JP5849011B2 - Solder resist composition, cured film, and method for producing cured film - Google Patents

Description

  The present invention relates to a solder resist composition. Furthermore, it is related also with the cured film using a soldering resist composition, and the manufacturing method of this cured film. The present invention also relates to a solid-state imaging device, a liquid crystal display device, or an organic EL display device including such a cured film.

Conventionally, when forming a permanent pattern such as a solder resist, when forming a photosensitive layer on a target member, a liquid composition is formed using a spin coating method, a screen printing method, or a spray printing method. And a method of transferring the photosensitive layer only onto a member using a vacuum laminator or a roll laminator. It has been. As a method of forming a permanent pattern such as a solder resist, for example, a photosensitive layer is formed on the silicon wafer on which the permanent pattern is formed, on a wired silicon wafer, or on a substrate such as a copper clad laminate by the above method. And a method of forming a permanent pattern by exposing the photosensitive layer in the laminate, developing the photosensitive layer after exposure to form a pattern, and then performing a curing treatment, etc. ing.
Such a permanent pattern of solder resist is widely used in solid-state imaging devices (image sensors) used in mobile phones, digital cameras, digital videos, surveillance cameras, and the like (Patent Document 1).

JP2012-003225A

  However, the solder resist composition is often used not only for pattern formation immediately after being adjusted, but also for pattern formation after it has been stored once. When this inventor examined various performances after preservation | save for a fixed period, it turned out that there exists a tendency for various performances to deteriorate. The object of the present invention is to provide a solder resist composition that is excellent in infrared light shielding properties and has little deterioration over time.

  Based on the above problems, the inventors of the present application have conducted intensive studies, and as a result, by using a specific polymerizable compound, it is possible to obtain a solder resist composition having excellent infrared light shielding properties and little deterioration after aging. I found it. In particular, as shown in the examples described later, even if the compound is similar to the specific polymerizable compound used in the present invention, a great difference occurs in deterioration after the lapse of time. You can see if it is.

（一般式（１）中、Ｌは、それぞれ、アルキレン基と−Ｏ−の組み合わせからなる基であり、Ａｃは、それぞれ、（メタ）アクリロイルオキシ基である。）
＜２＞一般式（１）中、Ｌは、−ＣＨ₂−と−Ｏ−の組み合わせからなる基である、＜１＞に記載のソルダーレジスト組成物。
＜３＞上記赤外線遮光性粒子が、タングステン化合物を含む、＜１＞または＜２＞に記載のソルダーレジスト組成物。
＜４＞上記赤外線遮光性粒子が、下記一般式（２）で表される、＜１＞または＜２＞に記載のソルダーレジスト組成物。
Ｍ_xＷ_yＯ_z・・・（２）
Ｍは金属、Ｗはタングステン、Ｏは酸素を表す。
０．００１≦ｘ／ｙ≦１．１
２．２≦ｚ／ｙ≦３．０
＜５＞一般式（２）において、Ｍがアルカリ金属である、＜４＞に記載のソルダーレジスト組成物。
＜６＞一般式（２）において、Ｍがセシウムである、＜４＞に記載のソルダーレジスト組成物。
＜７＞一般式（１）において、Ｌは、−Ｃ₂Ｈ₄−と−Ｏ−の組み合わせからなる基である、＜１＞〜＜６＞のいずれかに記載のソルダーレジスト組成物。
＜８＞さらに、重合開始剤を含有する、＜１＞〜＜７＞のいずれかに記載のソルダーレジスト組成物。
＜９＞さらに、α−アミノケトン系重合開始剤を含有する、＜１＞〜＜７＞のいずれかに記載のソルダーレジスト組成物。
＜１０＞さらに、アルカリ可溶性バインダーを含む、＜１＞〜＜９＞のいずれかに記載のソルダーレジスト組成物。
＜１１＞固形分濃度が３０〜８０質量％である、＜１＞〜＜１０＞のいずれかに記載のソルダーレジスト組成物。
＜１２＞＜１＞〜＜１１＞のいずれかに記載のソルダーレジスト組成物を硬化してなる硬化膜。
＜１３＞＜１２＞に記載の硬化膜を含む、固体撮像素子、液晶表示装置または有機ＥＬ表示装置。
＜１４＞＜１＞〜＜１１＞のいずれかに記載のソルダーレジスト組成物を基板上に適用する工程と、該ソルダーレジスト組成物をパターン露光する工程を含む、パターン硬化膜の製造方法。
＜１５＞＜１＞〜＜１１＞のいずれかに記載のソルダーレジスト組成物を基板上に適用する工程、該ソルダーレジスト組成物を露光する工程を含む、固体撮像素子、液晶表示装置または有機ＥＬ表示装置の製造方法。
＜１６＞さらに、溶剤、アルカリ可溶性樹脂（好ましくは、全固形分の３０〜８０質量％）、重合開始剤、界面活性剤、増感剤、紫外線吸収剤、シランカップリング剤、フィラー（好ましくは、全固形分の１〜６０質量％）および分散剤の少なくとも１種を含む、＜１＞〜＜１１＞のいずれかに記載のソルダーレジスト組成物。
＜１７＞さらに、溶剤、アルカリ可溶性樹脂および重合開始剤を含む、＜１＞〜＜１１＞および＜１６＞のいずれかに記載のソルダーレジスト組成物。
＜１８＞膜厚２５μｍとしたときの、波長１２００ｎｍにおける膜の透過率が２％以下である、＜１＞〜＜１１＞、＜１６＞および＜１７＞のいずれかに記載のソルダーレジスト組成物。
＜１９＞２５℃における粘度が１０〜３０００ｍＰａ・ｓである、＜１＞〜＜１１＞、＜１６＞〜＜１８＞のいずれかに記載のソルダーレジスト組成物。
＜１９＞一般式（１）で表される、ソルダーレジスト組成物の経時劣化防止剤。
一般式（１）

