JP2013254047A - Radiation-sensitive composition, color filter, and method of manufacturing color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-sensitive composition with little residue, excellent dimensional stability, and little change in the line width after a post exposure time delay.SOLUTION: The radiation-sensitive composition contains polymers, polymerizable compounds, and polymerization initiators. The polymers include a polymer obtained by polymerizing monomer components including a compound represented by a specified general formula (ED). The polymerizable compounds include a (meth)acrylate compound which has an acid group and two or more functional groups. (In the general formula (ED), Rand Reach represent a hydrogen atom or a C1-C25 hydrocarbon group which may have a substituent.)

Description

  The present invention relates to a radiation-sensitive composition, a color filter formed using the same, and a method for producing a color filter. The present invention also relates to a solid-state imaging device (in particular, a CMOS sensor or an organic CMOS sensor), a liquid crystal display device, or an organic EL display device having such a color filter.

  Conventionally, a composition for a colored layer of a color filter used for an image sensor or the like has been studied. For example, in Patent Documents 1 and 2, improvement of the rectangularity of the pattern and reduction of the residue are studied. On the other hand, Patent Document 3 discusses improvements in resist solvent resolubility, surface smoothness, and background contamination.

JP 2010-49029 A JP 2010-78729 A JP 2006-161035 A

Here, demands for color filters are becoming stricter, and there is a tendency for further reduction of residues and improvement of dimensional stability.
Further, not only the exposure / development process is performed immediately after the radiation-sensitive composition is prepared, but also the exposure / development may be performed after a lapse of time. In this case, when this inventor examined, it turned out that it exists in the tendency which produces line width thickening.
An object of the present invention is to provide a radiation-sensitive composition that has little residue, excellent dimensional stability, and little change in line width after leaving. .

（一般式（ＥＤ）中、Ｒ¹およびＲ²は、それぞれ、水素原子または置換基を有していてもよい炭素数１〜２５の炭化水素基を表す。）
＜２＞重合体の合計量に対する、酸基を有し、かつ、２官能以上の（メタ）アクリレート化合物の割合（酸基を有し、かつ、２官能以上の（メタ）アクリレート化合物／全重合体×１００）が１〜５０質量％の範囲である、＜１＞に記載の感放射線性組成物。
＜３＞前記重合性化合物として、さらに、酸基を有し、かつ、２官能以上の（メタ）アクリレート化合物以外の重合性化合物を含む、＜１＞または＜２＞に記載の感放射線性組成物。
＜４＞前記重合性化合物のうち、酸基を有し、かつ、２官能以上の（メタ）アクリレート化合物の割合が、１〜５０質量％である、＜３＞に記載の感放射線性組成物。
＜５＞紫外線吸収剤、溶剤、密着改良剤、重合禁止剤および界面活性剤から選択される、少なくとも１種を含む、＜１＞〜＜４＞のいずれかに記載の感放射線性組成物。
＜６＞＜１＞〜＜５＞のいずれかに記載の感放射線性組成物を硬化してなる硬化膜。
＜７＞＜１＞〜＜５＞のいずれかに記載の感放射線性組成物を硬化してなる着色層を有するカラーフィルタ。
＜８＞（１）＜１＞〜＜５＞のいずれかに記載の感放射線性組成物を基板上に適用する工程、
（２）適用された感放射線性組成物を露光する工程、
（３）露光した感放射線性組成物を現像する工程、および、
（４）現像した後の感放射線性組成物を熱硬化するポストベーク工程、を含むことを特徴とする硬化膜の製造方法。
＜９＞（１）＜１＞〜＜５＞のいずれかに記載の感放射線性組成物を基板上に適用する工程、
（２）適用された感放射線性組成物を露光する工程、
（３）露光した感放射線性組成物を現像する工程、および、
（４）現像した後の感放射線性組成物を熱硬化するポストベーク工程、を含むことを特徴とするカラーフィルタの製造方法。
＜１０＞＜７＞に記載のカラーフィルタまたは＜９＞に記載の製造方法により製造されたカラーフィルタを有する固体撮像素子、液晶表示装置または有機ＥＬ表示装置。 Under such circumstances, the inventors have studied and found that the above-described problems can be solved by using a specific polymer and a polymerizable compound in combination. In the present invention, by using a specific polymer and a polymerizable compound in combination, it becomes possible to improve the development speed of the composition, and as a result, it has succeeded in reducing residue and improving dimensional stability. . Furthermore, it becomes possible to suppress the phase separation in the composition, and succeeded in reducing the line width thickening after leaving.
Specifically, the above problem has been solved by the following <1>, preferably by <2> to <10>.
<1> A polymer, a polymerizable compound and a polymerization initiator are included, and the polymer includes a polymer obtained by polymerizing a monomer component including a compound represented by the following general formula (ED), The radiation sensitive composition which has an acid group as a polymeric compound, and contains the (meth) acrylate compound more than bifunctional.

(In General Formula (ED), R ¹ and R ² each represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)
<2> Ratio of (meth) acrylate compound having an acid group and having two or more functional groups with respect to the total amount of the polymer (having an acid group and having two or more functional (meth) acrylate compounds / total weight) <1> The radiation-sensitive composition according to <1>, wherein the combination x 100) is in the range of 1 to 50% by mass.
<3> The radiation-sensitive composition according to <1> or <2>, further comprising a polymerizable compound other than a bifunctional or higher-functional (meth) acrylate compound as the polymerizable compound. object.
<4> The radiation-sensitive composition according to <3>, wherein the polymerizable compound has an acid group and a proportion of a bifunctional or higher-functional (meth) acrylate compound is 1 to 50% by mass. .
<5> The radiation-sensitive composition according to any one of <1> to <4>, including at least one selected from an ultraviolet absorber, a solvent, an adhesion improver, a polymerization inhibitor, and a surfactant.
<6> A cured film obtained by curing the radiation-sensitive composition according to any one of <1> to <5>.
<7> A color filter having a colored layer formed by curing the radiation-sensitive composition according to any one of <1> to <5>.
<8> (1) A step of applying the radiation-sensitive composition according to any one of <1> to <5> on a substrate,
(2) a step of exposing the applied radiation-sensitive composition;
(3) a step of developing the exposed radiation-sensitive composition, and
(4) A method for producing a cured film, comprising a post-baking step of thermosetting the radiation-sensitive composition after development.
<9> (1) A step of applying the radiation-sensitive composition according to any one of <1> to <5> on a substrate,
(2) a step of exposing the applied radiation-sensitive composition;
(3) a step of developing the exposed radiation-sensitive composition, and
(4) A method for producing a color filter, comprising a post-baking step of thermosetting the radiation-sensitive composition after development.
<10> A solid-state imaging device, a liquid crystal display device, or an organic EL display device having the color filter according to <7> or the color filter manufactured by the manufacturing method according to <9>.

  According to the present invention, it has become possible to provide a radiation-sensitive composition with little residue, excellent dimensional stability, and little change in line width after leaving.

FIG. 1 is a schematic cross-sectional view showing the configuration of a multilayer imaging device (organic CMOS). FIG. 2 is a diagram illustrating an example of the entire configuration including peripheral circuits of the image sensor illustrated in FIG.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl. In the present specification, “monomer” and “polymerizable compound” are synonymous. The monomer in the present invention is distinguished from an oligomer and a polymer and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what 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).
Moreover, in this specification, a viscosity value points out the value in 25 degreeC.

 Radiation-sensitive composition of the present invention (hereinafter sometimes referred to as “composition of the present invention”), cured film, color filter, solid-state imaging device (for example, CMOS sensor, organic CMOS sensor) liquid crystal display device, organic EL display An apparatus, a manufacturing method of a cured film, a solid-state imaging device, a liquid crystal display device or an organic EL display device will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

（一般式（ＥＤ）中、Ｒ¹およびＲ²は、それぞれ、水素原子または置換基を有していてもよい炭素数１〜２５の炭化水素基を表す。）
以下、これらの詳細について説明する。 The composition of the present invention contains a polymer, a polymerizable compound and a polymerization initiator, and a polymer obtained by polymerizing a monomer component containing a compound represented by the following general formula (ED) as the polymer. And the polymerizable compound includes an acid group and a bifunctional or higher functional (meth) acrylate compound.

(In General Formula (ED), R ¹ and R ² each represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)
Details of these will be described below.

（一般式（ＥＤ）中、Ｒ¹およびＲ²は、それぞれ、水素原子または置換基を有していてもよい炭素数１〜２５の炭化水素基を表す。）
一般式（ＥＤ）で示される化合物（以下「エーテルダイマー」と称することもある。）を含む単量体成分を重合してなる重合体を配合することにより、本発明の組成物は、耐熱性とともに透明性にも極めて優れた硬化塗膜を形成しうる。前記エーテルダイマーを示す前記一般式（ＥＤ）中、Ｒ¹またはＲ²で表される置換基を有していてもよい炭素数１〜２５の炭化水素基としては、特に制限はないが、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、ｔ−アミル基、ステアリル基、ラウリル基、２−エチルヘキシル基等の直鎖状または分岐状のアルキル基；フェニル等のアリール基；シクロヘキシル基、ｔ−ブチルシクロヘキシル基、ジシクロペンタジエニル基、トリシクロデカニル基、イソボルニル基、アダマンチル基、２−メチル−２−アダマンチル基等の脂環式基；１−メトキシエチル基、１−エトキシエチル基等のアルコキシで置換されたアルキル基；ベンジル等のアリール基で置換されたアルキル基；等が挙げられる。これらの中でも特に、メチル基、エチル基、シクロヘキシル基、ベンジル基等のような酸や熱で脱離しにくい１級または２級炭素の置換基が耐熱性の点で好ましい。 <Polymer>
The composition of this invention contains the polymer formed by superposing | polymerizing the monomer component containing the compound represented by the following general formula (ED).

(In General Formula (ED), R ¹ and R ² each represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)
By blending a polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) (hereinafter sometimes referred to as “ether dimer”), the composition of the present invention has heat resistance. At the same time, a cured coating film having excellent transparency can be formed. In the general formula (ED) showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ or R ² is not particularly limited. Linear or branched, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, t-amyl group, stearyl group, lauryl group, 2-ethylhexyl group Alkyl group; aryl group such as phenyl; fat such as cyclohexyl group, t-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, 2-methyl-2-adamantyl group A cyclic group; an alkyl group substituted with an alkoxy group such as a 1-methoxyethyl group and a 1-ethoxyethyl group; an alkyl group substituted with an aryl group such as benzyl; Etc. Among these, a primary or secondary carbon substituent 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.

 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-propenoate, 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-butylcyclohexyl) 2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 '-[oxybis (Methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, and the like. 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 structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

  In this invention, it is preferable that the structural unit derived from an ether dimer is 1-50 mol% of the whole, and it is more preferable that it is 1-20 mol%.

Other monomers may be copolymerized with the ether dimer.
Other monomers that can be copolymerized with the ether dimer include, for example, a monomer for introducing an acid group, a monomer for introducing a radical polymerizable double bond, and an epoxy group. Monomers and other copolymerizable monomers other than these may be mentioned. Only 1 type may be used for such a monomer and it may use 2 or more types.

Examples of the monomer for introducing an acid group include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid, monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, maleic anhydride, and anhydride. And monomers having a carboxylic anhydride group such as itaconic acid. Among these, (meth) acrylic acid is particularly preferable.
The monomer for introducing an acid group may be a monomer that can give an acid group after polymerization, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, Examples thereof include a monomer having an epoxy group such as glycidyl (meth) acrylate, and a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate. When using a monomer for introducing a radical polymerizable double bond, when using a monomer capable of imparting an acid group after polymerization, it is necessary to perform a treatment for imparting an acid group after polymerization. The treatment for adding an acid group after polymerization varies depending on the type of monomer, and examples thereof include the following treatment. In the case of using a monomer having a hydroxyl group, for example, a treatment of adding an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride or the like can be mentioned. In the case of using a monomer having an epoxy group, for example, a compound having an amino group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol is added, or, for example, (meth) acrylic For example, a treatment of adding an acid anhydride such as succinic acid anhydride, tetrahydrophthalic acid anhydride, maleic acid anhydride to the hydroxyl group generated after adding an acid such as an acid can be mentioned. In the case of using a monomer having an isocyanate group, for example, a treatment of adding a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid can be mentioned.

  When the polymer formed by polymerizing the monomer component containing the compound represented by the general formula (ED) contains a monomer for introducing an acid group, the content ratio is not particularly limited, In a monomer component, 5-70 mass% is preferable, More preferably, it is 10-60 mass%.

  Examples of the monomer for introducing a radical polymerizable double bond include, for example, monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride Monomers having a group; monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether; . When using a monomer for introducing a radical polymerizable double bond, it is necessary to perform a treatment for imparting a radical polymerizable double bond after polymerization. The treatment for imparting a radical polymerizable double bond after polymerization differs depending on the type of monomer that can impart a radical polymerizable double bond to be used, and examples thereof include the following treatment. If a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid is used, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p- ) Treatment of adding a compound having an epoxy group such as vinylbenzyl glycidyl ether and a radically polymerizable double bond. In the case of using a monomer having a carboxylic anhydride group such as maleic anhydride or itaconic anhydride, a treatment for adding a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth) acrylate Is mentioned. If a monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzylglycidyl ether is used, (meth) The process which adds the compound which has acid groups, such as acrylic acid, and a radically polymerizable double bond is mentioned.

