single bond or a divalent linking group, the single bond or divalent linking group is linked to another silicon atom of the compound (C).
X ₁₁ represents a single bond or a divalent linking group.
R _P represents a monovalent group containing a polymerizable group.

R ₁₁ preferably represents a monovalent substituent. When R ₁₁ is a single bond or a divalent linking group, the structural unit represented by the general formula (A) is another structural unit represented by the general formula (A) or a general formula (C ) And other silicon-containing repeating units such as a structural unit represented by the above-described single bond or divalent linking group.
Examples of the divalent linking group represented by R ₁₁ include an oxygen atom, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, or a combination thereof.
The alkylene group represented by R ₁₁ is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
The alkenylene group represented by R ₁₁ is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms, and may have an unsaturated double bond at an arbitrary position.
The alkynylene group represented by R ₁₁ is preferably an alkynylene group having 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms, and may have an unsaturated triple bond at an arbitrary position.
The arylene group represented by R ₁₁ is preferably an arylene group having 6 to 20 carbon atoms, and more preferably 6 to 10 carbon atoms.
The divalent linking group represented by R ₁₁ may be a group formed by combining at least two selected from the group consisting of an oxygen atom, an alkylene group, an alkenylene group, an alkynylene group, and an arylene group. And a group formed by combining at least two selected from the group consisting of alkylene groups. The total carbon number in the group formed by combining at least two of these is preferably 1 to 40, more preferably 1 to 20, and still more preferably 1 to 10.
The divalent linking group represented by R ₁₁ may have a substituent, and the substituent is an alkyl group (preferably having 1 to 10 carbons, more preferably 1 to 6 carbons, and still more preferably carbon. 1 to 4), an aryl group (preferably 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms), an alkoxy group (preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms), aryloxy A group (preferably having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms), an acyloxy group (preferably having 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms), an acyl group (preferably having 2 to 2 carbon atoms). 10, more preferably 2 to 4 carbon atoms), an alkoxycarbonyl group (preferably 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms), an amino group, a heterocyclic group (preferably 2 to 20 carbon atoms, and more). Preferably carbon number 2-10), halogen atoms and the like.
From the viewpoint of low refractive index, the single bond or divalent linking group represented by R ₁₁ is an oxygen atom, an alkylene group, or a combination of at least two selected from the group consisting of an oxygen atom and an alkylene group. And an oxygen atom or an alkylene group is more preferable.

Examples of the monovalent substituent represented by R ₁₁ include an alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms), and a cycloalkyl group (preferably 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, still more preferably 3 to 7 carbon atoms, an alkenyl group (preferably 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms), an alkynyl group (preferably Has 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms, an aryl group (preferably 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms), an alkoxy group (preferably 1 to 10 carbon atoms, more Preferably C1-C4) etc. are mentioned. These groups may have a substituent, and examples of the substituent include those similar to the specific examples of the substituent which the divalent linking group represented by R ₁₁ described above may have.
When R ₁₁ represents a monovalent substituent, R ₁₁ preferably represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or an alkoxy group, more preferably an alkyl group or an alkoxy group, still more preferably It is a C1-C6 alkyl group or a C1-C4 alkoxy group, Most preferably, it is a methyl group.

The single bond or divalent linking group represented by X ₁₁ is preferably a divalent linking group. Specific examples and preferred ranges of the divalent linking group represented by X ₁₁ are the same as the specific examples and preferred ranges of the divalent linking group represented by R ₁₁ .

Specific examples of the polymerizable groups contained in the monovalent group represented by R _P include the same groups as the examples of the polymerizable group in the developable binder resin.
A monovalent group containing a polymerizable group represented by R _P is a monovalent group containing a polymerizable group represented by R _P is not particularly limited as long as it contains a polymerizable group described above, the aforementioned polymerizable Group itself or a polymerizable group, and an oxygen atom, a sulfur atom, an alkylene group, a cycloalkylene group, an arylene group, -C (O) O-, -C (O) N (R ^L )-, -C (O ) S—, —N (R ^L ) —, —Si (R ^L ) ₂ — and at least one selected from the group consisting of a linking group combining these, and a monovalent group. May be. Preferably, the above-described polymerizable group itself, or the polymerizable group, and an oxygen atom, an alkylene group, a cycloalkylene group, an arylene group, —C (O) O—, —C (O) N (R ^L ) —, and It is a monovalent group formed by combining at least one selected from the group consisting of a linking group formed by combining these. Here, ^RL represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms), and is preferably a hydrogen atom.

The total number of carbon atoms of the monovalent group represented by R _P (i.e., the total number of carbon atoms of residues represented by R _P) is not particularly limited, is generally from 2 to 40, preferably 2 to 30 More preferably, it is 2-20. The molecular weight of the monovalent group represented by R _P (i.e., the molecular weight of residue represented by _{R P)} is not particularly limited, but typically in the range of 20 to 2000, preferably lies at 20 to 1000 More preferably, it is 20-500.
The number of polymerizable groups contained in the monovalent group represented by R _P is not particularly limited, generally is 1-6, preferably 1-4, more preferably 1 or 2 It is a piece. From the viewpoint of imparting scratch resistance, two or more are preferably contained.

  The structural unit represented by the general formula (A) may be a structural unit represented by the following general formula (A-1) or (A-2).

In the formula, _RAP represents a monovalent group containing an alkali-soluble group and a polymerizable group.
R _A represents a monovalent group containing an alkali-soluble group.
R _{11, X 11} and _{R P} are each the same meaning as _{R 11, X 11} and _{R P} in formula (A), specific examples and preferred examples are also the same.

A monovalent group containing an alkali-soluble group and a polymerizable group represented by R _AP is not particularly limited as long as it contains both an alkali-soluble group and a polymerizable group, and an alkali-soluble group and a polymerizable group, an oxygen atom, Sulfur atom, alkylene group, alkenylene group, alkynylene group, cycloalkylene group, arylene group, —C (O) O—, —C (O) N (R ^L ) —, —C (O) S—, —N ( It may be a monovalent group formed by combining at least one selected from the group consisting of R ^L ) —, —Si (R ^L ) ₂ —, and a linking group formed by combining these. Preferably, the alkali-soluble group and the polymerizable group described above, an oxygen atom, an alkylene group, an alkenylene group, a cycloalkylene group, an arylene group, —C (O) O—, —C (O) N (R ^L ) —, and It is a monovalent group formed by combining at least one selected from the group consisting of a linking group formed by combining these. Here, ^RL is the same as described above.
Here, specific examples of the polymerizable group and the alkali-soluble group include groups similar to the above-described specific examples of the polymerizable group and the alkali-soluble group described in the developing binder resin.

Included in the monovalent group represented by R _AP, the number of alkali-soluble group is not particularly limited, is generally 1-6, preferably 1-4, more preferably 1 or 2 It is a piece.
Included in the monovalent group represented by R _AP, the number of polymerizable groups is not particularly limited, is generally 1-6, preferably 1-4, more preferably 1 or 2 It is a piece. From the viewpoint of imparting scratch resistance, two or more are preferably contained.