（一般式（１）中、Ｌは、アルキレン基と−Ｏ−の組み合わせからなる基であり、Ａｃは（メタアクリロイルオキシ基である。） Specifically, the above problem has been solved by the following means <1>, preferably by <2> to <20>.
<1> A solder resist composition comprising a compound represented by the general formula (1) and infrared ray shielding particles.
General formula (1)

(In General Formula (1), each L is a group composed of a combination of an alkylene group and -O-, and each Ac is a (meth) acryloyloxy group.)
<2> In the general formula (1), L is a solder resist composition according to <1>, which is a group composed of a combination of —CH ₂ — and —O—.
<3> The solder resist composition according to <1> or <2>, wherein the infrared light shielding particles include a tungsten compound.
<4> The solder resist composition according to <1> or <2>, wherein the infrared light shielding particles are represented by the following general formula (2).
M _x W _y O _z (2)
M represents a metal, W represents tungsten, and O represents oxygen.
0.001 ≦ x / y ≦ 1.1
2.2 ≦ z / y ≦ 3.0
<5> The solder resist composition according to <4>, wherein M is an alkali metal in the general formula (2).
<6> The solder resist composition according to <4>, wherein in general formula (2), M is cesium.
<7> In the general formula (1), L is a solder resist composition according to any one of <1> to <6>, which is a group composed of a combination of —C ₂ H ₄ — and —O—.
<8> The solder resist composition according to any one of <1> to <7>, further containing a polymerization initiator.
<9> The solder resist composition according to any one of <1> to <7>, further comprising an α-aminoketone polymerization initiator.
<10> The solder resist composition according to any one of <1> to <9>, further including an alkali-soluble binder.
The solder resist composition in any one of <1>-<10> whose <11> solid content concentration is 30-80 mass%.
<12> A cured film obtained by curing the solder resist composition according to any one of <1> to <11>.
<13> A solid-state imaging device, a liquid crystal display device or an organic EL display device comprising the cured film according to <12>.
<14> A method for producing a patterned cured film, comprising a step of applying the solder resist composition according to any one of <1> to <11> on a substrate and a step of pattern exposure of the solder resist composition.
<15> A solid-state imaging device, a liquid crystal display device, or an organic EL, comprising a step of applying the solder resist composition according to any one of <1> to <11> onto a substrate, and a step of exposing the solder resist composition Manufacturing method of display device.
<16> Further, a solvent, an alkali-soluble resin (preferably, 30 to 80% by mass of the total solid content), a polymerization initiator, a surfactant, a sensitizer, an ultraviolet absorber, a silane coupling agent, and a filler (preferably The solder resist composition according to any one of <1> to <11>, comprising 1 to 60% by mass of a total solid content) and at least one dispersant.
<17> The solder resist composition according to any one of <1> to <11> and <16>, further comprising a solvent, an alkali-soluble resin, and a polymerization initiator.
<18> The solder resist composition according to any one of <1> to <11>, <16> and <17>, wherein the transmittance of the film at a wavelength of 1200 nm is 2% or less when the film thickness is 25 μm. .
<19> The solder resist composition according to any one of <1> to <11> and <16> to <18>, which has a viscosity at 25 ° C. of 10 to 3000 mPa · s.
<19> An agent for preventing deterioration of a solder resist composition with time, represented by the general formula (1).
General formula (1)