  When the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) contains a monomer for introducing a radical polymerizable double bond, the content ratio is particularly limited. Although not, 5-70 mass% is preferable in all the monomer components, More preferably, it is 10-60 mass%.

Examples of the monomer for introducing an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. Can be mentioned.
When the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) contains a monomer for introducing an epoxy group, the content ratio is not particularly limited, In a monomer component, 5-70 mass% is preferable, More preferably, it is 10-60 mass%.

  Examples of other copolymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate n. -Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2- (meth) acrylic acid 2- (Meth) acrylic acid esters such as hydroxyethyl; aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; butadiene, isoprene and the like Butadiene or substituted butadiene compounds; ethylene, propylene, vinyl chloride Ethylene or substituted ethylene compound such as acrylonitrile, vinyl esters such as vinyl acetate; and the like. Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance.

  When the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) contains another copolymerizable monomer, the content ratio is not particularly limited, but is 95% by mass. The following is preferable, and it is more preferable that it is 85 mass% or less.

The weight average molecular weight of the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) is not particularly limited, but is formed by the viscosity of the colored radiation-sensitive composition and the composition. From the viewpoint of the heat resistance of the coating film, it is preferably 2000 to 200000, more preferably 5000 to 100000, and still more preferably 5000 to 20000.
Moreover, when the polymer formed by polymerizing the monomer component containing the compound represented by the general formula (ED) has an acid group, the acid value is preferably 30 to 500 mgKOH / g, more preferably 50. It should be ˜400 mg KOH / g.

A polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) can be easily obtained by polymerizing at least the above-mentioned monomer essentially containing an ether dimer. . At this time, the cyclization reaction of the ether dimer proceeds simultaneously with the polymerization to form a tetrahydropyran ring structure.
The polymerization method applied to the synthesis of the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) is not particularly limited, and various conventionally known polymerization methods can be adopted. However, it is particularly preferable to use a solution polymerization method. Specifically, for example, in accordance with the method for synthesizing the polymer (a) described in JP-A-204-300204, a polymer formed by polymerizing a monomer component containing a compound represented by the general formula (ED) Can combine

  Hereinafter, although the exemplary compound of the polymer formed by superposing | polymerizing the monomer component containing the compound represented by general formula (ED) is shown, this invention is not limited to these. The composition ratio of the exemplary compounds shown below is mol%.

本発明では特に、ジメチル−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート（以下「ＤＭ」と称する）、ベンジルメタクリレート（以下「ＢｚＭＡ」と称する）、メタクリル酸メチル（以下「ＭＭＡ」と称する）、メタクリル酸（以下「ＭＡＡ」と称する）、グリシジルメタクリレート（以下「ＧＭＡ」と称する）を共重合させた重合体が好ましい。特に、ＤＭ：ＢｚＭＡ：ＭＭＡ：ＭＡＡ：ＧＭＡのモル比が５〜１５：４０〜５０：５〜１５：５〜１５：２０〜３０であることが好ましい。本発明で用いる共重合体を構成する成分の９５質量％以上がこれらの成分であることが好ましい。また、かかる重合体の重量平均分子量は９０００〜２００００であることが好ましい。
本発明で用いる重合体は、重量平均分子量（ＧＰＣ法で測定されたポリスチレン換算値）が１０００〜２×１０⁵であることが好ましく、２０００〜１×１０⁵であることがより好ましく、５０００〜５×１０⁴であることがさらに好ましい。

In the present invention, in particular, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate (hereinafter referred to as “DM”), benzyl methacrylate (hereinafter referred to as “BzMA”), methyl methacrylate (hereinafter referred to as “MMA”). ), Methacrylic acid (hereinafter referred to as “MAA”), and glycidyl methacrylate (hereinafter referred to as “GMA”). In particular, the molar ratio of DM: BzMA: MMA: MAA: GMA is preferably 5-15: 40-50: 5-15: 5-15: 20-30. It is preferable that 95% by mass or more of the components constituting the copolymer used in the present invention is these components. Moreover, it is preferable that the weight average molecular weights of this polymer are 9000-20000.
The polymer used in the present invention preferably has a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 ⁵ , more preferably 2000 to 1 × 10 ⁵ , and 5000 to More preferably, it is 5 × 10 ⁴ .

The composition of the present invention preferably contains a polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) in a proportion of 50% by mass or more of the total polymer component, It is preferably contained in a proportion of not less than mass%, more preferably not less than 95 mass%. In particular, the composition of the present invention is preferably a polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) in which substantially all the polymers are represented.
The composition of the present invention may contain only one type of the above polymer or two or more types. When two or more types are included, the total amount is preferably within the above range.

  The composition of the present invention may contain a polymer other than the above-mentioned polymer (hereinafter sometimes referred to as “other polymer”). As the other polymer, an alkali-soluble resin (hereinafter sometimes referred to as “other alkali-soluble resin”) is preferable. Other alkali-soluble resins are not particularly limited as long as they are alkali-soluble, but are preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. From the viewpoint of development control, acrylic resins and acrylamide resins are preferable. Resins and acrylic / acrylamide copolymer resins are preferred.
Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, but are soluble in a solvent and can be developed with a weak alkaline aqueous solution. Of these, (meth) acrylic acid is particularly preferred. These acid groups may be used alone or in combination of two or more.
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 order to introduce an acid group into an alkali-soluble binder, 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”) .) May be polymerized 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.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and experimental conditions are determined. It can also be done.

  As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenolic resins such as novolak resins, etc., acid cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to polymers having a hydroxyl group. Can be mentioned. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macro Examples of N-substituted maleimide monomers described in JP-A-10-300922 such as monomers and polymethylmethacrylate macromonomers include N-phenylmaleimide and N-cyclohexylmaleimide. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

In the present invention, an alkali-soluble phenol resin can also be preferably used. Examples of the alkali-soluble phenol resin include novolak resins and vinyl polymers.
Examples of the novolac resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A.
Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, and benzaldehyde.
The said phenols and aldehydes can be used individually or in combination of 2 or more types.

  Specific examples of the novolak resin include, for example, a condensation product of metacresol, paracresol or a mixture thereof and formalin.

  The novolak resin may be adjusted in molecular weight distribution by means of fractionation or the like. Moreover, you may mix the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C and bisphenol A, with the said novolak resin.

  Moreover, in order to improve the crosslinking efficiency of the composition in the present invention, an alkali-soluble resin having a polymerizable group may be used. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. Examples of the above-mentioned polymer containing a polymerizable group include: Dynal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd., manufactured by), Biscote R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industry Co., Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), and the like. As an alkali-soluble resin containing these polymerizable groups, an isocyanate group and an OH group are reacted in advance to leave one unreacted isocyanate group and a compound containing a (meth) acryloyl group and an acrylic resin containing a carboxyl group; Urethane-modified polymerizable double bond-containing acrylic resin obtained by the above reaction, unsaturated group-containing acrylic obtained by reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule Resin, acid pendant type epoxy acrylate resin, OH group-containing acrylic resin and polymerizable double bond-containing acrylic resin obtained by reacting a polymerizable double bond, OH group-containing acrylic resin and isocyanate Resin obtained by reacting a compound having a polymerizable group, Japanese Patent Application Laid-Open No. 2002-229207 And a resin obtained by performing a basic treatment on a resin having an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position described in JP-A-2003-335814 Etc. are preferable.

Moreover, it is also preferable to use (a) polyimide, polybenzoxazole or a precursor thereof as the alkali-soluble resin. Polyimide and polybenzoxazole are resins having a cyclic structure of an imide ring or an oxazole ring in the main chain structure. The polyimide precursor and the polybenzoxazole precursor are resins having an amide bond in the main chain, and become the aforementioned polyimide or polybenzoxazole by dehydrating and ring-closing by heat treatment or chemical treatment. By containing these resins, a composition having excellent insulating properties can be obtained. Examples of the polyimide precursor include polyamic acid, polyamic acid ester, polyamic acid amide, and polyisoimide. Examples of the polybenzoxazole precursor include polyhydroxyamide, polyaminoamide, polyamide, and polyamideimide. In any case, the number of repeating structural units is preferably 10 to 100,000. Two or more of these may be contained, or a copolymer having two or more of these structural units may be contained. In the case of curing by heat treatment at a low temperature of 250 ° C. or lower, polyimide is more preferable from the viewpoint of chemical resistance.
Polyimide is generally obtained by dehydrating and ring-closing polyamic acid, which is one of polyimide precursors obtained by reacting tetracarboxylic dianhydride and diamine, by heating or chemical treatment such as acid or base. It has a carboxylic acid residue and a diamine residue.
In the present invention, the polyimide preferably has a structural unit represented by the following general formula (3). Two or more of these may be contained, or a copolymer with another structural unit may be used.

上記一般式（３）中、Ｒ¹−（Ｒ³）_pはテトラカルボン酸残基を表す。Ｒ¹は４〜１０価の有機基であり、芳香族環または環状脂肪族基を有する炭素原子数５〜４０の４〜１０価の有機基が好ましい。
テトラカルボン酸残基を構成する酸二無水物としては、例えば、ピロメリット酸二無水物、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物、２，２’，３，３’−ビフェニルテトラカルボン酸二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、２，２’，３，３’−ベンゾフェノンテトラカルボン酸二無水物、２，２−ビス（３，４−ジカルボキシフェニル）プロパン二無水物、２，２−ビス（２，３−ジカルボキシフェニル）プロパン二無水物、１，１−ビス（３，４−ジカルボキシフェニル）エタン二無水物、１，１−ビス（２，３−ジカルボキシフェニル）エタン二無水物、ビス（３，４−ジカルボキシフェニル）メタン二無水物、ビス（２，３−ジカルボキシフェニル）メタン二無水物、ビス（３，４−ジカルボキシフェニル）スルホン二無水物、ビス（３，４−ジカルボキシフェニル）エーテル二無水物、１，２，５，６−ナフタレンテトラカルボン酸二無水物、９，９−ビス（３，４−ジカルボキシフェニル）フルオレン酸二無水物、９，９−ビス｛４−（３，４−ジカルボキシフェノキシ）フェニル｝フルオレン酸二無水物、２，３，６，７−ナフタレンテトラカルボン酸二無水物、２，３，５，６−ピリジンテトラカルボン酸二無水物、３，４，９，１０−ペリレンテトラカルボン酸二無水物、２，２−ビス（３，４−ジカルボキシフェニル）ヘキサフルオロプロパン二無水物、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物および下記に示す構造を有する酸二無水物などの芳香族テトラカルボン酸二無水物や、ブタンテトラカルボン酸二無水物、１，２，３，４−シクロペンタンテトラカルボン酸二無水物などの脂肪族テトラカルボン酸二無水物などを挙げることができる。これらを２種以上用いてもよい。

In the general formula (3), R ^1- (R ³ ) _p represents a tetracarboxylic acid residue. R ¹ is a 4 to 10 valent organic group, preferably a 4 to 10 valent organic group having 5 to 40 carbon atoms and having an aromatic ring or a cyclic aliphatic group.
Examples of the acid dianhydride constituting the tetracarboxylic acid residue include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4. '-Biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2' , 3,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) Methane dianhydride, bis (2,3- Dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic Acid dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluoric acid dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluoric acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2, 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, and the structure shown below Aromatic tetracarboxylic dianhydrides such as dianhydrides, aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydrides, 1,2,3,4-cyclopentanetetracarboxylic dianhydrides, etc. Can be mentioned. Two or more of these may be used.

Ｒ¹⁰は酸素原子、Ｃ（ＣＦ₃）₂、Ｃ（ＣＨ₃）₂またはＳＯ₂を表す。Ｒ¹¹およびＲ¹²は水素原子、水酸基またはチオール基を表す。
上記一般式（３）中、Ｒ²−（Ｒ⁴）_qはジアミン残基を表す。Ｒ²は２〜８価の有機基であり、芳香族環または環状脂肪族基を有する炭素原子数５〜４０の２〜８価の有機基が好ましい。
ジアミン残基を構成するジアミンとしては、例えば、３，４’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルメタン、３，４’−ジアミノジフェニルスルホン、４，４’−ジアミノジフェニルスルホン、３，４’−ジアミノジフェニルスルヒド、４，４’−ジアミノジフェニルスルヒド、１，４−ビス（４−アミノフェノキシ）ベンゼン、ベンジン、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、１，５−ナフタレンジアミン、２，６−ナフタレンジアミン、ビス（４−アミノフェノキシフェニル）スルホン、ビス（３−アミノフェノキシフェニル）スルホン、ビス（４−アミノフェノキシ）ビフェニル、ビス｛４−（４−アミノフェノキシ）フェニル｝エーテル、１，４−ビス（４−アミノフェノキシ）ベンゼン、２，２’−ジメチル−４，４’−ジアミノビフェニル、２，２’−ジエチル−４，４’−ジアミノビフェニル、３，３’−ジメチル−４，４’−ジアミノビフェニル、３，３’−ジエチル−４，４’−ジアミノビフェニル、２，２’，３，３’−テトラメチル−４，４’−ジアミノビフェニル、３，３’，４，４’−テトラメチル−４，４’−ジアミノビフェニル、２，２’−ジ（トリフルオロメチル）−４，４’−ジアミノビフェニル、９，９−ビス（４−アミノフェニル）フルオレンや、これらの芳香族環の水素原子の少なくとも一部をアルキル基やハロゲン原子で置換した化合物、シクロヘキシルジアミン、メチレンビスシクロヘキシルアミンなどの脂肪族ジアミン、および下記に示す構造を有するジアミンなどが挙げられる。これらを２種以上用いてもよい。

R ¹⁰ represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ . R ¹¹ and R ¹² represent a hydrogen atom, a hydroxyl group or a thiol group.
In the general formula (3), R ² — (R ⁴ ) _q represents a diamine residue. R ² is a divalent to octavalent organic group, preferably a divalent to octavalent organic group having 5 to 40 carbon atoms having an aromatic ring or a cyclic aliphatic group.
Examples of the diamine constituting the diamine residue include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, and 3,4'-diamino. Diphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m-phenylene Diamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, Bis {4- (4-aminophenoxy) f Nil} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4,4′-diaminobiphenyl, 3,3 '-Dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2', 3,3'-tetramethyl-4,4'-diaminobiphenyl, 3, 3 ′, 4,4′-tetramethyl-4,4′-diaminobiphenyl, 2,2′-di (trifluoromethyl) -4,4′-diaminobiphenyl, 9,9-bis (4-aminophenyl) Fluorene, compounds in which at least some of the hydrogen atoms of these aromatic rings are substituted with alkyl groups or halogen atoms, aliphatic diamines such as cyclohexyldiamine and methylenebiscyclohexylamine, and the structures shown below. Such as a diamine having the like. Two or more of these may be used.