A monovalent group containing an alkali-soluble group represented by R _A is a monovalent group containing an alkali-soluble group represented by R _A is not particularly limited as long as it contains an alkali-soluble group described above, the aforementioned alkali-soluble A group itself or an alkali-soluble group, an oxygen atom, a sulfur atom, an alkylene group, a cycloalkylene group, an arylene group, -C (O) O-, -C (O) N (R ^L )-, -C (O ) S—, —N (R ^L ) —, —Si (R ^L ) ₂ — and at least one selected from the group consisting of a linking group combining these, and a monovalent group. May be. Preferably, the alkali-soluble group itself or the alkali-soluble group, an oxygen atom, an alkylene group, a cycloalkylene group, an arylene group, —C (O) O—, —C (O) N (R ^L ) — and It is a monovalent group formed by combining at least one selected from the group consisting of a linking group formed by combining these. Here, ^RL is the same as described above.

The total number of carbon atoms of the monovalent group represented by R _{AP (i.e.,} the total number of carbon atoms of residues represented by _{R AP)} is not particularly limited, is generally 3 to 40, preferably 3 to 30 More preferably, it is 3-20. The molecular weight of the monovalent group represented by R _{AP (i.e.,} the molecular weight of residue represented by _{R AP)} is not particularly limited, but typically in the range of 50 to 2000, preferably lies at 50 to 1000 More preferably, it is 50-500.
The number of alkali-soluble group contained in the monovalent group represented by R _A, the total number of carbon atoms and a molecular weight of the monovalent group represented by R _A (i.e., the total number of carbon atoms of residues represented by R _A And molecular weight) are the same as those in _RAP described above.

  The compound having the structural unit represented by the general formula (A) may further have a structural unit represented by the following general formula (B).

R _{11, X 11} and _{R A} are each the same meaning as _{R 11, X 11} and _{R A} in formula (A) and (A-2), specific examples and preferred examples are also the same.

(Polymer containing structural units containing silicon atoms)
In the form in which the compound (C) is a compound having the structural unit represented by the general formula (A), the compound (C) is a polymer including the structural unit represented by the general formula (A). Preferably, the form of the polymer is not particularly limited, and examples thereof include known linear polymers, cage-type polysiloxanes, ladder-type polysiloxanes, and the like. In this embodiment, the compound (C) is preferably a resin from the viewpoint of resolution and coatability, and a resin containing a silicon atom in the main chain of the resin can further reduce the refractive index. It is preferable from the viewpoint. Examples of the resin that is a linear polymer include linear polysiloxane, linear polycarbosilane, and the like. Among these, linear polysiloxane is more preferable from the viewpoint of raw material availability. .

(Cage type polysiloxane, ladder type polysiloxane)
A cage-type polysiloxane and a ladder-type polysiloxane are one type of compounds having a silsesquioxane structure. The silsesquioxane structure is a structure in which each silicon atom is bonded to three oxygen atoms and each oxygen atom is bonded to two silicon atoms (the number of oxygen atoms is 1.5 with respect to the number of silicon atoms). is there. Specific examples of the cage-type polysiloxane and the ladder-type polysiloxane include those described in, for example, JP-A-2010-78834.

(Resin that is a linear polymer)
The resin that is a linear polymer is not particularly limited as long as it is a resin that is a linear polymer having the above structural unit, but from the viewpoint of coatability, developability, pattern formability, and raw material availability. It is preferable to be selected.
In the resin which is a linear polymer of the present invention, the structural unit represented by the general formula (A), the structural unit represented by the general formula (A-1), and the general formula (A-2) The structural unit represented by formula (B) and the structural unit represented by the general formula (B) preferably constitute the main chain of the resin as the compound (C), respectively, and constitute the main chain of the linear polysiloxane. More preferably.
The content of the structural unit represented by the general formula (A) (that is, the repeating unit) is preferably 5 to 95 mol%, and preferably 10 to 90 mol% with respect to all the repeating units of the resin. Is more preferable. When the structural unit represented by the general formula (A) (that is, the repeating unit) has a (meth) acryloyl group, a (meth) acrylamide group or a thio (meth) acryloyl group as a polymerizable group, in the general formula (A) The content of the structural unit represented is more preferably 5 to 50 mol%, and still more preferably 10 to 45 mol%, based on all repeating units of the resin. The structural unit represented by the general formula (A) (that is, the repeating unit) has a carbon-carbon unsaturated group other than a (meth) acryloyl group, a (meth) acrylamide group and a thio (meth) acryloyl group as a polymerizable group. In this case, the content of the structural unit represented by the general formula (A) is more preferably 40 to 90 mol%, and even more preferably 60 to 90 mol%, based on all the repeating units of the resin. preferable.
The resin which is a linear polymer may or may not contain the structural unit represented by the above general formula (B), but when it is contained, the structural unit represented by the general formula (B) ( That is, the content of the repeating unit) is preferably 5 to 50 mol%, more preferably 10 to 45 mol%, based on all the repeating units of the resin.

  The polymer containing the structural unit represented by the general formula (A) may further contain other structural units other than the above-described structural units. Examples of such a structural unit include a structural unit represented by the following general formula (C).

In general formula (C), R ₂₁ and R ₂₂ each independently represent a single bond or a divalent linking group, or a hydrogen atom or a monovalent substituent. However, R ₂₁ and R ₂₂ do not have an alkali-soluble group or a polymerizable group. When R ₂₁ and R ₂₂ are each independently a single bond or a divalent linking group, the single bond or divalent linking group is linked to another silicon atom of the compound (C).
X ₂₁ represents a single bond or a divalent linking group.

The single bond or divalent linking group, or the hydrogen atom or monovalent substituent represented by R ₂₁ and R ₂₂ is preferably a divalent linking group or a monovalent substituent.
Specific examples and preferred examples of the divalent linking group and monovalent substituent represented by R ₁₁ described above include the divalent linking group and monovalent substituent represented by R ₂₁ and R ₂₂ , respectively. can be mentioned as well, R ₂₁ and R ₂₂ has no alkali-soluble group and a polymerizable group.
The single bond or divalent linking group represented by X ₂₁ is preferably a divalent linking group. Specific examples and preferred examples of the divalent linking group represented by R ₁₁ are the same as the divalent linking group represented by X ₂₁ .

  The resin which is a linear polymer may or may not contain the structural unit represented by the above general formula (C), but when it is contained, the structural unit represented by the general formula (C) ( That is, the content of the repeating unit) is preferably 5 to 95 mol%, more preferably 10 to 90 mol%, based on all the repeating units of the resin.

  The polymer is prepared by modifying a commercially available silicon atom-containing polymer to introduce an alkali-soluble group or a polymerizable group, an organohalosilane corresponding to each monomer constituent unit having an alkali-soluble group or a polymerizable group, and / or Or it is obtained by the method of carrying out the cohydrolysis condensation of the 2 or more types of mixture of organoalkoxysilane.