(In General Formula (1), L is a group consisting of a combination of an alkylene group and —O—, and Ac is a (methacryloyloxy group).

  It has become possible to provide a solder resist composition that has excellent infrared shielding properties and little deterioration over time.

It is a schematic sectional drawing which shows the structure of the camera module provided with the solid-state image sensor which concerns on embodiment of this invention. 1 is a schematic cross-sectional view of a solid-state image sensor according to an embodiment of the present invention. It is a schematic sectional drawing of the board | substrate A used in Example 2-1 and Example 2-2. 2 is a schematic cross-sectional view showing a state where a light shielding film is formed on a substrate A. FIG. It is a schematic sectional drawing of the board | substrate B used in Example 2-1 and Example 2-2. 4 is a schematic cross-sectional view showing a state where a light shielding film is formed on a substrate B. FIG. It is a top view which shows an example of a wafer level lens array. It is the sectional view on the AA line shown in FIG. It is a figure which shows the state which is supplying the molding material used as a lens to a board | substrate. 10A to 10C are diagrams illustrating a procedure for forming a lens on a substrate with a mold. 10A to 10C are schematic views illustrating a process of forming a patterned light-shielding film on a substrate on which a lens is molded. It is sectional drawing which shows an example of a wafer level lens array. 10A to 10C are schematic views illustrating another aspect of the light shielding film forming step. FIG. 10A to FIG. 10C are schematic views showing a process of molding a lens on a substrate having a patterned light-shielding film. It is drawing of the pattern in the exposure used for the Example.

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 “monomer” 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.
In the present invention, infrared refers to electromagnetic waves having a wavelength of 700 to 2500 nm.

Solder resist composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”), cured film, solid-state imaging device, liquid crystal display device, organic EL display device, pattern cured film manufacturing method, solid-state imaging device, A manufacturing method of the liquid crystal display device or the 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.
The solder resist composition of the present invention comprises a compound represented by the general formula (1) and infrared light shielding particles.

（一般式（１）中、Ｌは、それぞれ、アルキレン基と−Ｏ−の組み合わせからなる基であり、Ａｃは、それぞれ、（メタ）アクリロイルオキシ基である。） <Compound represented by the general formula (1)>
The composition of this invention contains the compound represented by General formula (1).
General formula (1)

(In General Formula (1), each L is a group composed of a combination of an alkylene group and -O-, and each Ac is a (meth) acryloyloxy group.)