Ｒ¹⁰は酸素原子、Ｃ（ＣＦ₃）₂、Ｃ（ＣＨ₃）₂またはＳＯ₂を表す。Ｒ¹¹〜Ｒ¹⁴は水素原子、水酸基またはチオール基を表す。
ポリベンゾオキサゾールは、ビスアミノフェノールとジカルボン酸、対応するジカルボン酸クロリド、ジカルボン酸活性エステルなどを反応させて得ることができる。一般に、ビスアミノフェノール化合物とジカルボン酸を反応させて得られるポリベンゾオキサゾール前駆体の１つであるポリヒドロキシアミドを、加熱あるいは無水リン酸、塩基、カルボジイミド化合物などの化学処理で脱水閉環することにより得ることができ、ジカルボン酸残基とビスアミノフェノール残基を有する。
ジカルボン酸残基を構成する酸としては、例えば、テレフタル酸、イソフタル酸、ジフェニルエーテルジカルボン酸、ビス（カルボキシフェニル）ヘキサフルオロプロパン、ビフェニルジカルボン酸、ベンゾフェノンジカルボン酸、トリフェニルジカルボン酸などが挙げられる。これらを２種以上用いてもよい。
ビスアミノフェノール残基を構成するジアミンとしては、例えば、下記に示す構造を有するジアミンなどが挙げられる。これらを２種以上用いてもよい。

R ¹⁰ represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ . R ^{11 to} R ¹⁴ represent a hydrogen atom, a hydroxyl group or a thiol group.
Polybenzoxazole can be obtained by reacting bisaminophenol with dicarboxylic acid, the corresponding dicarboxylic acid chloride, dicarboxylic acid active ester and the like. In general, polyhydroxyamide, which is one of the polybenzoxazole precursors obtained by reacting bisaminophenol compounds with dicarboxylic acids, is subjected to dehydration and ring closure by heating or chemical treatment of phosphoric anhydride, base, carbodiimide compounds, etc. It has a dicarboxylic acid residue and a bisaminophenol residue.
Examples of the acid constituting the dicarboxylic acid residue include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyldicarboxylic acid, benzophenone dicarboxylic acid, and triphenyldicarboxylic acid. Two or more of these may be used.
Examples of the diamine constituting the bisaminophenol residue include diamines having the structure shown below. Two or more of these may be used.

Ｒ¹⁰は酸素原子、Ｃ（ＣＦ₃）₂、Ｃ（ＣＨ₃）₂またはＳＯ₂を表す。Ｒ¹¹〜Ｒ¹⁴は水素原子、水酸基またはチオール基を表し、各ジアミンにおいて少なくとも一つは水酸基である。
ポリイミド前駆体は、例えば、テトラカルボン酸二無水物（一部を酸無水物、モノ酸クロリド化合物またはモノ活性エステル化合物に置換してもよい）とジアミン化合物を反応させて得られ、テトラカルボン酸残基とジアミン残基を有する。
ポリベンゾオキサゾール前駆体は、例えば、ビスアミノフェノール化合物とジカルボン酸を反応させて得られ、ジカルボン酸残基とビスアミノフェノール残基を有する。
本発明において、ポリイミド前駆体およびポリベンゾオキサゾール前駆体は下記一般式（４）で表される構造単位を有するものが好ましい。これらを２種以上含有してもよいし、他の構造単位との共重合体であってもよい。

R ¹⁰ represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ . R ^{11 to} R ¹⁴ represent a hydrogen atom, a hydroxyl group or a thiol group, and at least one of each diamine is a hydroxyl group.
The polyimide precursor is obtained, for example, by reacting a tetracarboxylic dianhydride (a part of which may be replaced with an acid anhydride, a monoacid chloride compound or a monoactive ester compound) and a diamine compound, and a tetracarboxylic acid. Has a residue and a diamine residue.
The polybenzoxazole precursor is obtained, for example, by reacting a bisaminophenol compound with a dicarboxylic acid, and has a dicarboxylic acid residue and a bisaminophenol residue.
In the present invention, the polyimide precursor and the polybenzoxazole precursor preferably have a structural unit represented by the following general formula (4). Two or more of these may be contained, or a copolymer with another structural unit may be used.

上記一般式（４）中、Ｒ⁵およびＲ⁶は２〜８価の有機基を表し、それぞれ同じでも異なっていてもよい。Ｒ⁷およびＲ⁸はフェノール性水酸基、スルホン酸基、チオール基、またはＣＯＯＲ⁹を表し、それぞれ同じでも異なっていてもよい。Ｒ⁹は水素原子または炭素原子数１〜２０の１価の炭化水素基を示す。ｒおよびｓは０〜６の整数を表す。ただしｒ＋ｓ＞０である。
上記一般式（４）中、Ｒ⁵−（Ｒ⁷）_rはジカルボン酸やテトラカルボン酸などの酸残基を表す。Ｒ⁵は２〜８価の有機基であり、芳香族環または環状脂肪族基を含有する炭素原子数５〜４０の２〜８価の有機基が好ましい。
酸残基を構成する酸としては、例えば、ジカルボン酸の例として、ポリベンゾオキサゾールのジカルボン酸残基を構成する酸として例示したものを挙げることができる。トリカルボン酸の例として、トリメリット酸、トリメシン酸、ジフェニルエーテルトリカルボン酸、ビフェニルトリカルボン酸などを挙げることができる。テトラカルボン酸の例としてピロメリット酸、３，３’，４，４’−ビフェニルテトラカルボン酸、２，３，３’，４’−ビフェニルテトラカルボン酸、２，２’，３，３’−ビフェニルテトラカルボン酸、３，３’，４，４’−ベンゾフェノンテトラカルボン酸、２，２’，３，３’−ベンゾフェノンテトラカルボン酸、２，２−ビス（３，４−ジカルボキシフェニル）ヘキサフルオロプロパン、２，２−ビス（２，３−ジカルボキシフェニル）ヘキサフルオロプロパン、１，１−ビス（３，４−ジカルボキシフェニル）エタン、１，１−ビス（２，３−ジカルボキシフェニル）エタン、ビス（３，４−ジカルボキシフェニル）メタン、ビス（２，３−ジカルボキシフェニル）メタン、ビス（３，４−ジカルボキシフェニル）スルホン、ビス（３，４−ジカルボキシフェニル）エーテル、１，２，５，６−ナフタレンテトラカルボン酸、２，３，６，７−ナフタレンテトラカルボン酸、２，３，５，６−ピリジンテトラカルボン酸、３，４，９，１０−ペリレンテトラカルボン酸および下記に示す構造を有するテトラカルボン酸などの芳香族テトラカルボン酸や、ブタンテトラカルボン酸、１，２，３，４−シクロペンタンテトラカルボン酸などの脂肪族テトラカルボン酸などを挙げることができる。これらを２種以上用いてもよい。

In the general formula (4), R ⁵ and R ⁶ represent divalent to octavalent organic groups, which may be the same or different. R ⁷ and R ⁸ represent a phenolic hydroxyl group, a sulfonic acid group, a thiol group, or COOR ⁹ and may be the same or different. R ⁹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. r and s represent the integer of 0-6. However, r + s> 0.
In the general formula (4), R ^5- (R ⁷ ) _r represents an acid residue such as dicarboxylic acid or tetracarboxylic acid. R ⁵ is a divalent to octavalent organic group, preferably a divalent to octavalent organic group having 5 to 40 carbon atoms and containing an aromatic ring or a cycloaliphatic group.
As an acid which comprises an acid residue, what was illustrated as an acid which comprises the dicarboxylic acid residue of polybenzoxazole as an example of dicarboxylic acid can be mentioned, for example. Examples of the tricarboxylic acid include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyltricarboxylic acid, and the like. Examples of tetracarboxylic acid include pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3′- Biphenyltetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 2,2 ′, 3,3′-benzophenonetetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexa Fluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,1-bis (3,4-dicarboxyphenyl) ethane, 1,1-bis (2,3-dicarboxyphenyl) ) Ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-di) Carboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9, Aromatic tetracarboxylic acids such as 10-perylenetetracarboxylic acid and tetracarboxylic acids having the structure shown below, and aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid And so on. Two or more of these may be used.

Ｒ¹⁰は酸素原子、Ｃ（ＣＦ₃）₂、Ｃ（ＣＨ₃）₂またはＳＯ₂を表す。Ｒ¹¹およびＲ¹²は水素原子、水酸基またはチオール基を表す。
これらのうち、トリカルボン酸、テトラカルボン酸では１つまたは２つのカルボキシ基が一般式（４）におけるＲ⁷基に相当する。また、上に例示したジカルボン酸、トリカルボン酸、テトラカルボン酸の水素原子を、一般式（４）におけるＲ⁷基、好ましくは水酸基やスルホン酸基、チオール基などで１〜４個置換したものがより好ましい。これらの酸は、そのまま、あるいは酸無水物、活性エステルとして使用できる。
上記一般式（４）中、のＲ⁶−（Ｒ⁸）_sはジアミンやビスアミノフェノールなどのアミン残基を表す。Ｒ⁸は２〜８価の有機基であり、芳香族環または環状脂肪族基を有する炭素原子数５〜４０の２〜８価の有機基が好ましい。
アミン残基を構成するジアミンとしては、例えば、ポリイミドのジアミン残基を構成するジアミンとして例示したものを挙げることができる。
また、これらの樹脂の末端を、水酸基、カルボキシ基、スルホン酸基またはチオール基を有するモノアミン、酸無水物、酸クロリド、モノカルボン酸により封止することが好ましい。これらを２種以上用いてもよい。主鎖末端に前述の基を有することにより、樹脂のアルカリ水溶液に対する溶解速度を好ましい範囲に容易に調整することができる。
モノアミンの好ましい例としては、５−アミノ−８−ヒドロキシキノリン、１−ヒドロキシ−７−アミノナフタレン、１−ヒドロキシ−６−アミノナフタレン、１−ヒドロキシ−５−アミノナフタレン、１−ヒドロキシ−４−アミノナフタレン、２−ヒドロキシ−７−アミノナフタレン、２−ヒドロキシ−６−アミノナフタレン、２−ヒドロキシ−５−アミノナフタレン、１−カルボキシ−７−アミノナフタレン、１−カルボキシ−６−アミノナフタレン、１−カルボキシ−５−アミノナフタレン、２−カルボキシ−７−アミノナフタレン、２−カルボキシ−６−アミノナフタレン、２−カルボキシ−５−アミノナフタレン、２−アミノ安息香酸、３−アミノ安息香酸、４−アミノ安息香酸、４−アミノサリチル酸、５−アミノサリチル酸、６−アミノサリチル酸、２−アミノベンゼンスルホン酸、３−アミノベンゼンスルホン酸、４−アミノベンゼンスルホン酸、３−アミノ−４，６−ジヒドロキシピリミジン、２−アミノフェノール、３−アミノフェノール、４−アミノフェノール、２−アミノチオフェノール、３−アミノチオフェノール、４−アミノチオフェノールなどが挙げられる。これらを２種以上用いてもよい。
酸無水物、酸クロリド、モノカルボン酸の好ましい例としては、無水フタル酸、無水マレイン酸、ナジック酸、シクロヘキサンジカルボン酸無水物、３−ヒドロキシフタル酸無水物などの酸無水物、３−カルボキシフェノール、４−カルボキシフェノール、３−カルボキシチオフェノール、４−カルボキシチオフェノール、１−ヒドロキシ−７−カルボキシナフタレン、１−ヒドロキシ−６−カルボキシナフタレン、１−ヒドロキシ−５−カルボキシナフタレン、１−メルカプト−７−カルボキシナフタレン、１−メルカプト−６−カルボキシナフタレン、１−メルカプト−５−カルボキシナフタレン、３−カルボキシベンゼンスルホン酸、４−カルボキシベンゼンスルホン酸などのモノカルボン酸類およびこれらのカルボキシ基が酸クロリド化したモノ酸クロリド化合物、テレフタル酸、フタル酸、マレイン酸、シクロヘキサンジカルボン酸、１，５−ジカルボキシナフタレン、１，６−ジカルボキシナフタレン、１，７−ジカルボキシナフタレン、２，６−ジカルボキシナフタレンなどのジカルボン酸類の１つのカルボキシ基だけが酸クロリド化したモノ酸クロリド化合物、モノ酸クロリド化合物とＮ−ヒドロキシベンゾトリアゾールやＮ−ヒドロキシ−５−ノルボルネン−２，３−ジカルボキシイミドとの反応により得られる活性エステル化合物が挙げられる。これらを２種以上用いてもよい。