  Other preferred examples of the compound (C) include a fluorene ring described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, and the like, and an ethylenically polymerizable group. Mention may also be made of compounds having two or more functions, cardo resins, and the like.

  As mentioned above, although each form of the compound (C) was demonstrated, the polystyrene conversion number average molecular weight (Mn) by the gel permeation chromatography (GPC) method of resin as a compound (C) is 400-50,000. Preferably, 600 to 40,000 is more preferable, and 800 to 30,000 is most preferable. It is preferable that the polystyrene conversion weight average molecular weight (Mw) by the gel permeation chromatography (GPC) method of the resin as the compound (C) of the present invention is 1,500 to 200,000, and 2,400 to 150,000. Is more preferable, and 3,000 to 120,000 is most preferable. If the weight average molecular weight and the number average molecular weight are within the above ranges, the resin as the compound (C) of the present invention has good solubility and can be cured without being dissipated during heating. it can. More specifically, if the number average molecular weight is 400 or more, good coatability and curability can be obtained, and if the number average molecular weight is 50,000 or less, good developability is obtained.

When the polymerizable group is an unsaturated group, from the viewpoint of improving photosensitivity, the unsaturated value of the compound (C) of the present invention is preferably 0.5 mmol / g or more, more preferably 0.7 mmol / g or more, 1.0 mmol / g or more is most preferable.
By making the unsaturated value of the compound (C) 0.5 mmol / g or more, that is, by increasing the number of unsaturated double bonds in this resin, photopolymerization and sensitivity are improved. By improving the polymerizability, adhesion to a solid surface such as a support and immobilization of hollow or porous particles contained are also improved. As a result, there are few defects in the hollow or porous particles in the pattern film during development, A pattern having a tapered or rectangular cross-sectional shape tends to be obtained, which is preferable.

  The acid value of the compound (C) of the present invention is preferably 20 to 300 mgKOH / g, more preferably 40 to 200 mgKOH / g, and particularly preferably 50 to 160 mgKOH / g. When the acid value is within this range, the development residue is less likely to remain during pattern formation, and the coating uniformity is further improved.

The compound (C) may be used alone or in combination of two or more. As described above, the compound (C) is a polymerizable compound, and the polymerizable compound is low. A form containing a molecular compound and a resin having a polymerizable group (developable binder resin) is preferable.
In this embodiment, the mass ratio between the low molecular compound and the developing binder resin is not particularly limited, but is preferably 10:90 to 90:10, and more preferably 20:80 to 80:20.

  The compound (C) is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and particularly preferably 15% by mass to 30% by mass with respect to the total solid content of the photosensitive composition.

  Moreover, it is preferable that a compound (C) has a refractive index of 1.55 or less, More preferably, it is 1.50 or less, Most preferably, it is 1.48 or less. Thereby, the refractive index of the pattern obtained can be reduced more reliably.

Specific examples of the compound (C) of the present invention are shown below, but the present invention is not limited to these specific examples. Numbers indicated in each unit representing each unit mole fraction in the resin molecule (where numbers in the side chain of the C-5 and C-31 is, -Si _{(CH 3)} 2 -O- repetition of Represents a number).

[5] (D) Organic solvent The photosensitive composition generally contains an organic solvent. The organic solvent is basically not particularly limited as long as the solubility of each component and the applicability of the photosensitive composition are satisfied, but in particular, considering the solubility, applicability, and safety of the ultraviolet absorber and binder. It is preferable to be selected.

  Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. Butyl lactate, alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), 3-oxy Propionic acid alkyl esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate and the like (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion) Ethyl acid )), 2-oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, 2-methoxypropionic acid) Ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example 2 -Methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2 -Ethyl oxobutanoate, 3-methoxybut And ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol monomethyl ether (PGME: also known as 1-methoxy-2-propanol), propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate (also known as 2-methoxyethyl acetate), ethylene glycol monoethyl ether acetate (also known as 2-ethoxyethyl acetate), diethylene glycol monobutyl acetate, propylene glycol monomethyl ether acetate (PGMEA: aka 1-methoxy-2-acetoxypropane), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones As preferable examples, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and aromatic hydrocarbons include, for example, toluene, xylene, ethylbenzene, and the like. Examples of the organic solvent include alcohols such as isopropanol and aprotic polar solvents such as N-methylpyrrolidone.

  It is also preferable to mix two or more of these organic solvents from the viewpoint of improving the solubility of the ultraviolet absorber (details will be described later) and the alkali-soluble resin, and improving the coated surface. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, methyl ethyl ketone, ethylbenzene, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.

  The content of the organic solvent in the photosensitive composition is preferably such that the total solid concentration of the composition is 5 to 80% by mass, more preferably 5 to 60% by mass, from the viewpoint of applicability. 10-50 mass% is especially preferable.

[6] Additives The photosensitive composition is a surfactant, adhesion promoter, and polymerization as long as the characteristics (heat resistance, mechanical strength, coatability, adhesion, etc.) of the film obtained using the composition are not impaired. You may add additives, such as an inhibitor, a ultraviolet absorber, antioxidant, an aggregation inhibitor, and a sensitizer.

<Surfactant>
Various surfactants may be added to the photosensitive composition from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

In particular, since the photosensitive composition contains a fluorosurfactant, the liquid properties (particularly fluidity) when prepared as a coating solution are further improved, so that the coating thickness is uniform and liquid-saving. Can be improved more.
That is, in the case of forming a film using a coating liquid to which a photosensitive composition containing a fluorosurfactant is applied, by reducing the interfacial tension between the coated surface and the coating liquid, The wettability is improved and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content in this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the photosensitive composition.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (above, manufactured by Asahi Glass Co., Ltd.), Solsperse 20000 (Nippon Rouble) Zole Co., Ltd.).

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, etc. It is.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

  Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by Big Chemie.
Only one type of surfactant may be used, or two or more types may be combined.
The photosensitive composition may or may not contain a surfactant, but when it is contained, the content of the surfactant is 0.001 mass relative to the total solid mass of the photosensitive composition of the present invention. % To 1% by mass, more preferably 0.01% to 0.1% by mass.

<Adhesion promoter>
The photosensitive composition of the present invention may contain any adhesion promoter as long as the object of the present invention is not impaired. Examples of the adhesion promoter include 3-glycidyloxypropyltrimethoxysilane, 1-methacryloxypropylmethyldimethoxysilane, 3-aminoglycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3- Examples include aminopropyltrimethoxysilane. In addition, the compounds described in paragraph No. [0048] of JP-A-2008-243945 are used.
The photosensitive composition of the present invention may or may not contain an adhesion promoter. However, when it is contained, the preferred amount of the adhesion promoter is not particularly limited, but it is usually the total solid content in the composition. Is preferably 10% by mass or less, particularly preferably 0.005 to 5% by mass.

<Polymerization inhibitor>
The photosensitive composition of the present invention may be added with a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the photosensitive composition. As hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2 Examples include '-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt, and the like.
It is preferable that content of a polymerization inhibitor is 0.0005 mass%-5 mass% with respect to the total solid of a photosensitive composition.