In general formula (1), each L is preferably a group consisting of a combination of —CH ₂ — and —O—, and preferably a group consisting of a combination of —C ₂ H ₄ — and —O—. More preferred is a group in which —C ₂ H ₄ — and —O— are alternately repeated. In this case, both the group bonded to L and the group bonded to Ac are preferably —C ₂ H ₄ —. Moreover, in the L, -C ₂ H ₄ - number of, preferably 1 to 4, 2 or 3 further preferred.
In the general formula (1), the number of atoms constituting the main chain of L (the number of atoms in the chain between Ac and O atoms) is preferably 3 to 12, and more preferably 4 to 10, respectively. The number of atoms constituting the main chain of L is 5, for example, when the L portion is —C ₂ H ₄ —O—C ₂ H ₄ —.
In General formula (1), it is preferable that four L is the same.
Ac is more preferably an acryloyloxy group.

The molecular weight of the compound represented by the general formula (1) is preferably 400 to 1100, and more preferably 600 to 1000.
The viscosity of the compound represented by the general formula (1) is preferably 100 to 900 mPa · s, and more preferably 200 to 500 mPa · s.

  It is preferable that the compound represented by General formula (1) is contained in the ratio of 1-30 mass% with respect to all the components except the solvent of the composition of this invention, and is contained in the ratio of 5-15 mass%. It is more preferable. Only one type of compound represented by the general formula (1) may be used, or two or more types may be used. In the case of two or more types, the total amount is preferably within the above range.

Although the preferable example of a compound represented by General formula (1) used by this invention below is shown, it cannot be overemphasized that this invention is not limited to these.

The composition of the present invention may contain a polymerizable compound other than the compound represented by the general formula (1).
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 chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and multimers thereof. 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 anurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A-51- 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 Preferred is a form that binds to

  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 and the like 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, further preferably 40% by mass or less, and more preferably 10% by mass. % Or less is more preferable, and it is more preferable not to contain substantially. “Substantially” means, for example, 5% by mass or less and preferably 2% by mass or less of the total amount of the polymerizable compound.

<Infrared light shielding particles>
The infrared light shielding particle used in the present invention refers to a compound corresponding to absorbance (500 nm) / absorbance (900 nm) <0.3. Infrared light shielding particles preferably have good transmission of light used for exposure. From such a viewpoint, the other infrared light shielding particles are selected from infrared absorbing dyes and infrared absorbing inorganic pigments. It is preferable. The infrared ray shielding particles used in the present invention are preferably tungsten compounds (compounds containing tungsten).

Tungsten compounds have high absorption with respect to infrared rays (light having a wavelength of about 800 to 1200 nm) (that is, high shielding properties against infrared rays (shielding properties)), and infrared shielding particles with low absorption with respect to visible light. It is. Therefore, according to the composition of the present invention, by containing the tungsten compound, it is possible to form a pattern having a high light-shielding property in the infrared region and a high light-transmitting property in the visible light region.
In addition, the tungsten compound has less absorption even for light having a shorter wavelength than that in the visible range used for exposure of a high-pressure mercury lamp, KrF, ArF, or the like used for image formation. Therefore, an excellent pattern can be obtained by combining such a tungsten compound with a polymerization initiator, a polymerizable compound, and an alkali-soluble binder.

Examples of the tungsten compound include a tungsten oxide compound, a tungsten boride compound, a tungsten sulfide compound, and the like, and a tungsten oxide compound represented by the following general formula (2) is more preferable.
M _x W _y O _z (2)
M represents a metal, W represents tungsten, and O represents oxygen.
0.001 ≦ x / y ≦ 1.1
2.2 ≦ z / y ≦ 3.0

  As the metal of M, alkali metal, alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Examples include Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, and Bi, and an alkali metal is preferable. The metal of M may be one type or two or more types.

  M is preferably an alkali metal, preferably Rb or Cs, and more preferably Cs.

When x / y is 0.001 or more, infrared rays can be sufficiently shielded, and when it is 1.1 or less, generation of an impurity phase in the tungsten compound can be more reliably avoided. it can.
When z / y is 2.2 or more, chemical stability as a material can be further improved, and when it is 3.0 or less, infrared rays can be sufficiently shielded.