R ¹⁰ represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ . R ¹¹ and R ¹² represent a hydrogen atom, a hydroxyl group or a thiol group.
Among these, in tricarboxylic acid and tetracarboxylic acid, one or two carboxy groups correspond to the R ⁷ group in the general formula (4). Further, dicarboxylic acids exemplified above, tricarboxylic acid, a hydrogen atom of the tetracarboxylic acid of the general formula (4) in the R ⁷ groups, preferably those 1-4 substituted by a hydroxyl group or a sulfonic acid group, a thiol group More preferred. These acids can be used as they are, or as acid anhydrides and active esters.
In the general formula (4), R ⁶ — (R ⁸ ) _s represents an amine residue such as diamine or bisaminophenol. R ⁸ is a divalent to octavalent organic group, preferably a divalent to octavalent organic group having 5 to 40 carbon atoms having an aromatic ring or a cyclic aliphatic group.
As a diamine which comprises an amine residue, what was illustrated as a diamine which comprises the diamine residue of a polyimide can be mentioned, for example.
Moreover, it is preferable to seal the terminal of these resins with a monoamine, acid anhydride, acid chloride, or monocarboxylic acid having a hydroxyl group, a carboxy group, a sulfonic acid group, or a thiol group. Two or more of these may be used. By having the aforementioned group at the end of the main chain, the dissolution rate of the resin in the alkaline aqueous solution can be easily adjusted to a preferred range.
Preferred examples of the monoamine include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-amino. Naphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid 4-aminosalicylic acid, 5-aminosalicylic acid, -Aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol , 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. Two or more of these may be used.
Preferred examples of the acid anhydride, acid chloride, and monocarboxylic acid include phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride and other acid anhydrides, 3-carboxyphenol 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7 Monocarboxylic acids such as carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, and the carboxy group is acid chloride Monoacid chloride compound, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxyl Monoacid chloride compound in which only one carboxy group of dicarboxylic acids such as naphthalene is acid chloride, reaction of monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide The active ester compound obtained by this is mentioned. Two or more of these may be used.

  As the alkali-soluble resin, in particular, a benzyl (meth) acrylate / (meth) acrylic acid copolymer and a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are suitable. In addition, a copolymer of 2-hydroxyethyl methacrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2-hydroxy -3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / Benzyl methacrylate / methacrylic acid copolymer.

The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and most preferably 70 to 120 mgKOH / g.
Further, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and most preferably 7,000 to 20,000.

In the present invention, the content of the total polymer in the radiation-sensitive composition is preferably 10 to 90% by mass with respect to the total solid content of the radiation-sensitive composition from the viewpoint of developability and the like, and is preferably 20 to 60%. % By weight is more preferable, and 30 to 50% by weight is particularly preferable.
In the present invention, the total solid content of the radiation-sensitive composition refers to all components excluding the solvent.

（一般式（２）中、Ａは酸基を表し、Ｌは、酸素原子、炭素原子および水素原子から選択される２種以上の原子から構成される、（ｎ１＋ｎ２）価の基であり、Ａｃは（メタ）アクリロイルオキシ基を示す。ｎ１は１〜３の整数を表す。ｎ２は２以上の整数を表す。）
Ａは、カルボン酸基、スルホンアミド基、ホスホン酸基、スルホン酸基が例示され、カルボン酸基が好ましい。
Ｌは、少なくとも炭素原子と水素原子を含む基であることが好ましい。Ｌを構成する炭素原子と酸素原子の合計数が、３〜１５あることが好ましく、６〜１２であることがより好ましい。
ｎ１は、１または２が好ましく、１がより好ましい。ｎ２は、６以下の整数が好ましく、２〜５の整数がより好ましく、３または４がさらに好ましい。 <Polymerizable compound>
The composition of the present invention contains at least an acid group and a bifunctional or higher functional (meth) acrylate compound as the polymerizable compound.
The (meth) acrylate compound having an acid group and having two or more functions is preferably represented by the following general formula (2).
General formula (2)

(In General Formula (2), A represents an acid group, L is a (n1 + n2) -valent group composed of two or more kinds of atoms selected from an oxygen atom, a carbon atom and a hydrogen atom; Represents a (meth) acryloyloxy group, n1 represents an integer of 1 to 3, and n2 represents an integer of 2 or more.
Examples of A include a carboxylic acid group, a sulfonamide group, a phosphonic acid group, and a sulfonic acid group, and a carboxylic acid group is preferable.
L is preferably a group containing at least a carbon atom and a hydrogen atom. The total number of carbon atoms and oxygen atoms constituting L is preferably 3 to 15, and more preferably 6 to 12.
n1 is preferably 1 or 2, and more preferably 1. n2 is preferably an integer of 6 or less, more preferably an integer of 2 to 5, and still more preferably 3 or 4.

In this invention, it is preferable that it is 1-50 mass%, and the ratio of the (meth) acrylate compound which has an acid group among all the polymeric compounds and is bifunctional or more is 1-20 mass%. It is more preferable.
Only one type or two or more types of (meth) acrylate compounds having an acid group and having two or more functional groups may be included. When two or more types are included, the total amount is within the above range.

  The composition of the present invention has the above acid group and a polymerizable compound other than a bifunctional or higher (meth) acrylate compound (hereinafter sometimes referred to as “other polymerizable compound”). It is preferable to have such a polymerizable compound.

 Specifically, the other polymerizable compound 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. These may be in any of chemical forms such as, for example, monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof, and multimers thereof, but are preferably monomers. The polymeric compound in this invention may be used individually by 1 type, and may use 2 or more types together.

More specifically, examples of monomers and prepolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And multimers thereof, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and multimers thereof. is there. 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 compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used 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.

The polymerizable compound is also preferably a compound having at least one addition-polymerizable ethylene group as a polymerizable monomer 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 annulate, glycerin and trimethylolethane; Urethane (meth) acrylates as described in JP-B-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates and the like, which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
Further, as other preferable polymerizable compounds, there are fluorene rings described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, etc., and an ethylenically polymerizable group is bifunctional. The above-mentioned compounds and cardo resins can also be used.

  Further, compounds having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group are disclosed in paragraphs [0254] to [0257] of JP-A-2008-292970. The compounds described are also suitable.

  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.
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 represents an -OC (= O) C (CH 3) = groups represented by 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.

  In addition, a compound which has been (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. Can be used as a polymerizable compound.

  Among these, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product); Nippon Kayaku Co., Ltd. Dipentaerythritol penta (meth) acrylate (manufactured by KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (manufactured by KAYARAD DPHA; Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are interposed via ethylene glycol and propylene glycol residues. These oligomer types can also be used.

 As a polymeric compound, it is a polyfunctional monomer, Comprising: You may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. The acid group may be introduced by reacting the group with a non-aromatic carboxylic acid anhydride. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

  In the present invention, the monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

 A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. If the acid value of the polyfunctional monomer is too low, the developing dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel is deteriorated. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is essential.

（式中、６個のＲは全てが下記式（２）で表される基であるか、または６個のＲのうち１〜５個が下記式（２）で表される基であり、残余が下記式（３）で表される基である。）

（式中、Ｒ¹は水素原子またはメチル基を示し、ｍは１または２の数を示し、「＊」は結合手であることを示す。）

（式中、Ｒ¹は水素原子またはメチル基を示し、「＊」は結合手であることを示す。）
このようなカプロラクトン構造を有する多官能性単量体は、例えば、日本化薬（株）からＫＡＹＡＲＡＤ ＤＰＣＡシリーズとして市販されており、ＤＰＣＡ−２０（上記式（１）〜（３）においてｍ＝１、式（２）で表される基の数＝２、Ｒ¹が全て水素原子である化合物）、ＤＰＣＡ−３０（同式、ｍ＝１、式（２）で表される基の数＝３、Ｒ¹が全て水素原子である化合物）、ＤＰＣＡ−６０（同式、ｍ＝１、式（２）で表される基の数＝６、Ｒ¹が全て水素原子である化合物）、ＤＰＣＡ−１２０（同式においてｍ＝２、式（２）で表される基の数＝６、Ｒ¹が全て水素原子である化合物）等を挙げることができる。
本発明において、カプロラクトン構造を有する多官能性単量体は、単独でまたは２種以上を混合して使用することができる。 Moreover, it is preferable to contain the polyfunctional monomer which has a caprolactone structure as a polymerizable monomer.
The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta Ε-caprolactone modified polyfunctionality obtained by esterifying polyhydric alcohol such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone ( Mention may be made of (meth) acrylates. Among these, a polyfunctional monomer having a caprolactone structure represented by the following formula (1) is preferable.

(In the formula, all 6 Rs are groups represented by the following formula (2), or 1 to 5 of 6 Rs are groups represented by the following formula (2), The remainder is a group represented by the following formula (3).)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.)
Such a polyfunctional monomer having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (1) to (3)). , Number of groups represented by formula (2) = 2, compound in which R ¹ is all hydrogen atoms, DPCA-30 (same formula, m = 1, number of groups represented by formula (2) = 3 , Compounds in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (2) = 6, compounds in which R ¹ are all hydrogen atoms), DPCA- 120 (a compound in which m = 2 in the same formula, the number of groups represented by formula (2) = 6, and all R ¹ are hydrogen atoms).
In this invention, the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.

The specific monomer in the present invention is preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).

In the general formulas (i) and (ii), each E independently represents — ((CH ₂ ) yCH ₂ O) — or — ((CH ₂ ) yCH (CH ₃ ) O) —, and y Each independently represents an integer of 0 to 10, and each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In said general formula (i), the sum total of acryloyl group and methacryloyl group is 3 or 4, m represents the integer of 0-10 each independently, and the sum of each m is an integer of 0-40. However, when the total of each m is 0, any one of X is a carboxyl group.
In the general formula (ii), the total number of acryloyl groups and methacryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. However, when the total of each n is 0, any one of X is a carboxyl group.

In the general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In the general formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In general formula (i) or formula (ii) in the _{- ((CH 2) yCH 2} O) - or _{- ((CH 2) yCH (} CH 3) O) - , the terminal oxygen atom side X The form which couple | bonds with is preferable.

  The compounds represented by the general formula (i) or (ii) may be used alone or in combination of two or more. In particular, in the general formula (ii), a form in which all six Xs are acryloyl groups is preferable.

  Moreover, as a total content in the specific monomer of the compound represented by general formula (i) or (ii), 20 mass% or more is preferable, and 50 mass% or more is more preferable.

  The compound represented by the general formula (i) or (ii) is a ring-opening skeleton obtained by ring-opening addition reaction of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known process. And a step of reacting, for example, (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton to introduce a (meth) acryloyl group. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (i) or (ii).

Among the compounds represented by the general formulas (i) and (ii), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), and among them, exemplary compounds (a) and ( b), (e) and (f) are preferred.

  Examples of commercially available products of the specific monomers represented by the general formulas (i) and (ii) include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and pliers manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six lenoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of the polymerizable compound include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Also suitable are urethane compounds having an ethylene oxide skeleton as described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Furthermore, 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 as polymerizable compounds. By using the compounds, it is possible to obtain a composition having a very excellent photosensitive speed.
Commercially available polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA- 306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.

（式中、Ｒ¹はアルキル基、Ｒ²は炭素以外の原子を含んでもよいｎ価の脂肪族基、Ｒ⁰はＨではないアルキル基、ｎは２〜４を表す。） A polyfunctional thiol compound having two or more mercapto (SH) groups in the same molecule is also suitable as the polymerizable compound. Particularly preferred are those represented by the following general formula (I).

(In the formula, R ¹ is an alkyl group, R ² is an n-valent aliphatic group that may contain atoms other than carbon, R ⁰ is an alkyl group that is not H, and n represents 2 to 4).

If the polyfunctional thiol compound represented by the general formula (I) is specifically exemplified, 1,4-bis (3-mercaptobutyryloxy) butane [formula (II)] having the following structural formula: 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triasian-2,4,6 (1H, 3H5H) -trione [formula (III)] and pentaerythritol tetrakis (3 -Mercaptobutyrate) [formula (IV)] and the like. These polyfunctional thiols can be used alone or in combination.

  About the compounding quantity of the polyfunctional thiol in a composition, it adds in 0.3-8.9 weight% with respect to the total solid except a solvent, More preferably, it adds in 0.8-6.4 weight%. Is desirable. By adding a polyfunctional thiol, the stability, odor, sensitivity, resolution, developability, adhesion, etc. of the composition can be improved.

 About these polymeric compounds, the details of usage methods, such as the structure, single use, combined use, addition amount, etc. can be arbitrarily set according to the final performance design of a 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 colored cured film, those having three or more functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic acid esters, methacrylic acid esters, styrene compounds, vinyl ether compounds). It is also effective to adjust both sensitivity and intensity by using together. Further, it is preferable to use a trifunctional or higher functional polymerizable compound having a different ethylene oxide chain length in that the developability of the composition can be adjusted and an excellent pattern forming ability can be obtained. In addition, the compatibility and dispersibility with other components (for example, photopolymerization initiators, colorants (pigments), binder polymers, etc.) contained in the composition are as follows. This is an important factor. For example, compatibility may be improved by using a low-purity compound or 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 substrate.