<Ultraviolet absorber>
The photosensitive composition of the present invention may contain an ultraviolet absorber.
As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and the like. Examples of benzophenone-based UV absorbers include 2,2′-dihydroxy-4- Methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- And hydroxy-4-octoxybenzophenone. Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3). '-Tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- ( 2'-hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2 -(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzoto Azole, 2- [2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl] benzotriazole and the like.

Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate, and the like. Furthermore, as an example of the triazine ultraviolet absorber, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) ) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) Mono (hydroxyphenyl) triazine compounds such as 1,3,5-triazine and 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-); -Methyl-4-propyloxyphenyl) -6- (4-methylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl-4-hexyloxyphenyl) -6 Bis (hydroxyphenyl) triazine compounds such as (2,4-dimethylphenyl) -1,3,5-triazine; 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-di Butoxyphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4,6-tris [2-hydroxy And tris (hydroxyphenyl) triazine compounds such as -4- (3-butoxy-2-hydroxypropyloxy) phenyl] -1,3,5-triazine.
In the present invention, the various ultraviolet absorbers may be used alone or in combination of two or more.
The photosensitive composition may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is 0.001% by mass or more to 1% by mass of the total solid content of the photosensitive composition. It is preferable that it is mass% or less, and it is more preferable that it is 0.01 mass% or more and 0.1 mass% or less.

As mentioned above, although each component of the photosensitive composition was demonstrated, the solution melt | dissolved in the above organic solvents may be sufficient as a photosensitive composition, and the solid substance which does not contain an organic solvent may be sufficient as it.
The photosensitive composition can be used for various applications typified by a low refractive index material, and the content of each component and the type of additive to be added are determined according to the purpose.
The photosensitive composition is preferably used for forming various films, and particularly preferably used for forming a low refractive index film.

  In the photosensitive composition, the metal content as an impurity is preferably sufficiently small. The metal concentration in the composition can be measured with high sensitivity by the ICP-MS method or the like, and the metal content other than the transition metal in that case is preferably 300 ppm or less, more preferably 100 ppm or less.

  The manufacturing method of a photosensitive composition is not specifically limited, When an organic solvent is included, it can obtain by adding each component of a composition to an organic solvent, and stirring.

  The above composition is preferably used for film formation after removing insolubles, gelled components and the like by filter filtration. The pore size of the filter used at that time is preferably 0.05 to 2.0 μm, more preferably 0.05 to 1.0 μm, and most preferably 0.05 to 0.5 μm. The material of the filter is preferably polytetrafluoroethylene, polyethylene, polypropylene, or nylon, and more preferably polytetrafluoroethylene, polyethylene, or nylon.

[7] Pattern Forming Method The pattern forming method of the present invention includes a step of forming a photosensitive film with a photosensitive composition, a step of exposing the photosensitive film, and a step of developing using a developer containing an organic solvent. The pattern forming method includes: (A) hollow or porous particles, (B) a compound that generates active species upon irradiation with actinic rays or radiation, and (C) the action of the active species. It is a pattern formation method which is a photosensitive composition containing the compound by which the solubility with respect to the developing solution containing an organic solvent reduces.
The present invention also relates to a pattern film obtained by this pattern forming method.
A method for forming a photosensitive film formed from the photosensitive composition used in the pattern forming method of the present invention is not particularly limited. For example, the photosensitive composition is spin-coated, roller-coated, dip-coated, or scanned. After applying to the substrate by any method such as spray method, bar coating method, ink jet method, etc., the solvent is removed by heat treatment as necessary to form a coating film (photosensitive film), and prebaking treatment is performed Can be formed.
Examples of substrates include silicon wafer substrates, SiO ₂ wafer substrates, SiN wafer substrates, glass substrates, substrates on which various metal layers are formed, plastic films, microlenses, and on-chip color filters for image sensors. Examples include a coated substrate.

  As a method of applying to the substrate, a spin coating method, a scanning method, and an ink jet method are preferable. Particularly preferred is a spin coating method. A commercially available apparatus can be used for the spin coating method. For example, a clean track series (manufactured by Tokyo Electron), a D-spin series (manufactured by Dainippon Screen), an SS series or a CS series (manufactured by Tokyo Ohka Kogyo Co., Ltd.) can be preferably used.

  The spin coating conditions may be any rotational speed, but from the viewpoint of in-plane uniformity of the film, a rotational speed of about 1300 rpm is preferable for a 300 mm diameter silicon substrate. In addition, the method for discharging the composition solution may be either dynamic discharge for discharging the composition solution onto a rotating substrate or static discharge for discharging the composition solution onto a stationary substrate. From the viewpoint of performance, dynamic ejection is preferable. In addition, from the viewpoint of suppressing the consumption of the composition, it is also possible to use a method in which only the main solvent of the composition is preliminarily discharged onto the substrate to form a liquid film, and then the composition is discharged from there. it can. The spin coating time is not particularly limited, but is preferably within 180 seconds from the viewpoint of throughput. Further, from the viewpoint of transporting the substrate, it is also preferable to perform processing (edge rinse, back rinse) so as not to leave the film at the edge portion of the substrate.

  Note that the photosensitive composition can be easily cleaned and removed using a known cleaning liquid even when it adheres to, for example, the nozzle of the coating apparatus discharge section, the piping section of the coating apparatus, or the inside of the coating apparatus. In this case, in order to perform more efficient cleaning and removal, it is preferable to use the solvent described above as the solvent contained in the photosensitive composition of the present invention as the cleaning liquid.

JP-A-7-128867, JP-A-7-146562, JP-A-8-278737, JP-A-2000-273370, JP-A-2006-85140, JP-A-2006-291191, The cleaning liquids described in JP 2007-2101 A, JP 2007-2102 A, JP 2007-281523 A and the like can also be suitably used as cleaning liquids for cleaning and removing the photosensitive composition of the present invention. .
As the cleaning liquid, it is preferable to use alkylene glycol monoalkyl ether carboxylate or alkylene glycol monoalkyl ether.
These solvents that can be used as the cleaning liquid may be used alone or in combination of two or more.
When mixing 2 or more types of solvent, the mixed solvent formed by mixing the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group is preferable. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. The mixed solvent is a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), and the ratio is particularly preferably 60/40.
In addition, in order to improve the permeability of the cleaning liquid to the photosensitive composition, the surfactant described above as a surfactant that can be contained in the photosensitive composition may be added to the cleaning liquid.

  The pre-bake processing method is not particularly limited, but generally used hot plate heating, heating method using a furnace, light irradiation heating using a xenon lamp by RTP (Rapid Thermal Processor), etc. are applied. be able to. A heating method using hot plate heating or furnace is preferable. A commercially available apparatus can be preferably used as the hot plate, and a clean track series (manufactured by Tokyo Electron), D-spin series (manufactured by Dainippon Screen), SS series or CS series (manufactured by Tokyo Ohka Kogyo Co., Ltd.) can be preferably used. As the furnace, Cx series (manufactured by Tokyo Electron) and the like can be preferably used. Examples of the prebaking condition include a condition of heating at 60 ° C. to 150 ° C. (preferably 60 ° C. to 120 ° C.) for about 0.5 minutes to 15 minutes using a hot plate or an oven.