Specific examples of the tungsten oxide compound represented by the general formula (2) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 and the} like, and Cs _0.33 WO ₃ Alternatively, Rb _0.33 WO ₃ is preferable, and Cs _0.33 WO ₃ is more preferable.

  The average particle size of the tungsten compound is preferably 800 nm or less, more preferably 400 nm or less, and even more preferably 200 nm or less. When the average particle diameter is in such a range, the tungsten fine particles are less likely to block visible light by light scattering, and thus the translucency in the visible light region can be further ensured. From the viewpoint of avoiding photoacid disturbance, the average particle size is preferably as small as possible. However, for reasons such as ease of handling during production, the average particle size of the tungsten fine particles is usually 1 nm or more.

The content of the tungsten compound is preferably 3% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 10% by mass or less with respect to the total solid mass of the composition of the present invention.
Two or more tungsten compounds can be used.

Tungsten compounds are commercially available, but when the tungsten compound is, for example, a tungsten oxide compound, the tungsten oxide compound is obtained by a method of heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere. (See Japanese Patent No. 4096205).
In addition, the tungsten oxide compound is also available as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.

Examples of infrared absorbing dyes include metal complex dyes such as cyanine dyes, phthalocyanine dyes, naphthalocyanine dyes, immonium dyes, aminoum dyes, quinolium dyes, pyrylium dyes, and Ni complex dyes.
The pigment | dye which can be used as infrared rays light-shielding particle | grains can also be obtained as a commercial item, for example, the following commercial pigment | dyes are mentioned suitably.
F0 Chemicals S0345, S0389, S0450, S0253, S0322, S0585, S0402, S0337, S0391, S0094, S0325, S0260, S0229, S0447, S0378, S0306, S0484
American Dye Source, Inc. Ltd. ADS795WS, ADS805WS, ADS819WS, ADS820WS, ADS823WS, ADS830WS, ADS850WS, ADS845MC, ADS870MC, ADS880MC, ADS890MC, ADS920MC, ADS990MC, ADS805PI, ADSW805PP, ADS810CO, ADS813MT, ADS815EI, ADS816EI, ADS818HT, ADS819MT, ADS819MT, ADS821NH, ADS822MT, ADS838MT , ADS840MT, ADS905AM, ADS956BP, ADS1040P, ADS1040T, ADS1045P, ADS1040P, ADS1050P, ADS1065A, ADS1065P, ADS1100T, ADS1120 F

YKR-4010, YKR-3030, YKR-3070, MIR-327, MIR-371, SIR-159, PA-1005, MIR-369, MIR-379, SIR-128, PA-1006, YKR, manufactured by Yamamoto Kasei Co., Ltd. -2080, MIR-370, YKR-3040, YKR-3081, SIR-130, MIR-362, YKR-3080, SIR-132, PA-1001
NK-123, NK-124, NK-1144, NK-2204, NK-2268, NK-3027, NKX-113, NKX-1199, NK-2674, NK-3508, NKX-114, manufactured by Hayashibara Biochemical Research Institute NK-2545, NK-3555, NK-3509, NK-3519

Among these dyes, phthalocyanine dyes and metal complex dyes are preferable from the viewpoint of heat resistance.
These dyes may be used alone, but for the purpose of expressing good light-shielding properties at 800-1200 nm, two or more of these dyes may be used in combination.

Examples of infrared absorbing inorganic pigments that can be used as other infrared shielding materials include zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red , Yellow lead, zinc yellow (zinc yellow 1 type, zinc yellow 2 type), ultramarine blue, procyan blue (potassium ferrocyanide), zircon gray, praseodymium yellow, chrome titanium yellow, chrome green, peacock, victoria green, Examples include bitumen (unrelated to Prussian blue), vanadium zirconium blue, chrome tin pink, ceramic red, salmon pink, etc., and black pigments such as Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti And a metal oxide, metal nitride or a metal oxide containing one or more metal elements selected from the group consisting of Ag and Ag It can be used such as a mixture of.
As the black pigment, titanium black, which is a black pigment containing titanium nitride, is preferable because it has a good shielding property in the infrared region with a wavelength of 800 to 1200 nm.
Titanium black can be obtained by a known method, and as commercially available products, for example, Ishihara Sangyo Co., Ltd., Ako Kasei Co., Ltd., Gemco Co., Ltd., Mitsubishi Materials Corporation, and Mitsubishi Materials You may use the titanium black by an electronic chemical company.