 These other polymerizable compounds in the composition of the present invention are preferably 80% by mass or less, more preferably 60% by mass or less, and further preferably 40% by mass or less. In the present invention, (meth) acrylate having no acid group is particularly preferable as the other polymerizable compound, and polyfunctional (meth) acrylate having no acid group is more preferable. In the present invention, the total amount of the (meth) acrylate having an acid group and having two or more functional groups and the (meth) acrylate having no acid group may occupy 80% by mass or more of the prepolymerizable compound. preferable.

  The composition of the present invention has a ratio of (meth) acrylate having an acid group and a bifunctional or higher functionality to the total amount of the polymer (having an acid group and having a bifunctional or higher (meth) acrylate / The total polymer × 100 (% by mass)) is preferably 1 to 50% by mass, more preferably 3 to 30% by mass, further preferably 5 to 20% by mass, and 5 to 15% by mass. % Is more preferable. By setting it as such a range, it exists in the tendency for a residue to reduce more.

<Polymerization initiator>
The composition of the present invention contains a polymerization initiator. The polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known polymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
The polymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

  Examples of the polymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives. Oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.

  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.).

  In addition, as polymerization initiators other than those described above, polyhalogen compounds (for example, four-phenyl acridine, such as 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane), N-phenylglycine, and the like. Carbon bromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, etc.), coumarins (for example, 3- (2-benzofuranoyl) -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′-carbo Rubis (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) -phenylphosphite 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.) Examples thereof include compounds described in JP-A Nos. 53-133428, 57-1819, 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-ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bisdicyclohexyl) Amino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzene Zophenone, 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, benzo Down 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.

As the polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long-wave light source such as 365 nm or 405 nm can also be used. As the acylphosphine-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

  As the polymerization initiator, an oxime compound is preferably used. Specific examples of the oxime initiator include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.

  Examples of oxime compounds such as oxime derivatives that are preferably used as a polymerization initiator in the present invention include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxyimibutane. 2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4- Toluenesulfonyloxy) iminobutan-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 15
6-162, Journal of Photopolymer Science and Technology (1995), pp. 6-162. 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) and IRGACURE-OXE02 (manufactured by BASF) are also suitably used as commercial products.

  Further, as oxime ester compounds other than those described above, compounds described in JP-T 2009-519904, in which an oxime is linked to the N-position of carbazole, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, A compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced at the dye site, a ketoxime compound described in International Patent Publication No. 2009-131189, the triazine skeleton and the oxime skeleton are identical A compound described in US Pat. No. 7,556,910 contained in the molecule, a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used. .

Preferably, it can also be suitably used for the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744. Among the cyclic oxime compounds, in particular, the cyclic oxime compounds fused to the carbazole dyes described in JP2010-32985A and JP2010-185072A have high light absorption and high sensitivity. preferable.
Further, the compound described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can be preferably used because it can achieve high sensitivity by regenerating active radicals from polymerization inert radicals. it can.

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 polymerization initiator is preferably a compound represented by the following formula (OX-1). The N—O bond of the oxime may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

(In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.)
In the formula (OX-1), 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, octadecyl 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-tolyl group, m-tolyl group, p -Tolyl group, xylyl group, o-cumenyl group, m-cumenyl group and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, full Oranthenyl, acenaphthylenyl, aceanthrylenyl, phenalenyl, fluorenyl, ant Ryl group, bianthracenyl group, teranthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrycenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, Examples thereof include a pentacenyl group, a tetraphenylenyl group, a hexaphenyl group, a hexacenyl group, a ruvicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an oberenyl 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, quinoxalinyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group 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 optionally substituted alkylthiocarbonyl group 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.

  In the formula (OX-1), 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 (OX-2) described later, and preferred examples are also the same.

In the formula (OX-1), examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, and an alkynylene 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.
Among them, A in the formula (OX-1) is an unsubstituted alkylene group, an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, dodecyl) from the viewpoint of increasing sensitivity and suppressing coloring due to heating. Group) substituted alkylene group, alkenyl group (eg vinyl group, allyl group) alkylene group, aryl group (eg phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl) Group, a phenanthryl group, and a styryl group) are preferable.

In the formula (OX-1), 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 (OX-1), it is preferable from the viewpoint of sensitivity that the structure of “SAr” formed by Ar in the formula (OX-1) and S adjacent thereto is a structure shown below. Me represents a methyl group, and Et represents an ethyl group.

  The oxime compound is preferably a compound represented by the following formula (OX-2).

(In Formula (OX-2), 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 to 0. (It is an integer of 5.)
R, A and Ar in the formula (OX-2) have the same meanings as R, A and Ar in the formula (OX-1), and preferred examples are also the same.

  In the formula (OX-2), the monovalent substituent represented by X includes an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, and a heterocyclic ring. Group and 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, as X in Formula (OX-2), an alkyl group is preferable 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.

  In the formula (OX-2), 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 (OX-2).

  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 (OX-3).

(In Formula (OX-3), 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 Formula (OX-3) have the same meanings as R, X, A, Ar, and n in Formula (OX-2), respectively, and preferred examples are also the same. is there.

  Specific examples (C-4) to (C-13) 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 high absorbance at 365 nm and 455 nm.

The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
For the molar extinction coefficient of the compound, a known method can be used. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Vary Inc., Carry-5 spectrphotometer) using an ethyl acetate solvent is used. It is preferable to measure at a concentration of / L.

  The polymerization initiator used in the present invention may be used in combination of two or more as required.

  As a polymerization initiator used in the composition of the present invention, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, Metallocene compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, 3-aryl substituted coumarins Compounds selected from the group consisting of compounds are preferred.

  More preferred are trihalomethyltriazine compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triallylimidazole dimer, onium compound, benzophenone compound, acetophenone compound, trihalomethyltriazine compound, α-aminoketone Most preferred is at least one compound selected from the group consisting of compounds, oxime compounds, triallylimidazole dimer, and benzophenone compounds.

  The content (in the case of 2 or more types) of the polymerization initiator contained in the composition of the present invention is 0.1% by mass or more and 50% by mass or less based on the total solid content of the composition. More preferably, it is 0.5 mass% or more and 30 mass% or less, More preferably, it is 1 mass% or more and 20 mass% or less. Within this range, good sensitivity and pattern formability can be obtained.

<Ultraviolet absorber>
The 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 a 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); 3-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- Dibutoxyphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4,6-tris [2- And tris (hydroxyphenyl) triazine compounds such as hydroxy-4- (3-butoxy-2-hydroxypropyloxy) phenyl] -1,3,5-triazine.

 In the composition of the present invention, it is also preferable to use a compound represented by the following general formula (I), which is a conjugated diene compound, as an ultraviolet absorber.

In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² May be the same as or different from each other, but do not represent a hydrogen atom at the same time.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-hexyl group, a cyclohexyl group, and an n-decyl group. Group, n-dodecyl group, n-octadecyl group, eicosyl group, methoxyethyl group, ethoxypropyl group, 2-ethylhexyl group, hydroxyethyl group, chloropropyl group, N, N-diethylaminopropyl group, cyanoethyl group, phenethyl group Group, benzyl group, pt-butylphenethyl group, pt-octylphenoxyethyl group, 3- (2,4-di-t-amylphenoxy) propyl group, ethoxycarbonylmethyl group, 2- (2-hydroxyethoxy) ) Ethyl group, 2-furylethyl group and the like, and methyl group, ethyl group, propyl group, n-butyl group and n-hexyl group are preferred. .
The alkyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent of the alkyl group having a substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, Halogen atom, acylamino group, acyl group, alkylthio group, arylthio group, hydroxy group, cyano group, alkyloxycarbonyl group, aryloxycarbonyl group, substituted carbamoyl group, substituted sulfamoyl group, nitro group, substituted amino group, alkylsulfonyl group, An arylsulfonyl group etc. are mentioned.

The aryl group having 6 to 20 carbon atoms represented by R ¹ and R ² may be a single ring or a condensed ring, and is any of a substituted aryl group having a substituent or an unsubstituted aryl group. There may be. For example, a phenyl group, 1-naphthyl group, 2-naphthyl group, anthryl group, phenanthryl group, indenyl group, acenabutenyl group, fluorenyl group, etc. can be mentioned. Examples of the substituent of the substituted aryl group having a substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a halogen atom, an acylamino group, an acyl group, an alkylthio group, an arylthio group, a hydroxy group, and a cyano group. Group, alkyloxycarbonyl group, aryloxycarbonyl group, substituted carbamoyl group, substituted sulfamoyl group, nitro group, substituted amino group, alkylsulfonyl group, arylsulfonyl group and the like. Of these, a substituted or unsubstituted phenyl group, 1-naphthyl group, and 2-naphthyl group are preferable.

R ¹ and R ² may form a cyclic amino group together with the nitrogen atom. Examples of the cyclic amino group include piperidino group, morpholino group, pyrrolidino group, hexahydroazepino group, piperazino group and the like.

Among the above, R ¹ and R ² are each a lower alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, tert-pentyl, hexyl, octyl). , 2-ethylhexyl, tert-octyl, etc.) or a substituted or unsubstituted phenyl group (for example, tolyl group, phenyl group, anisyl group, mesityl group, chlorophenyl group, 2,4-di-t-amylphenyl group, etc.) preferable. It is also preferred that R ¹ and R ² are bonded to form a ring (for example, a piperidine ring, a pyrrolidine ring, a morpholine ring) containing the nitrogen atom represented by N in the formula.

In the general formula (I), R ³ and R ⁴ represent an electron withdrawing group. Here, the electron-withdrawing group is an electron-withdrawing group having Hammett's substituent constant σ _p value (hereinafter simply referred to as “σ _p value”) of 0.20 or more and 1.0 or less. Preferably, it is an electron withdrawing group having a σ _p value of 0.30 or more and 0.8 or less.
Hammett's rule is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, which is widely accepted today. . Substituent constants obtained by Hammett's rule include σ _p value and σ _m value, and these values are described in many general books. For example, JA Dean edition “Lang's Handbook of Chemistry” "Twelfth edition, 1979 (Mc Graw-Hill)" and "Chemical domain special issue", 122, 96-103, 1979 (Nanedo), Chemical Reviews, 91, 165-195, 1991 detailed. In the present invention, it does not mean that the values known in the literature described in these documents are limited to only certain substituents, but within the range when measured based on Hammett's law even if the value is unknown. Of course, it is included as long as it is included.

Specific examples of the electron withdrawing group having a σ _p value of 0.20 or more and 1.0 or less include an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, Dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, at least An alkyl group substituted with two or more halogen atoms, an alkoxy group substituted with at least two halogen atoms, an aryloxy group substituted with at least two halogen atoms, or at least two halogen atoms Substituted alkylamines Group, an alkylthio group substituted with at least two halogen atoms, an aryl group substituted with another electron-withdrawing group with a σ _p value of 0.20 or more, a heterocyclic group, a chlorine atom, a bromine atom, an azo group Or a selenocyanate group. Of these substituents, the group that can further have a substituent may further have a substituent as described above.

Among the above, in the present invention, R ³ is preferably a group selected from a cyano group, —COOR ⁵ , —CONHR ⁵ , —COR ⁵ , —SO ₂ R ⁵ , and R ⁴ is a cyano group. A group selected from the group, —COOR ⁶ , —CONHR ⁶ , —COR ⁶ , —SO ₂ R ⁶ is preferred. R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms represented by R ⁵ and R ^{6 have the same} meanings as those in the above R ¹ and R ² , and the preferred embodiments are also the same.
Among these, as R ³ and R ⁴ , acyl group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, sulfamoyl group are preferable. In particular, an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, and a sulfamoyl group are preferable.
R ³ and R ⁴ may be bonded to each other to form a ring.

In addition, at least one of R ¹ , R ² , R ³ , and R ⁴ may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. It may be a copolymer with another monomer. In the case of the copolymer, other monomers include acrylic acid, α-chloroacrylic acid, α-alacrylic acid (for example, esters derived from acrylic acids such as methacrylic acid, preferably lower alkyl esters and amides such as Acrylamide, methacrylamide, t-butyl acrylamide, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, octyl methacrylate , And lauryl methacrylate, methylene bisacrylamide, etc.), vinyl esters (eg, vinyl acetate, vinyl propionate, vinyl laurate, etc.), acrylonitrile, methacrylonitrile Tolyl, aromatic vinyl compounds (for example, styrene and its derivatives such as vinyl toluene, divinylbenzene, vinyl acetophenone, sulfostyrene, and styrene sulfinic acid), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether ( For example, vinyl ethyl ether), maleic acid ester, N-vinyl-2-pyrrolidone, N-vinylpyridine, 2- and 4-vinylpyridine, and the like.
Of these, acrylic acid esters, methacrylic acid esters, and aromatic vinyl compounds are particularly preferable.
Two or more of the above comonomer compounds can also be used together. For example, n-butyl acrylate and divinylbenzene, styrene and methyl methacrylate, methyl acrylate and methacrylate acid, or the like can be used.

  Hereinafter, preferable specific examples [Exemplary compounds (1) to (14)] of the compound represented by the general formula (I) are shown. However, the present invention is not limited to these.

The compounds represented by the general formula (I) in the present invention are disclosed in JP-B-44-29620, JP-A-53-128333, JP-A-61-169831, JP-A-63-53543, They can be synthesized by the methods described in Japanese Utility Model Laid-Open Nos. 63-53544 and 63-56651.
Examples of commercially available products include diethylamino-phenylsulfonyl-pentadienoate ultraviolet absorbers (trade name: DPO, manufactured by Fuji Film Fine Chemicals).
In the present invention, the various ultraviolet absorbers may be used alone or in combination of two or more.