The step of exposing the photosensitive film is performed through a mask as necessary.
Examples of actinic rays or radiation that can be applied to this exposure include infrared light, g-rays, h-rays, i-rays, KrF light, ArF light, X-rays, and electron beams. From the viewpoint of exposure amount, sensitivity, and resolution, i-line, KrF light, ArF light, and electron beam are preferable, and from the viewpoint of versatility, i-line and KrF light are most preferable. When using the i-line to the irradiation light is ^preferably irradiated at an exposure dose of ^{100mJ / cm 2 ~10000mJ / cm 2} . When using KrF light, it is preferable to irradiate with an exposure dose of 30 mJ / cm ^{2 to} 300 mJ / cm ² .
In addition, the exposed composition layer can be heated at 70 ° C. to 180 ° C. for about 0.5 minutes to 15 minutes using a hot plate or oven before the next development processing, if necessary.

  Subsequently, the exposed portion of the photosensitive film is developed on the exposed composition layer to obtain a pattern film (development process), and development is performed with a developer (development process). Thereby, a negative pattern (resist pattern) can be formed.

Organic developers that can be used when developing with a developer containing an organic solvent include polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. A developer containing can be used.
Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 3-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, 3-hexanone, Diisobutylketone, methylamylketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate, etc. Can be mentioned.
Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3. -Ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate and the like can be mentioned. In particular, alkyl acetates such as methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, and amyl acetate are preferred.
Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2. -Alcohols such as pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol; glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl Ether, may be mentioned glycol monoethyl ether and methoxymethyl butanol.
Examples of the ether solvent include anisole, dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than the above or water within the range having performance. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.
That is, the content of the organic solvent with respect to the developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less with respect to the total amount of the developer.
In particular, the developer containing an organic solvent is a developer containing at least one solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. preferable.

The vapor pressure of the developer containing the organic solvent is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the developing solution to 5 kPa or less, evaporation of the developing solution on the substrate or in the developing cup is suppressed, temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface is improved. It improves.
Specific examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl Ketone solvents such as isobutyl ketone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxy Esters such as butyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate Agent, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol Alcohol solvents such as n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether Glycol ether solvents such as triethylene glycol monoethyl ether and methoxymethylbutanol , Ether solvents such as tetrahydrofuran, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, amide solvents of N, N-dimethylformamide, aromatic hydrocarbon solvents such as toluene and xylene, octane, decane, etc. And aliphatic hydrocarbon solvents.
Specific examples having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, and methylcyclohexanone. , Ketone solvents such as phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate (3- Ethyl ethoxypropionate), 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate, etc. Solvent, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol, etc. Glycol solvents such as alcohol solvents, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl Glycol ether solvents such as ether and methoxymethylbutanol, N-methyl-2-pyrrolidone, N, N-di Chill acetamide, N, N-dimethylformamide amide solvents, aromatic hydrocarbon solvents such as xylene, octane, aliphatic hydrocarbon solvents decane.

An appropriate amount of a surfactant can be added to the developer as necessary.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, US Pat. No. 5,405,720, etc. The surfactants described in US Pat. Nos. 5,360,692, 5,298,881, 5,296,330, 5,346,098, 5,576,143, 5,294,511, and 5,824,451 can be mentioned. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.
The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

As a developing method using an organic developer, for example, a method in which a substrate is immersed in a tank filled with the developer for a certain period of time (dip method), a developer is raised on the surface of the substrate by surface tension, and is allowed to stand for a certain period of time. Method of developing (paddle method), method of spraying developer on the substrate surface (spray method), and method of continuously discharging developer while scanning the developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (Dynamic dispensing method) can be applied. The development time varies depending on the composition of the photosensitive composition, but is usually about 30 to 120 seconds at 25 ° C.
When the various development methods described above include a step of discharging the developer from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is Preferably it is 2 mL / sec / mm ² or less, More preferably, it is 1.5 mL / sec / mm ² or less, More preferably, it is 1 mL / sec / mm ² or less. Although there is no particular lower limit of the flow rate, 0.2 mL / sec / mm ² or more is preferable in consideration of throughput.
By setting the discharge pressure of the discharged developer to be in the above range, it tends to be able to reduce pattern defects resulting from the development residue after development.
The details of this mechanism are not clear, but perhaps by setting the discharge pressure within the above range, the pressure applied by the developer to the resist film will decrease, and the resist film / resist pattern may be inadvertently cut or collapsed. This is considered to be suppressed.
The developer discharge pressure (mL / sec / mm ² ) is a value at the developing nozzle outlet in the developing device.

  Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.

  Moreover, you may implement the process of stopping image development, after the process of developing, substituting with another solvent.

  It is preferable to include a rinsing step (step of washing with a rinsing solution containing an organic solvent) after development with a developing solution containing an organic solvent.

The rinsing solution used in the rinsing step after development with a developer containing an organic solvent is not particularly limited as long as the pattern is not dissolved, and a solution containing a general organic solvent can be used. As the rinsing liquid, a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is used. It is preferable.
Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent and the ether solvent used as the rinsing liquid include those described above as the organic solvent used in the developer. It is done.
More preferably, after the development, a cleaning step is performed using a rinse solution containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents. Even more preferably, after the development, a washing step is performed using a rinse solution containing an alcohol solvent or an ester solvent. Even more preferably, after the development, a washing step using a rinsing solution containing a monohydric alcohol is performed. Particularly preferably, after the development, a washing step is performed using a rinsing liquid containing a monohydric alcohol having 5 or more carbon atoms. Here, examples of the monohydric alcohol used in the rinsing step after development include linear, branched, and cyclic monohydric alcohols. Specifically, 1-butanol, 2-butanol, 3-methyl- 1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2- Heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and particularly preferable monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4 -Use methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. Rukoto can.

  A plurality of these components may be mixed, or may be used by mixing with an organic solvent other than the above.

The water content in the rinse liquid is preferably less than 10% by mass, more preferably less than 5% by mass, and particularly preferably less than 3% by mass. By setting the water content to less than 10% by mass, good development characteristics can be obtained.
That is, the amount of the organic solvent used in the rinse liquid is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, based on the total amount of the rinse liquid. Most preferably, it is at least 100% by mass.

  The vapor pressure of the rinsing solution used after development with a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and 0.12 kPa or more and 3 kPa or less at 20 ° C. Is most preferred. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

  An appropriate amount of a surfactant can be added to the rinse solution.

  In the rinsing step, the developed wafer is cleaned using a rinsing solution containing the organic solvent. The cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid on the substrate surface (spray method), and the like can be applied. Among them, a cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate.

  In the pattern forming method of the present invention, development with an alkaline developer may be performed after development with a developer containing an organic solvent.

Examples of the alkaline 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, diethylamine, Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, fourth amines such as tetramethylammonium hydroxide and tetraethylammonium hydroxide Alkalinity such as 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, etc., cyclic amines such as quaternary ammonium salts, pyrrole and pihelidine Aqueous solution can be used .
Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.
In particular, a 0.3% mass aqueous solution of tetramethylammonium hydroxide is desirable.