Titanium black refers to black particles having titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride. As the titanium black particles, particles whose surfaces are modified may be used as necessary for the purpose of improving dispersibility and suppressing aggregation.
Examples of the surface modification method include a method in which the surface is coated with one or more selected from silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, and zirconium oxide, and Japanese Patent Application Laid-Open No. 2007-302836. You may surface-treat with a water-repellent substance as shown in the paragraph numbers [0010] to [0027] of the publication.

  Titanium black is produced by heating a mixture of titanium dioxide and metal titanium in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, No. 61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610). It is not a thing.

The particle size of the titanium black particles is not particularly limited, but is preferably 3 to 2000 nm, more preferably 10 to 500 nm, from the viewpoint of dispersibility and colorability.
The specific surface area of titanium black is not particularly limited, but the water repellency after surface treatment of such titanium black with a water repellent becomes a predetermined performance. ² / g approximately, and preferably from 20 to 100 m ² / g approximately.

  The particle diameter of the inorganic pigment used as the other infrared light shielding particles is preferably 3 nm to 0.01 mm in average particle diameter, and the average particle diameter is 10 nm from the viewpoints of dispersibility, light shielding properties, and sedimentation over time. It is preferably ˜1 μm.

  Only one type of infrared light shielding particle may be used, or two or more types may be used. Infrared light-shielding particles are preferably contained in a proportion of 1 to 30% by mass and more preferably in a proportion of 5 to 15% by mass with respect to all components except the solvent of the composition of the present invention.

<Other ingredients>
The composition of the present invention may contain at least one of a solvent, an alkali-soluble resin, a polymerization initiator, a surfactant, a sensitizer, an ultraviolet absorber, a silane coupling agent, a filler, and a dispersant. , Solvent, alkali-soluble resin, and polymerization initiator. Furthermore, an optional component selected from a surfactant, a sensitizer, an ultraviolet absorber, a silane coupling agent, and a filler may be included.
Furthermore, crosslinking agents, curing accelerators, elastomers, organic carboxylic acids or organic carboxylic acid anhydrides, thermal curing accelerators, thermal polymerization inhibitors, plasticizers, colorants (color pigments or dyes), and adhesion promotion to the substrate surface Agents and other auxiliary agents (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) May be.
Hereinafter, these components will be described in detail.

<Solvent>
In general, the composition of the present invention can be constituted using a solvent. The solvent is basically not particularly limited as long as the solubility of each component and the coating property of the composition are satisfied. Moreover, when preparing the composition in this invention, you may use 2 or more types of solvents.

  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, methyl lactate, ethyl lactate, Alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate (Eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)) ), 2-Oki Propionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropion) Propyl acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, 2-methoxy-2-methyl Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. And examples of ethers 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 and the like, and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone, and aromatic hydrocarbons such as toluene and xylene Len and the like are preferred.

  It is also preferable to mix two or more of these solvents from the viewpoints of the solubility of the ultraviolet absorber and the alkali-soluble resin, the improvement of the coated surface, and the like. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

  When the composition of the present invention contains a solvent, the content of the solvent in the composition is preferably such that the total solid concentration of the composition is 5 to 80% by mass from the viewpoint of applicability. -60 mass% is still more preferable, and 10-50 mass% is especially preferable.

<Alkali-soluble resin>
The composition of the present invention preferably further contains an alkali-soluble resin. By containing an alkali-soluble resin, developability and pattern formation are improved.

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.