  As content in the radiation sensitive composition of this invention of the ultraviolet absorber demonstrated above, when this ultraviolet absorber is included, 0.01 mass%-30 mass% with respect to the total solid of a composition Is preferable, 0.01% by mass to 20% by mass is more preferable, 0.01% by mass to 15% by mass is particularly preferable, and 3% by mass to 10% by mass is most preferable. When the content of this ultraviolet absorber is 0.01% by mass or more, the light shielding ability at the time of exposure is good and the pattern line width due to excessive progress of polymerization is prevented, and the desired line width is easily obtained. Further, the generation of peripheral residues (development residues) is further suppressed. On the other hand, when it is 30% by mass or less, the light shielding ability at the time of exposure is not too strong, and the polymerization proceeds better.

<Solvent>
In general, the radiation-sensitive composition of the present invention can be constituted using a solvent (usually an organic solvent).
The solvent is basically not particularly limited as long as the solubility of each component and the coating property of the radiation-sensitive composition are satisfied, but particularly considering the solubility, coating property, and safety of the UV absorber and the binder. It is preferable to be selected. Moreover, when preparing the radiation sensitive composition of this invention, it is preferable that at least 2 type of solvent is included.

  Examples of the solvent 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, alkyl esters, methyl lactate, Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc .; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, 2-methoxypropion Acid ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy- 2-methylpropio Methyl acid, 2-ethoxy-2-methylpropionic acid ethyl, etc; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

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, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc .;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone are preferred; aromatic hydrocarbons such as toluene and xylene are preferred.

  As described above, these solvents may be used in combination of two or more from the viewpoints of solubility of the ultraviolet absorber and alkali-soluble resin, improvement of the coated surface, and the like. In particular, methyl 3-ethoxypropionate, 3 -Ethyl ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol A mixed solution composed of two or more selected from methyl ether acetate is preferably used.

  The content of the solvent in the radiation-sensitive composition is preferably such that the total solid concentration of the composition is 5 to 90% by mass, more preferably 5 to 87% by mass, from the viewpoint of applicability. 10-85 mass% is especially preferable, and 50-85 mass% is further more preferable.

<Adhesion improver>
In order to improve the adhesion between each layer or the adhesion between the photosensitive layer and the substrate, a known so-called adhesion improving agent can be used for each layer. Preferred examples of the adhesion improver include adhesion improvers described in JP-A-5-11439, JP-A-5-341532, JP-A-6-43638, and the like. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 3-morpholino Methyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, and 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole Amino group-containing benzotriazole, silane coupling agents, and the like.
As the adhesion improving agent, a silane coupling agent is preferable.

The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group that can be chemically bonded to an inorganic material. In addition, it preferably has a group that interacts or forms a bond with an organic resin and exhibits an affinity, and such a group has a (meth) acryloyl group, a phenyl group, a mercapto group, a glycidyl group, and an oxetanyl group. Among them, those having a (meth) acryloyl group or a glycidyl group are preferable.
That is, the silane coupling agent used in the present invention is preferably a compound having an alkoxysilyl group and a (meth) acryloyl group or an epoxy group, and specifically, a (meth) acryloyl-tri having the following structure. Examples include methoxysilane compounds and glycidyl-trimethoxysilane compounds.

In addition, the silane coupling agent in the present invention is also preferably a silane compound having at least two types of functional groups having different reactivity in one molecule, and particularly preferably having an amino group and an alkoxy group as functional groups. Examples of such silane coupling agents include N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-amino. Propyl-trimethoxysilane (trade name KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (trade name KBE-602 manufactured by Shin-Etsu Chemical Co., Ltd.) ), Γ-aminopropyl-trimethoxysilane (trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-triethoxysilane (trade name KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltri Methoxysilane (trade name KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.)

  0.001 mass%-20 mass% are preferable with respect to all the components except the solvent of the composition of this invention, as for content of the said adhesion improving agent, 0.01-10 mass% is more preferable, 0.1 mass % To 5% by mass is particularly preferable.

<Polymerization inhibitor>
In the composition of the present invention, it is desirable to add 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 composition.
Examples of the polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6- t-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
0.005-5 mass% is preferable with respect to the mass of all the compositions, and, as for the addition amount of a polymerization inhibitor, 0.01-5 mass% is more preferable.

<Surfactant>
Various surfactants may be added to the composition of the present invention 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 composition of the present invention contains a fluorosurfactant, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved. Sex can be improved more.
That is, when a film is formed using a coating liquid to which a composition containing a fluorosurfactant is applied, the wettability to the coated surface is reduced by reducing the interfacial tension between the coated surface and the coating liquid. 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 within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the 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 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.

  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, Sol Perth 20000 (manufactured by Nippon Lubrizol Corporation), and the like.

  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.
As for the addition amount of surfactant, 0.001 mass%-2.0 mass% are preferable with respect to the total mass of a composition, More preferably, they are 0.005 mass%-1.0 mass%.

<Other additives>
In the radiation-sensitive composition of the present invention, various additives such as a polymerization inhibitor, a surfactant, a filler, a polymer compound other than the above, an antioxidant, an anti-aggregation agent and the like are blended as necessary. I can do it.
Specific examples of these additives include fillers such as glass and alumina; antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; And an aggregation inhibitor such as sodium polyacrylate.

The radiation-sensitive composition of the present invention is an organic carboxylic acid, preferably a molecular weight of 1000, in order to promote alkali solubility in the ultraviolet-irradiated part of the radiation-sensitive composition and to further improve developability. The following low molecular weight organic carboxylic acids can be contained.
Specific examples of the organic carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid Aliphatic dicarboxylic acids such as acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid Acid; Aliphatic tricarboxylic acid such as tricarballylic acid, aconitic acid, and camphoronic acid; Aromatic monocarboxylic acid such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellito Aromatic polycarboxylic acids such as acids, trimesic acid, merophanoic acid, pyromellitic acid; Other carboxylic acids such as phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, and umberic acid It is done.

In addition, the radiation-sensitive composition of the present invention has a small amount of a colorant (a known dye or pigment (such as carbon black or titanium black) as long as it can form a white (transparent) pattern of a solid-state imaging device. May be included), but it is preferable not to include a colorant.
Specifically, the content of the colorant in the total solid content of the radiation-sensitive composition is preferably 3.0% by mass or less, more preferably 1.0% by mass or less from the viewpoint of the transmittance of the transparent pattern. 0% by mass (that is, a form containing no colorant) is particularly preferable.

The radiation-sensitive composition of the present invention described above is preferably used for transparent materials, particularly for pixel formation of solid-state imaging devices (particularly, transparent pixels that are transparent patterns).
From the viewpoint of being suitably used for such applications, the radiation-sensitive composition of the present invention has a transmittance of 90% or more over the entire wavelength region of 400 nm to 700 nm (more preferably, when the film has a thickness of 1 μm) (more preferably 95% or more).

<Filter filtration>
The composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. If it is conventionally used for the filtration use etc., it can use without being specifically limited.
As a filter used for filter filtration, if it is a filter conventionally used for the filtration use etc., it can use without being specifically limited.
Examples of the filter material include: a fluororesin such as PTFE (polytetrafluoroethylene); a polyamide resin such as nylon-6 and nylon-6, 6; a polyolefin resin such as polyethylene and polypropylene (PP) (high density, Including ultra high molecular weight); Among these materials, polypropylene (including high density polypropylene) is preferable.

The pore size of the filter is not particularly limited, but is, for example, about 0.01 to 20.0 μm, preferably about 0.01 to 5 μm, and more preferably about 0.01 to 2.0 μm.
By setting the pore size of the filter within the above range, fine particles can be more effectively removed and turbidity can be further reduced.
Here, the pore size of the filter can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (former Nihon Microlith Co., Ltd.), or Kitz Micro Filter Co., Ltd. .

In the filter filtration, two or more filters may be used in combination.
For example, the filtration can be performed first using a first filter and then using a second filter having a pore diameter different from that of the first filter.
At that time, the filtering by the first filter and the filtering by the second filter may be performed only once or may be performed twice or more, respectively.
As the second filter, a filter formed of the same material as the first filter described above can be used.

The radiation-sensitive composition of the present invention is cured and can be preferably used as a cured film for various elements. Specifically, a colored layer of a color filter can be given.
As an element containing the color filter of this invention, a solid-state image sensor (for example, CMOS image sensor, organic CMOS image sensor), a liquid crystal display device, and an organic EL display device are illustrated.
The method for producing the cured film of the present invention comprises:
(1) a step of applying the radiation-sensitive composition of the present invention on a substrate;
(2) a step of exposing the applied radiation-sensitive composition, and (3) a step of developing the exposed radiation-sensitive composition, and
(4) It is disclosed as a method for producing a cured film comprising a post-baking step of thermosetting the radiation-sensitive composition after development.

≪Color filter and manufacturing method≫
The method for producing a color filter of the present invention comprises (1) a step of applying the radiation-sensitive composition of the present invention on a substrate (film formation step), and (2) a step of exposing the applied radiation-sensitive composition ( (Exposure step), (3) a step of developing the exposed radiation-sensitive composition, and (4) a post-baking step (development step) of thermosetting the radiation-sensitive composition after development. Moreover, the process of hardening the said film | membrane or pattern by heating and exposure may be included if necessary.
The color filter of the present invention is obtained by the above production method.
In the method for producing a color filter of the present invention, since the radiation-sensitive composition of the present invention that has excellent resolution and suppresses deterioration of pattern rectangularity in post-baking in a post-process is used, the pixel (pattern) rectangular shape is used. It is possible to obtain a color filter that is excellent in performance and capable of displaying a fine and high-quality image.
The term “color” in the color filter of the present invention refers to “color” in a broad sense, and is a concept that includes chromatic colors such as red, blue, and green as well as achromatic colors such as transparency. That is, the pattern of the color filter of the present invention may be a chromatic pattern such as red, blue, or green, or an achromatic pattern such as transparency.
The color filter of the present invention may be a combination of at least one chromatic color pattern such as red, blue, and green and at least one achromatic color pattern such as transparency. Examples of such a color filter include a red pattern (red pixel), a blue pattern (blue pixel), a green pattern (green pixel), and a transparent pattern (transparent pixel).

  In the present invention, the “transparent pattern” refers to a pattern that exhibits high transmittance over the entire visible light region. Preferably, when the film thickness is 1 μm, the transmittance over the entire wavelength region of 400 nm to 700 nm is obtained. A pattern that is 90% or more (more preferably 95% or more) is preferable.

Hereinafter, as an example of a method for producing a color filter of the present invention, a method for forming a transparent pattern using a color filter for an image sensor will be described.
As the substrate, it is preferable to use a silicon wafer or a substrate provided with another layer on the silicon wafer.

  As a method for applying the radiation-sensitive composition, coating is preferable. For example, various methods such as a spray method, a roll coating method, and a spin coating method can be used.

In the exposure, pattern exposure is performed by irradiating light (preferably ultraviolet rays) through a photomask.
As ultraviolet rays used at least in the exposure, at least one of g-line, h-line and i-line is preferable, and i-line is more preferable.
As the exposure machine, for example, a stepper can be suitably used.

Development is performed by developing the exposed film with an alkaline developer.
Examples of the alkali developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; primary amines such as ethylamine and n-propylamine; Secondary amines such as n-propylamine; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine; alkanolamines such as dimethylethanolamine, methyldiethanolamine, triethanolamine; pyrrole, piperidine, N- Cyclic tertiary amines such as methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene; pyridine , Collidine, Cytidine, aromatic tertiary amines such as quinoline; tetramethylammonium hydroxide, the aqueous solution of quaternary ammonium salts such as tetraethyl ammonium hydroxide may be used.

  In addition, an appropriate amount of a water-soluble solvent such as methanol or ethanol and / or a surfactant can be added to the alkaline developer.

  As a developing method, any of a liquid filling method, a dipping method, a shower method and the like may be used, and the developing time is usually 30 to 180 seconds.

  After alkali development, for example, washing with running water is performed for 30 to 90 seconds, and the pattern is formed by drying with compressed air or compressed nitrogen, for example.

  Next, after exposing the pattern after alkali development again with ultraviolet rays, preferably, for example, on a hot plate, oven or the like, at a predetermined temperature, for example, 150 to 250 ° C., for a predetermined time, for example, on the hot plate A predetermined transparent pattern can be formed by performing post-baking for 5 to 30 minutes in an oven for 30 to 90 minutes.

  The transparent pattern thus formed has an array of a plurality of rectangular pixels on the substrate, and one side (maximum side) of the pixel is generally 1.0 to 20 μm or less. Of these, 5 μm or less is preferable, 4 μm or less is more preferable, and 3 μm or less is particularly preferable from the viewpoint of effective use of a substrate such as a silicon wafer, miniaturization of a device using a solid-state image sensor, and high-speed operation of the solid-state image sensor.

  Further, the thickness of the pixel in the color filter of the present invention is not particularly limited, but it tends to be thin from the viewpoint of effective use of a substrate such as a silicon wafer and shading of a device using a solid-state imaging device, and is 2 μm or less. Is preferable, 1.5 μm or less is more preferable, and 1.0 μm or less is particularly preferable.