  As a developing method using an alkaline developer, the method described in the developing method using an organic developer can be similarly employed.

  After the alkali development, it is preferable to include a step of washing with a rinse solution.

  As the rinsing liquid in the rinsing treatment, pure water can be used, and an appropriate amount of a surfactant can be added and used.

In addition, the pattern forming method of the present invention preferably includes a heating step (Post Bake) after the rinsing step performed subsequent to the developing step with an organic developer or an alkali developer. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step can be performed by heating the pattern film with a heating device such as a hot plate or oven. In this post-baking, the heating temperature is usually 120 to 250 ° C., preferably 160 to 250 ° C. 230 ° C. The heating time varies depending on the heating means, but is usually about 5 to 30 minutes when heated on a hot plate, and is usually about 30 to 90 minutes when heated in an oven.
Further, in the post-baking, a step baking method in which heating is performed twice or more can be adopted.

After the development process, if necessary, post-heating and / or post-exposure may be performed on the formed pattern film to further accelerate the curing of the pattern film (post-curing process by hardening process).
Thereby, light resistance, climate resistance, and film strength can be improved, and low refractive index properties can also be improved.

  The hardening process means that the pattern film on the substrate is further cured to give the film more solvent resistance and the like. As the method of hardening, it is preferable to perform heat treatment (firing). For example, a polymerization reaction during post-heating of the polymerizable group remaining in the resin can be used. The conditions for the post-heat treatment are preferably 100 to 600 ° C., more preferably 200 to 500 ° C., particularly preferably 200 ° C. to 450 ° C., preferably 1 minute to 3 hours, more preferably 1 minute to 2 hours, Especially preferably, it is the range of 1 minute-1 hour. The post-heating treatment may be performed in several times.

Further, in the present invention, not by heat treatment but by irradiating with high energy rays such as light irradiation and radiation irradiation, the polymer may still cause a polymerization reaction between the remaining polymerizable groups to be hardened. Good. Examples of high energy rays include electron beams, ultraviolet rays, and X-rays, but are not particularly limited to these methods.
The energy when an electron beam is used as the high energy beam is preferably 0.1 to 50 keV, more preferably 0.2 to 30 keV, and particularly preferably 0.5 to 20 keV. The total dose of the electron beam is preferably 0.01 to 5 μC / cm ² , more preferably 0.01 to ² μC / cm ² , and particularly preferably 0.01 to 1 μC / cm ² . The substrate temperature at the time of irradiation with an electron beam is preferably 0 to 500 ° C, more preferably 20 to 450 ° C, and particularly preferably 20 to 400 ° C. The pressure is preferably 0 to 133 kPa, more preferably 0 to 60 kPa, and particularly preferably 0 to 20 kPa.
From the viewpoint of preventing oxidation of the polymer, the atmosphere around the substrate is preferably an inert atmosphere such as Ar, He, or nitrogen. Further, a gas such as oxygen, hydrocarbon, or ammonia may be added for the purpose of reaction with plasma, electromagnetic waves, or chemical species generated by interaction with an electron beam. The electron beam irradiation may be performed a plurality of times. In this case, the electron beam irradiation conditions need not be the same each time, and may be performed under different conditions each time.

Ultraviolet rays may be used as the high energy rays. The irradiation wavelength region when ultraviolet rays are used is preferably 160 to 400 nm, and the output is preferably 0.1 to 2000 mWcm ⁻² immediately above the substrate. The substrate temperature at the time of ultraviolet irradiation is preferably 250 to 450 ° C., more preferably 250 to 400 ° C., and particularly preferably 250 to 350 ° C. From the viewpoint of preventing oxidation of the polymer of the present invention, the atmosphere around the substrate is preferably an inert atmosphere such as Ar, He, or nitrogen. Further, the pressure at that time is preferably 0 to 133 kPa.

  The film may be hardened by performing heat treatment and high energy ray treatment irradiation such as light irradiation and radiation irradiation simultaneously or sequentially.

  As a dry film thickness, a coating film having a thickness of about 0.05 to 1.5 μm can be formed by a single coating and a thickness of about 0.1 to 3 μm can be formed by a second coating.

The application of the pattern forming method of the present invention is not particularly limited, but as described above, it is preferably used for producing a low refractive index film.
Therefore, the present invention also relates to a low refractive index film that is a pattern film obtained by the above-described pattern forming method of the present invention.
Furthermore, the present invention also relates to an optical device having the low refractive index film.
The present invention also relates to a solid-state imaging device including such an optical device.
Hereinafter, such a low refractive index film (for example, an antireflection film) will be described in detail. However, the preferable range of the following various physical properties in the low refractive index film is a preferable range particularly in the application of the low refractive index film, but is not limited to the application.

<Low refractive index film>
The pattern film obtained using the composition described above exhibits excellent low refractive index properties. Specifically, the refractive index (wavelength 633 nm, measurement temperature 25 ° C.) of the pattern film is preferably 1.35 or less, more preferably 1.23-1.34, and 1.25-1 .33 is particularly preferred. Within the above range, it is useful as an antireflection film described later.

<Antireflection film>
As a suitable usage mode of the pattern film obtained by the composition used in the pattern forming method of the present invention described above, an antireflection film may be mentioned. In particular, it is suitable as an antireflection film for optical devices (for example, microlenses for image sensors, plasma display panels, liquid crystal displays, organic electroluminescence, etc.).
The lower the reflectance when used as an antireflection film, the better. Specifically, the specular average reflectance in the wavelength region of 450 to 650 nm is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less. The reflectance is preferably as small as possible, and most preferably 0.
The haze of the antireflection film is preferably 3% or less, more preferably 1% or less, and most preferably 0.5% or less. The reflectance is preferably as small as possible, and most preferably 0.

  When the above-described film is used as a single-layer type antireflection film, if the refractive index of the transparent substrate is nG, the refractive index n of the antireflection film is √nG, that is, 1/2 of the refractive index of the transparent substrate. Preferably it is a power. For example, since the refractive index of optical glass is 1.47 to 1.92 (wavelength 633 nm, measurement temperature 25 ° C.), n of the single-layer antireflection film formed on the optical glass is 1.21 to 1. .38 is preferred. In addition, it is preferable that the film thickness of the antireflection film in that case is 10 nm-10 micrometers.

When the above-described film is used as a multilayer antireflection film, the film is used as a low refractive index layer, and includes, for example, a high refractive index layer, a hard coat layer, and a transparent substrate under the film. be able to. At this time, the high refractive index layer may be formed directly on the substrate without providing the hard coat layer. Further, an intermediate refractive index layer may be further provided between the high refractive index layer and the low refractive index layer, or between the high refractive index layer and the hard coat layer.
Below, each layer in the case of a multilayer type is explained in full detail.

(1) Low refractive index layer
A low refractive index layer is comprised from the pattern film obtained using the composition of this invention as mentioned above. The refractive index and thickness of the low refractive index layer will be described.

(I) Refractive index The refractive index (wavelength 633 nm, measurement temperature 25 ° C.) of the pattern film obtained using the composition of the present invention, that is, the refractive index of the low refractive index film (also referred to as a low refractive index layer) is 1. It is preferable to be 35 or less. The reason for this is that when the low refractive index film has a refractive index of 1.35 or less, the antireflective effect can be reliably exhibited when combined with a high refractive index film (also referred to as a high refractive index layer). Because.
The refractive index of the low refractive index film is more preferably 1.34 or less, and further preferably 1.33 or less. When a plurality of low refractive index films are provided, at least one of them may have a refractive index value within the above-described range.

  Moreover, when providing a low refractive index layer, since the more excellent antireflection effect is acquired, it is preferable to make the refractive index difference between high refractive index layers into 0.05 or more values. Since the difference in refractive index between the low refractive index layer and the high refractive index layer is 0.05 or more, a synergistic effect in these antireflection film layers can be easily obtained, and the antireflection effect can be obtained more reliably. It is easy to be done. Therefore, it is more preferable to set the refractive index difference between the low refractive index layer and the high refractive index layer to a value within the range of 0.1 to 0.8, and within the range of 0.15 to 0.7. More preferably, it is a value.

(Ii) Thickness The thickness of the low refractive index layer is not particularly limited, but is preferably 20 to 300 nm, for example. When the thickness of the low refractive index layer is 20 nm or more, adhesion to the high refractive index film as a base is surely obtained. On the other hand, when the thickness is 300 nm or less, optical interference hardly occurs and the antireflection effect is further improved. It is easy to get reliably. Therefore, the thickness of the low refractive index layer is more preferably 20 to 250 nm, and still more preferably 20 to 200 nm. In order to obtain higher antireflection properties, when a plurality of low refractive index layers are provided to form a multilayer structure, the total thickness may be set to 20 to 300 nm.

(2) High refractive index layer Although it does not restrict | limit especially as a curable composition for forming a high refractive index layer, As a film formation component, an epoxy resin, a phenol resin, a melamine resin, an alkyd system It is preferable to include one kind or a combination of two or more kinds of resin, cyanate resin, acrylic resin, polyester resin, urethane resin, siloxane resin and the like. With these resins, a strong thin film can be formed as the high refractive index layer, and as a result, the scratch resistance of the antireflection film can be remarkably improved.
However, the refractive index of these resins alone is usually 1.45 to 1.62, which may not be sufficient to obtain high antireflection performance. Therefore, it is preferable to make refractive index 1.70-2.20 by mix | blending a high refractive index inorganic particle, for example, metal oxide particle. Moreover, as a hardening form, although the curable composition which can be thermosetting, ultraviolet curing, and electron beam curing can be used, the ultraviolet curable composition with favorable productivity is used more suitably.

  The thickness of the high refractive index layer is not particularly limited, but is preferably 20 to 30,000 nm, for example. When the thickness of the high refractive index layer is 20 nm or more, when combined with the low refractive index layer, the antireflection effect and the adhesion to the substrate can be more reliably obtained, while the thickness is 30,000 nm or less. In addition, optical interference is unlikely to occur, and the antireflection effect is easily obtained more reliably. Therefore, the thickness of the high refractive index layer is more preferably 20 to 1,000 nm, and further preferably 50 to 500 nm. In order to obtain higher antireflection properties, when a plurality of high refractive index layers are provided to form a multilayer structure, the total thickness may be set to 20 to 30,000 nm. In addition, when providing a hard-coat layer between a high refractive index layer and a board | substrate, the thickness of a high refractive index layer can be 20-300 nm.

(3) Hard coat layer The constituent material of the hard coat layer used in the antireflection film of the present invention is not particularly limited. Examples of such a material include one kind of siloxane resin, acrylic resin, melamine resin, epoxy resin, or a combination of two or more kinds.

  Moreover, although it does not restrict | limit especially also about the thickness of a hard-coat layer, it is preferable to set it as 1-50 micrometers, and it is more preferable to set it as 5-10 micrometers. When the thickness of the hard coat layer is 1 μm or more, the adhesion of the antireflection film to the substrate can be more reliably improved. On the other hand, when the thickness is 50 μm or less, it can be easily formed uniformly.

(4) Substrate The type of the substrate used for the low refractive index film of the present invention is not particularly limited. For example, glass, polycarbonate resin, polyester resin, acrylic resin, triacetyl cellulose resin (TAC), etc. And a transparent substrate and a silicon wafer. By using an antireflection film including these substrates, it is excellent in the field of application of a wide range of antireflection films such as a lens part of a camera, a screen display part of a television (CRT), a color filter or a photographing element in a liquid crystal display device. An antireflection effect can be obtained.

  The pattern film obtained by using the composition used in the pattern forming method of the present invention can also be used as a surface protective film and a retardation film for optical devices (for example, microlenses).

  The composition used in the pattern forming method of the present invention can be suitably used particularly as a coating application for microlenses (herein, the concept of microlens includes the concept of microlens array).

  The pattern film obtained from the pattern forming method of the present invention is formed using the above photosensitive composition, and has a low refractive index, a small amount of development residue, and is formed with high resolution. Liquid crystal display elements such as liquid crystal televisions, mobile phones and projectors, imaging optical systems for on-chip color filters such as facsimiles, electronic copiers, solid-state image sensors, and optical fiber connectors, etc. It is extremely useful as a film to be formed.

  In particular, by forming the pattern film of the present invention on the surface of the microlens using the pattern forming method of the present invention, a high-definition microlens coated with the film having the above characteristics can be easily produced with a high product yield. Can be formed.

  EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited by these examples. In addition, Examples 1-3, 5-10, 12, 19, 22, 24-30, and 32 are reference examples.

<Preparation of photosensitive composition>
The components shown in Tables 1 to 3 below were dissolved in the solvents shown in Tables 1 to 3 below, and filtered through a polytetrafluoroethylene filter having a pore size of 0.2 μm. A sex composition was prepared.
The symbols in compounds (B) and (C) in Tables 1 to 3 correspond to those described above as specific examples of each component.

  The following commercially available products were used as the hollow or porous particles.

Snowtex MIBK-SD-L: 30 mass% dispersion of porous silica manufactured by Nissan Chemical Co., Ltd. Snowtex MIBK-ST: 20 mass% dispersion of porous silica manufactured by Nissan Chemical Co., Ltd. SILINUX SP-PN (b) : Hollow silica powder through rear 2320 manufactured by Nittetsu Mining Co., Ltd. 20% by weight dispersion silica through rear 1110 of hollow silica manufactured by JGC Catalysts & Chemicals Inc. 20% dispersion PL-1-IPA of hollow silica manufactured by JGC Catalysts & Chemicals Co., Ltd. : 12.5 mass% dispersion of porous silica made by Fuso Chemical Co., Ltd. PL-1-TOL: 40 mass% dispersion of porous silica made by Fuso Chemical Co., Ltd. PL-2L-PGME: Porous made by Fuso Chemical Co., Ltd. 20% by mass dispersion of silica PL-2L-MEK: 20% by mass dispersion of porous silica manufactured by Fuso Chemical Co., Ltd. AERODIS G1220: Porous silica manufactured by EVONIK 20 mass% dispersion of mosquito AERODISP 1030: 20 mass% dispersion of porous silica manufactured by EVONIK, Inc .: 20 mass% dispersion of hollow silica, manufactured by JGC Catalysts & Chemicals

  The following commercially available products were used as the particle dispersant.