  The color filter of the present invention can be used for a liquid crystal display device, a solid-state imaging device (for example, a CMOS sensor or an organic CMOS sensor), or an organic EL device, and is particularly suitable for solid-state imaging applications. When used in a liquid crystal display device, it contains a metal complex dye with excellent spectral characteristics and heat resistance as a colorant, but there are few alignment defects of liquid crystal molecules due to a decrease in specific resistance, and the color of the display image is good Excellent display characteristics.

<Liquid crystal display device>
Since the color filter of the present invention has colored pixels that are excellent in hue and excellent in light resistance, it is particularly suitable as a color filter for liquid crystal display devices. A liquid crystal display device provided with such a color filter can display a high-quality image having a good display image color tone and excellent display characteristics.

  For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issued in the first year). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The color filter of the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
The color filter of the present invention is a bright and high-definition COA (Color-filter On Array).
It is also possible to use the method. In a COA type liquid crystal display device, the required characteristics for the color filter layer require the required characteristics for the interlayer insulating film in addition to the normal required characteristics as described above, that is, low dielectric constant and peeling liquid resistance. Sometimes. In the color filter of the present invention, the (A) metal complex dye and the (B) complex-forming compound of the present invention are contained in the above ratio and cured, and the specific resistance of the liquid crystal material It is considered that the decrease is drastically prevented, and the alignment inhibition of the liquid crystal molecules, that is, the decrease in display characteristics is solved. As a result, it is excellent in good hues such as color purity, so that it is possible to provide a COA liquid crystal display device with high resolution and excellent long-term durability. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
Further, the colored layer formed by the COA method has a side length of about 1 to 15 μm in order to connect the ITO electrode arranged on the colored layer and the terminal of the driving substrate below the colored layer. It is necessary to form a conduction path such as a rectangular through hole or a U-shaped depression, and the dimension of the conduction path (that is, the length of one side) is preferably 5 μm or less, but the present invention is used. Thus, it is possible to form a conduction path of 5 μm or less. These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trends in the market (issued by Toray Research Center Research Division 2001)".

The liquid crystal display device of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. Regarding these materials, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding backlighting, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Yukiaki Yagi), etc. Have been described.

  When the color filter of the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, but further, red, green and blue LED light sources (RGB-LED). By using as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.

<Solid-state imaging device>
The solid-state image sensor of the present invention includes the above-described color filter for a solid-state image sensor of the present invention. The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter for the solid-state imaging device of the present invention, and is not particularly limited as long as the configuration functions as a solid-state imaging device. A configuration is mentioned.

A transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is provided on a support, A device having a light-shielding film made of tungsten or the like that is opened only in the light-receiving portion of the diode, and a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion; The color filter for a solid-state imaging device of the present invention is provided on the protective film.
Further, a configuration having light collecting means (for example, a microlens, etc., the same shall apply hereinafter) on the device protective layer and under the color filter (on the side close to the support), or a structure having the light collecting means on the color filter. Etc.
In addition, a CMOS image sensor of organic CMOS or Quantum Film may be used.

-Organic CMOS (Organic Seamoth Image Sensor)-
An organic CMOS sensor includes a thin panchromatic photosensitive organic photoelectric conversion film and a CMOS signal readout substrate as a photoelectric conversion layer, and an organic material plays a role of capturing light and converting it into an electric signal. It is a two-layered hybrid structure in which the inorganic material plays a role of taking out to the outside. In principle, the aperture ratio can be 100% with respect to incident light. The organic photoelectric conversion film is a structure-free continuous film that can be laid on a CMOS signal reading substrate, and therefore does not require an expensive fine processing process and is suitable for pixel miniaturization.
An example of an image sensor that is an organic CMOS will be described with reference to the drawings.

FIG. 1 is a schematic cross-sectional view showing the configuration of a multilayer imaging device (organic CMOS).
An image sensor 100 shown in FIG. 1 includes a substrate 101, an insulating layer 102, a connection electrode 103, a pixel electrode 104, a connection portion 105, a connection portion 106, an organic layer 107, a counter electrode 108, and a buffer layer. 109, a sealing layer 110, a color filter 111, a partition 112, a light shielding layer 113, a protective layer 114, a counter electrode voltage supply unit 115, and a readout circuit 116.
By using the above-described color filter of the present invention as the color filter 111, an image pickup element with low noise and good color reproducibility can be obtained.

  The substrate 101 is a glass substrate or a semiconductor substrate such as silicon. An insulating layer 102 is formed on the substrate 101. A plurality of pixel electrodes 104 and a plurality of connection electrodes 103 are formed on the surface of the insulating layer 102.

The organic layer 107 includes at least a photoelectric conversion layer. The photoelectric conversion layer generates a charge in response to received light, and is a layer made of an inorganic or organic photoelectric conversion material. The organic layer 107 is provided on the plurality of pixel electrodes 104 so as to cover them. The organic layer 107 has a constant thickness on the pixel electrode 104, but has an approximately trapezoidal shape that is inclined toward the substrate 101 at the end thereof.
Note that the organic layer 107 includes not only a layer formed of only an organic material but also a layer in which a part of the layer includes an inorganic material.

  The counter electrode 108 is an electrode facing the pixel electrode 104, and is provided on the organic layer 107 so as to cover it. The counter electrode 108 is made of a conductive material (for example, ITO or the like) that is transparent to incident light in order to make light incident on the organic layer 107. The counter electrode 108 is formed up to the connection electrode 103 disposed outside the organic layer 107 and is electrically connected to the connection electrode 103.

  The connection part 106 is embedded in the insulating layer 102 and is a plug or the like for electrically connecting the connection electrode 103 and the counter electrode voltage supply part 115. The counter electrode voltage supply unit 115 is formed on the substrate 101 and supplies a predetermined voltage to the counter electrode 104 via the connection unit 106 and the connection electrode 103. When the voltage to be supplied to the counter electrode 104 is higher than the power supply voltage of the image sensor 100, the power supply voltage is boosted by a booster circuit such as a charge pump to generate the predetermined voltage.

  The pixel electrode 104 is an electrode for collecting charges for collecting charges generated in the organic layer 107 between the pixel electrode 104 and the counter electrode 108 facing the pixel electrode 104. The readout circuit 116 is provided on the substrate 101 corresponding to each of the plurality of pixel electrodes 104, and reads out a signal corresponding to the charge collected by the corresponding pixel electrode 104. The reading circuit 116 is constituted by, for example, a CCD, a MOS circuit, a TFT circuit, or the like, and is shielded from light by a light shielding layer (not shown).

  The buffer layer 109 is formed on the counter electrode 108 so as to cover the counter electrode 108. The sealing layer 110 is formed on the buffer layer 109 so as to cover the buffer layer 109. The color filter 111 is formed at a position facing each pixel electrode 104 on the sealing layer 110. The partition walls 112 are provided in the gaps between the color filters 111 and improve the light transmission efficiency of the color filters 111. The light shielding layer 113 is formed in a region other than the region where the color filter 111 and the partition 112 are provided on the sealing layer 110, and prevents light from entering the peripheral circuit. The protective layer 114 is formed on the color filter 111, the partition 112, and the light shielding layer 113, and protects the entire image sensor.

  In the example of FIG. 1, the pixel electrode 104 and the connection electrode 103 are embedded in the surface portion of the insulating layer 102, but they may be formed on the insulating layer 102. In addition, although two sets of the connection electrode 103, the connection unit 106, and the counter electrode voltage supply unit 115 are provided, one set may be provided. As in the example of FIG. 1, by supplying a voltage from both ends of the counter electrode 108 to the counter electrode 108, a voltage drop at the counter electrode 108 can be suppressed. The number of sets may be increased or decreased as appropriate in consideration of the chip area of the element.

  The image sensor 100 has a plurality of pixel portions. The plurality of pixel portions are two-dimensionally arranged in a state where the substrate 101 is viewed in plan from the light incident side. The pixel portion includes a pixel electrode 104, an organic layer 107, a counter electrode 108 facing the pixel electrode 104, a sealing layer 110, a color filter 111, a partition 112, and a readout circuit 116.

  Next, a configuration example of the peripheral circuit will be described. The readout circuit 116 described above preferably employs a CCD or CMOS circuit for general image sensor applications. From the viewpoint of noise and high speed, it is preferable to employ a CMOS circuit. The configuration example of the peripheral circuit described below is a configuration example when a CMOS circuit is used as the reading circuit 116.

  FIG. 2 is a diagram illustrating an example of the entire configuration including peripheral circuits of the image sensor illustrated in FIG. As shown in FIG. 2, in addition to the configuration shown in FIG. 1, the image sensor 100 includes a vertical driver 121, a timing generator 122, a signal processing circuit 123, a horizontal driver 124, an LVDS 125, and serial conversion. A portion 126 and a pad 127.

  The pixel area shown in FIG. 2 corresponds to the first area shown in FIG. Each block in the pixel area represents a readout circuit 116. As the peripheral circuit of the image sensor, substantially the same peripheral circuit as that used in a general CMOS image sensor can be adopted. This imaging device is different from the peripheral circuit configuration of a general CMOS image sensor in that a counter electrode voltage supply unit 115 is added.

  The pad 127 is an interface used for input / output with the outside. The timing generator 122 supplies timing for driving the image sensor, and performs readout control such as thinning readout and partial readout. The signal processing circuit 123 is provided corresponding to each column of the reading circuit 116. The signal processing circuit 123 performs correlated double sampling (CDS) processing on the signal output from the corresponding column, and converts the processed signal into a digital signal. The signal processed by the signal processing circuit 123 is stored in a memory provided for each column. The vertical driver 121 performs control of reading a signal from the reading circuit 116. The horizontal driver 124 performs control to sequentially read out one row of signals stored in the memory of the signal processing circuit 123 and output the signals to the LVDS 125. The LVDS 125 transmits a digital signal in accordance with LVDS (Low voltage differential signaling). The serial conversion unit 126 converts the input parallel digital signal into a serial signal and outputs it.

  Note that the serial conversion unit 126 may be omitted. Further, the signal processing circuit 123 performs only correlated double sampling processing, and an AD conversion circuit may be provided instead of the LVDS 125. In addition, the signal processing circuit 123 may perform only correlated double sampling processing, and the LVDS 125 and the serial conversion unit 126 may be omitted. In this case, an AD conversion circuit may be provided outside the imaging element chip. Further, the signal processing circuit 123, the LVDS 125, and the serial conversion unit 126 may be disposed in one and the other of the regions adjacent to the pixel region. At this time, half of the columns of the readout circuit 116 (for example, odd columns) are processed by one signal processing unit 123 in the region adjacent to the pixel region, and the other half (for example, even columns) are adjacent to the pixel region. It is good also as a structure processed by the other signal processing part 123 of an area | region.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

<Synthesis of polymer>
<Synthesis Example 1-Polymer 1>
A solution having the following composition was prepared in a monomer dropping container.
・ Dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate (hereinafter referred to as “DM”) 13 parts ・ Benzyl methacrylate (hereinafter referred to as “BzMA”) 63 parts ・ Methyl methacrylate (hereinafter referred to as “MMA”) 15 parts) Methacrylic acid (hereinafter referred to as "MAA") 38 parts t-Butylperoxy-2-ethylhexanoate 2 parts Diethylene glycol dimethyl ether 32 parts

A solution having the following contents was prepared in a container for dropping a chain transfer agent.
-6 parts of n-dodecanethiol-20 parts of diethylene glycol dimethyl ether 188 parts of diethylene glycol dimethyl ether were placed in a reaction vessel (separable flask with a cooling tube), and after nitrogen substitution, the temperature of the reaction vessel was raised to 90 ° C.

After confirming temperature stability, dripping was started from the monomer dropping container and the chain transfer agent dropping container, and dropping of the monomer and the chain transfer agent was completed in 140 minutes while maintaining the temperature of 90 ° C.
60 minutes after the completion of dropping, the temperature was further raised, the temperature of the reaction vessel was raised to 110 ° C., and maintained at 110 ° C. for 180 minutes. Thereafter, the inside of the reaction vessel was replaced with air.

Next, a compound having the following composition was charged into the reaction vessel and reacted for 9 hours at a temperature of 110 ° C.
・ Glycidyl methacrylate (hereinafter referred to as “GMA”) 41 parts ・ 2,2′-methylenebis (4-methyl-6-tert-butylphenol) 0.2 part ・ Triethylamine 0.4 part After completion of the reaction, add 27 parts of diethylene glycol dimethyl ether The polymer 1 was obtained by cooling to room temperature.

<Synthesis Example 2-Polymer 2>
A solution having the following composition was prepared in a monomer dropping container.
-DM 22 parts-BzMA 70 parts-MMA 10 parts-MAA 34 parts-t-butylperoxy-2-ethylhexanoate 2 parts-diethylene glycol dimethyl ether 34 parts

A solution having the following contents was prepared in a container for dropping a chain transfer agent.
・ 6 parts of n-dodecanethiol ・ 20 parts of diethylene glycol dimethyl ether

188 parts of diethylene glycol dimethyl ether was placed in a reaction vessel (separable flask with a cooling tube), and after replacing with nitrogen, the reaction vessel was heated to raise the temperature of the reaction vessel to 90 ° C.
After confirming temperature stability, dripping was started from the monomer dropping container and the chain transfer agent dropping container, and dropping of the monomer and the chain transfer agent was completed in 140 minutes while maintaining the temperature of 90 ° C.
60 minutes after the completion of dropping, the temperature was further raised, the temperature of the reaction vessel was raised to 110 ° C., and maintained at 110 ° C. for 180 minutes. Thereafter, the inside of the reaction vessel was replaced with air.