EMULSOGEN COL-020: alkyl ether carboxylic acid made by Clariant Disperbyk-101: polyamide amine phosphate perex made by BYK Chemie SS-L: sodium alkyl diphenyl ether disulfonate made by Kao Corporation

<Preparation of low refractive index pattern film>
The photosensitive composition obtained above was applied onto a silicon wafer by spin coating, and then heated on a hot plate at 100 ° C. for 2 minutes to obtain a photosensitive film having a thickness of 0.3 μm.
Next, using the i-line stepper FPA-3000i5 + (manufactured by Canon Inc.), the obtained photosensitive film is a dot array having different wavelengths from 0.5 micron square to 100 micron square at a wavelength of 365 nm. Exposed through a pattern mask.
The exposed photosensitive film was subjected to paddle development at 23 ° C. for 60 seconds using the developer shown in Table 4 below. Then, it rinsed using the rinse liquid shown in following Table 4 with a spin shower, and also water-washed with the pure water, and obtained the transparent pattern with a film thickness of 0.3 micrometer.

<Resolution and residue evaluation>
The obtained transparent pattern was observed 30000 times from the top of the silicon wafer using a length measuring SEM (S-7800H, manufactured by Hitachi, Ltd.). The minimum size of the obtained dot pattern is shown in Table 5 as the resolution. A lower numerical value of this minimum size means higher resolution.
Further, Table 5 shows the case where the residue was observed around the pattern as x and the case where the residue was not observed as ◯.

<Measurement of refractive index of low refractive index pattern film>
The photosensitive resin composition obtained above was applied onto a silicon wafer, and then heated at 100 ° C. for 2 minutes on a hot plate to obtain a transparent film. The value measured at 25 ° C. at a wavelength of 633 nm in this transparent film was taken as the refractive index using an ellipsometer (VASE) manufactured by JA Woollam Japan.
The respective results are shown in Table 5.

From the results of Table 5, it was found that when the photosensitive composition of the present invention was used, a pattern having a low refractive index and a small amount of development residue could be formed with high resolution.
On the other hand, Comparative Example 2 which does not contain a compound corresponding to the compound (C) of the present invention could not be resolved (pattern formation) (in Table 5, the residue of Comparative Example 2 could not be measured because the pattern could not be formed). Not.)

Claims (22)

Photosensitivity containing (A) hollow or porous particles, (B) a compound that generates active species upon irradiation with actinic rays or radiation, and (C ′) a polymerizable compound having an unsaturated value of 5.35 mmol / g or more. a composition,
The photosensitive composition whose content of the said hollow or porous particle (A) with respect to the total solid of the said photosensitive composition is 76 mass%-95 mass% .   Photosensitivity containing (A) hollow or porous particles, (B) a compound that generates active species upon irradiation with actinic rays or radiation, and (C ′) a polymerizable compound having an unsaturated value of 5.35 mmol / g or more. A composition comprising:
  The photosensitive composition whose said compound (C ') is a compound which has a structural unit represented by the following general formula (A).

  In general formula (A), R ₁₁ Represents a single bond or a divalent linking group, or a monovalent substituent. R ₁₁ Is a single bond or a divalent linking group, the single bond or divalent linking group is linked to another silicon atom of the compound (C ′).
  X ₁₁ Represents a single bond or a divalent linking group.
  R _P Represents a monovalent group containing a polymerizable group. The photosensitive composition of Claim 2 whose compound which has a structural unit represented by the said general formula (A) is resin, and contains the silicon atom in the principal chain of resin. In the general formula (A), X ₁₁ represents a single bond, or an oxygen atom, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, or represent a combination thereof, the photosensitive composition according to claim 2 or 3 . In the general formula (A), R ₁₁ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or an alkoxy group, photosensitive composition according to any one of claims 2-4. The photosensitive composition of Claim 1 in which the said polymeric compound contains the low molecular compound of molecular weight 2000 or less. The photosensitive composition of Claim 1 in which the said polymeric compound contains resin which has a polymeric group. The photosensitive composition of Claim 7 in which the said resin has a radical or cationically polymerizable repeating unit. The photosensitive composition of Claim 8 whose said radical or cation polymerizable repeating unit is a repeating unit represented by either of following General formula (1)-(3).

In the general formulas (1) to (3), A ²¹ , A ²² and A ²³ each independently represents an oxygen atom, a sulfur atom or —N (R ⁴¹ ) —, and R ⁴¹ represents a hydrogen atom or an alkyl group. Represent.
G ²¹ , G ²² and G ²³ each independently represent a divalent linking group.
X ²¹ and Z ²¹ each independently represent an oxygen atom, a sulfur atom or —N (R ⁴² ) —, and R ⁴² represents a hydrogen atom or an alkyl group.
Y ²¹ represents a single bond, an oxygen atom, a sulfur atom, a phenylene group, or —N (R ⁴³ ) —, and R ⁴³ represents a hydrogen atom or an alkyl group.
R ^{21 to} R ⁴⁰ each independently represent a hydrogen atom or a monovalent substituent.   The photosensitive composition of any one of Claims 2-5 in which the said polymeric compound contains the low molecular weight compound of molecular weight 2000 or less.   Photosensitivity containing (A) hollow or porous particles, (B) a compound that generates active species upon irradiation with actinic rays or radiation, and (C ′) a polymerizable compound having an unsaturated value of 5.35 mmol / g or more. A composition comprising:
  The photosensitive composition whose said compound (C ') is a compound represented by either of following formula (C-13)-(C-18), (C-20), and (C-21).

The content of the hollow or porous particles (A) with respect to the total solid content of the photosensitive composition is 76 mass% to 95 mass%, and any one of claims 2 to 5, 10 and 11. Photosensitive composition. The photosensitive composition of any one of Claims 1-12 whose refractive index of the said hollow or porous particle | grain is 1.10-1.40. The photosensitive composition according to any one of claims 1 to 13 for use in coating applications of the microlenses. Pattern film obtained by photosensitive composition according to any one of claims 1-14. A low refractive index film which is the pattern film according to claim 15 . An optical device having the low refractive index film according to claim 16 . A solid-state imaging device comprising the optical device according to claim 17 .   Photosensitivity containing (A) hollow or porous particles, (B) a compound that generates active species upon irradiation with actinic rays or radiation, and (C ′) a polymerizable compound having an unsaturated value of 5.35 mmol / g or more. Pattern film obtained by the composition.   A low refractive index film, which is the pattern film according to claim 19.   An optical device having the low refractive index film according to claim 20.   A solid-state imaging device comprising the optical device according to claim 21.