Next, a compound having the following composition was charged into the reaction vessel and reacted for 9 hours at a temperature of 110 ° C.
-43 parts of GMA-0.2 parts of 2,2'-methylenebis (4-methyl-6-t-butylphenol)-0.4 parts of triethylamine After completion of the reaction, 39 parts of diethylene glycol dimethyl ether was added and cooled to room temperature to give polymer 2. Got.

<Synthesis Example 3-Polymer 3>
A solution having the following composition was prepared in a monomer dropping container.
・ BzMA 100 parts ・ MMA 16 parts ・ MAA 23 parts ・ t-butylperoxy-2-ethylhexanoate 2 parts ・ Diethylene glycol dimethyl ether 36 parts

A solution having the following contents was prepared in a container for dropping a chain transfer agent.
・ 4 parts of n-dodecanethiol ・ 20 parts of diethylene glycol dimethyl ether

188 parts of diethylene glycol dimethyl ether was placed in a reaction vessel (separable flask with a cooling tube), and after replacing with nitrogen, the reaction vessel was heated to raise the temperature of the reaction vessel to 90 ° C.
After confirming temperature stability, dripping was started from the monomer dropping container and the chain transfer agent dropping container, and dropping of the monomer and the chain transfer agent was completed in 140 minutes while maintaining the temperature of 90 ° C.
60 minutes after the completion of dropping, the temperature was further raised, the temperature of the reaction vessel was raised to 110 ° C., and maintained at 110 ° C. for 180 minutes. Thereafter, the inside of the reaction vessel was replaced with air.

Next, a compound having the following composition was charged into the reaction vessel and reacted for 9 hours at a temperature of 110 ° C.
GMA 15 parts 2,2′-methylenebis (4-methyl-6-tert-butylphenol) 0.2 part Triethylamine 0.4 part After completion of the reaction, the mixture was cooled to room temperature to obtain a polymer 3.

The solid contents of the polymers 1 to 3 obtained from the above synthesis examples were measured. Moreover, it analyzed about the component derived from each raw material monomer using < ¹ > H-NMR. Further, the weight average molecular weight was measured by GPC. The evaluation results are shown in Table 1 below.

<Example 1> Formation of transparent pattern of color filter for solid-state imaging device <Preparation of planarization film resist solution>
The following components were mixed and stirred with a homogenizer stirrer to prepare a flattening film resist solution.
Resist solution composition for flattening film ・ Propylene glycol monomethyl ether acetate solution of benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (20%, weight average molecular weight 30000, manufactured by Fujikura Kasei Co., Ltd.) , Product name Acrybase FF-187) 22 parts dipentaerythritol hexaacrylate 6.5 parts (product name KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.)
Propylene glycol monomethyl ether acetate (manufactured by Daicel Chemical Industries, Ltd., product name MMPGAC) 13.8 parts Ethyl-3-ethoxypropionate (manufactured by Nagase Sangyo Co., Ltd., product name ethyl-3 ethoxypropionate) ... 12.3 parts halomethyltriazine compound (compound I below) (manufactured by PANCHIM, product name triazine PP) 0.3 parts

<Fabrication of planarization film>
The flattening film resist solution obtained above was applied onto a 6-inch silicon wafer by spin coating. Subsequently, heat treatment was performed on a hot plate at a surface temperature of 100 ° C. for 120 seconds to obtain a uniform coating film having a thickness of about 1.0 μm on the silicon wafer. Next, the coating film was cured in an oven at 230 ° C. for 1 hour to obtain a flattened film.

<Adjustment of radiation-sensitive composition>
The following components were stirred and mixed using a magnetic stirrer to prepare the radiation-sensitive composition of the present invention.

・溶剤（プロピレングリコールモノメチルエーテル アセテート、ＰＧＭＥＡ）
５２．７重量部
・溶剤（シクロヘキサノン） １１．４重量部
・シランカップリング剤（信越シリコーン、ＫＢＭ−６０２） ０．１重量部
・重合禁止剤（ｐ−メトキシフェノール）（関東化学製） ０．１重量部
・界面活性剤（製造元：ＤＩＣ、品番：メガファックＦ−７８１−Ｆ） ０．１重量部 Composition of radiation-sensitive composition Polymer 1 20.5 parts by weight Polymerizable compound 1 (Aronix M-510, manufactured by Toa Gosei) 12.2 parts by weight Oxime polymerization initiator (manufacturer: BASF, product number: IRGACURE) OXE-02)
1.1 parts by weight / UV absorber (the following compound) 1.8 parts by weight

・ Solvent (propylene glycol monomethyl ether acetate, PGMEA)
52.7 parts by weight-Solvent (cyclohexanone) 11.4 parts by weight-Silane coupling agent (Shin-Etsu Silicone, KBM-602) 0.1 part by weight-Polymerization inhibitor (p-methoxyphenol) (manufactured by Kanto Chemical) 1 part by weight-surfactant (manufacturer: DIC, product number: Megafak F-781-F) 0.1 part by weight

<Preparation of coating film>
After applying the radiation-sensitive composition obtained from the above by spin coating on the planarized film of the silicon wafer, the coating film surface temperature is 100 ° C. for 120 seconds, heat-treated with a hot plate, and dried. A coating film having a thickness of about 0.8 μm after drying was formed.

<Formation of transparent pattern of color filter for solid-state image sensor>
Next, an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.) is passed through a mask pattern in which 1.2 μm square pixels are arranged in a 4 mm × 3 mm region on the substrate with respect to the coating film after drying. ) At an exposure amount of 100 mJ / cm ² .

The pattern-exposed coating film was subjected to paddle development for 60 seconds at room temperature using a 60% aqueous solution of an organic alkaline developer CD-2000 (Fuji Film Electronics Materials Co., Ltd.), and then spin showered for another 20 seconds. And rinsed with pure water. Thereafter, it was further washed with pure water. Thereafter, water droplets were blown with high-pressure air, the substrate was naturally dried, and post-baked with a hot plate at 220 ° C. for 300 seconds to form a transparent pattern on the silicon wafer.
As described above, a 1.0 μm square transparent pattern was produced on the planarized film of the silicon wafer to obtain a transparent pattern of a color filter for a solid-state imaging device.

Next, under the same conditions as those for producing a transparent pattern on the planarized film of the silicon wafer, the radiation-sensitive composition was applied onto Corning 1737 (manufactured by Corning) to form a coating film, The coating film was subjected to various processes such as overall exposure, development, rinsing, washing with water, and post-baking in this order to form a transparent film having a thickness of 1 μm, which was used as a transmittance measurement sample.
Next, the transmittance of this transparent film was measured using MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.). The transmittance was 93% or more over the entire wavelength region of 400 nm to 700 nm.

<Evaluation>
The following evaluation and measurement were performed on the transparent pattern on the planarized film of the silicon wafer obtained as described above. The results of evaluation and measurement are shown in the following table.

Residue The pixel pattern (1.0 μm square) of the post-baking color filter is 30,000 times from the upper side of the color filter on the silicon wafer using a length measuring SEM (S-7800H, manufactured by Hitachi, Ltd.) And the presence or absence of generation of residues was visually evaluated according to the following evaluation criteria.
The smaller the development residue, the better the pattern resolution.
5: 5 or less 4: 6-10 pieces 3: 11-20 pieces 2: 21-50 pieces 1: 51 pieces or more

Dimensional uniformity The pattern size of the central part and the end part (corner part) of square pixels in a 1/3 inch size area (4.8 mm × 3.6 mm, hereinafter referred to as “one shot”) on the substrate. The difference was measured. Specifically, the absolute value | Δa | (= | a1−a2 |) of the difference between the pattern size a1 at the center of the pattern and the pattern size a2 at the end in one shot was measured. An image diagram is shown below.

Evaluation was made according to the following criteria.
5: ≦ 0.01
4: 0.01 <| Δa | ≦ 0.03
3: 0.03 <| Δa | ≦ 0.05
2: 0.05 <| Δa | ≦ 0.10
1: 0.10 <| Δa |

Line width change after application About pattern size b1 when patterning is performed by performing an exposure process after coating, and pattern size b2 when patterning is performed by performing an exposure process after coating and leaving for 72 hours after coating. Each was carried out in the same manner as the above dimensional stability, the value of Δa was determined, and the absolute value | Δb | (= | b1-b2 |) of the difference was evaluated as follows.
5: ≦ 0.01
4: 0.01 <| Δb | ≦ 0.03
3: 0.03 <| Δb | ≦ 0.05
2: 0.05 <| Δb | ≦ 0.10
1: 0.10 <| Δb |

<Other examples and comparative examples>
In the said Example 1, the kind of polymer and the kind of polymeric compound were changed as follows, others were performed similarly, and the radiation sensitive composition of an Example and a comparative example was obtained.
M / B has an acid group and has a bifunctional or higher functionality (meth) acrylate compound / total polymer × 100.

-Polymer 4: Daicel Chemical Industries, Cyclomer ACA230AA)
Polymerizable compound 2 (TO-2349, manufactured by Toa Gosei)
Polymerizable compound 3 (A-DPH-12E, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Polymerizable compound 4 (KAYARAD DPHA, manufactured by Nippon Kayaku)
Polymerizable compound 5 (Aronix M-305, manufactured by Toagosei)

As shown in the above table, when the radiation-sensitive composition has a polymer represented by the general formula (1), an acid group, and a trifunctional or tetrafunctional (meth) acrylate compound, It was found that there were few residues, and excellent dimensional uniformity and line width change after laying were obtained. In particular, the weight ratio of the total amount of the polymer and the acid group and the total amount of the bifunctional or higher (meth) acrylate (having the acid group and the bifunctional or higher (meth) acrylate / total weight) It was found that the residue was further improved when the coalescence was in the range of 1 to 50% by mass.
In particular, the pattern size of 1.0 μm square is highly significant in that such a high residue is small and excellent in both dimensional uniformity and line width change after placement can be obtained.

In the above embodiment, an example in which a transparent pattern of a color filter is formed on a silicon wafer has been described. However, when a solid-state imaging device is manufactured, the silicon wafer is formed using a photodiode, a light shielding film, a device protection film, and the like. What is necessary is just to substitute for the board | substrate for solid-state image sensors with formed.
For example, on a silicon wafer on which a photodiode and a transfer electrode are formed, a light shielding film made of tungsten having an opening only in the light receiving portion of the photodiode is formed, and the entire surface of the formed light shielding film and the photodiode light receiving portion (openings in the light shielding film). A device protective layer made of silicon nitride is formed so as to cover the portion. Next, on the formed device protective layer, a transparent pattern (transparent pixel) is formed by the same method as in the above embodiment, and a red pixel, a blue pixel, and a green pixel are formed by a known method. To do. Next, by forming a microlens as a condensing means on the obtained color filter, a solid-state imaging device (CCD, CMOS, organic CMOS, etc.) with good color reproducibility can be produced.

DESCRIPTION OF SYMBOLS 100 Image sensor 101 Board | substrate 102 Insulating layer 103 Connection electrode 104 Pixel electrode 105 Connection part 106 Connection part 107 Organic layer 108 Counter electrode 109 Buffer layer 110 Sealing layer 111 Color filter 112 Partition 113 Light shielding layer 114 Protection layer 115 Counter electrode voltage supply part 116 Reading circuit 121 Vertical driver 122 Timing generator 123 Signal processing circuit 124 Horizontal driver 125 LVDS
126 Serial Converter 127 Pad

Claims (10)

Containing a polymer, a polymerizable compound and a polymerization initiator,
As the polymer, including a polymer obtained by polymerizing a monomer component containing a compound represented by the following general formula (ED),
A radiation-sensitive composition having an acid group and containing a bifunctional or higher functional (meth) acrylate compound as the polymerizable compound.

(In General Formula (ED), R ¹ and R ² each represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.) Ratio of (meth) acrylate compound having an acid group and bifunctional or higher with respect to the total amount of the polymer ((meth) acrylate compound having an acid group and bifunctional or higher) / total polymer × 100 ) In the range of 1 to 50% by mass. The radiation-sensitive composition according to claim 1 or 2, further comprising a polymerizable compound other than a bifunctional or higher-functional (meth) acrylate compound as the polymerizable compound. 4. The radiation-sensitive composition according to claim 3, wherein the polymerizable compound has an acid group and a proportion of a bifunctional or higher-functional (meth) acrylate compound is 1 to 50 mass%. The radiation sensitive composition of any one of Claims 1-4 containing at least 1 sort (s) selected from a ultraviolet absorber, a solvent, an adhesion improving agent, a polymerization inhibitor, and surfactant. The cured film formed by hardening | curing the radiation sensitive composition of any one of Claims 1-5. The color filter which has a colored layer formed by hardening | curing the radiation sensitive composition of any one of Claims 1-5. (1) The process of applying the radiation sensitive composition of any one of Claims 1-5 on a board | substrate,
(2) a step of exposing the applied radiation-sensitive composition;
(3) a step of developing the exposed radiation-sensitive composition, and
(4) A method for producing a cured film, comprising a post-baking step of thermosetting the radiation-sensitive composition after development. (1) The process of applying the radiation sensitive composition of any one of Claims 1-5 on a board | substrate,
(2) a step of exposing the applied radiation-sensitive composition;
(3) a step of developing the exposed radiation-sensitive composition, and
(4) A method for producing a color filter, comprising a post-baking step of thermosetting the radiation-sensitive composition after development. A solid-state imaging device, a liquid crystal display device, or an organic EL display device having the color filter according to claim 7 or the color filter manufactured by the manufacturing method according to claim 9.

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