（式（ＥＤ）中、Ｒ¹およびＲ²は、それぞれ独立して、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。）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。）を必須とする単量体成分を重合してなるポリマーを、アルカリ可溶性樹脂として含むことも好ましい。これにより、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中、Ｒ¹および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；フェニル基等のアリール基；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基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。 As an alkali-soluble resin, the following general formula (ED)

(In formula (ED), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.) It is also preferable to include a polymer obtained by polymerizing a monomer component essential to “ether dimer” as an alkali-soluble resin. Thereby, the composition of this invention can form the cured coating film which was very excellent also in heat resistance and transparency. In the general formula showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, but for example, a methyl group Linear or branched alkyl such as 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, etc. Group; aryl group such as phenyl group; alicyclic group such as cyclohexyl group, t-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, 2-methyl-2-adamantyl group, etc. An alkyl group substituted with an alkoxy group such as a 1-methoxyethyl group or a 1-ethoxyethyl group; an alkyl group substituted with an aryl group such as benzyl; Can be mentioned. 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.

As the alkali-soluble phenol resin, it can be suitably used when the composition of the present invention is a positive composition. 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, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic 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.

  When the alkali-soluble resin is contained, the content in the composition is preferably 30 to 80% by mass, and more preferably 50 to 70% by mass with respect to the total solid content of the composition. One kind of alkali-soluble resin may be used, or two or more kinds may be used, and when two or more kinds are included, the total amount falls within the above range.

<Polymerization initiator>
The composition of the present invention preferably further contains a polymerization initiator from the viewpoint of further improving sensitivity.
As a polymerization initiator in this invention, what is known as a polymerization initiator described below can be used.
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, the cyclic oxime compounds fused to the carbazole dyes described in JP2010-32985A and JP2010-185072A in particular have high light absorptivity from the viewpoint of 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, pleiadenyl 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 alkylthiocarbonyl group which may have a substituent include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, and an octadecylthiocarbonyl group. Examples thereof include a group and a trifluoromethylthiocarbonyl group.

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

  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.

<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”, “Tore 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 Chemical Co., Ltd.,“ BYK307 ”,“ BYK323 ”,“ BYK330 ”manufactured by BYK 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%.

<Sensitizer>
The composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the polymerization initiator and increasing the photosensitive wavelength. As the sensitizer that can be used in the present invention, those that sensitize the above-mentioned photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism are preferable. Examples of the sensitizer that can be used in the present invention include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.

Examples of preferred sensitizers include those belonging to the following compounds and having an absorption wavelength in the range of 330 nm to 450 nm.
For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (2,4-diethylthioxanthone, isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg, Thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthrone) Laquinone), squalium (for example, squalium), acridine orange, coumarins (for example, 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, Distyrylbenzenes, carbazoles, porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone , Aromatic ketone compounds such as Michler's ketone, and heterocyclic compounds such as N-aryloxazolidinones.
These commercially available products can be appropriately selected and used, and examples thereof include Kayacure DETX-S (Nippon Kayaku thioxanthone compound).
Further, in European Patent No. 568,993, US Pat. No. 4,508,811, No. 5,227,227, JP-A-2001-125255, JP-A-11-271969, etc. And the like.
The composition may or may not contain a sensitizer, but when it is contained, the content of the sensitizer is 0.01% by mass or more and 10% by mass with respect to the total solid mass of the composition of the present invention. % Or less, more preferably 0.1% by mass or more and 2% by mass or less.

<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.
The composition of the present invention may or may not contain an ultraviolet absorber, but when it is included, the content of the ultraviolet absorber is 0.001% by mass relative to the total solid mass of the composition of the present invention. The content is preferably 1% by mass or less and more preferably 0.01% by mass or more and 0.1% by mass or less.

<Silane coupling agent>
A silane coupling agent can be used for the composition of this invention from a viewpoint of the adhesive improvement with the further board | substrate.
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.)

  In the case of using a silane coupling agent, the addition amount is preferably in the range of 0.1% by mass to 5.0% by mass in the total solid content in the composition used in the present invention, and 0.2% by mass. % To 3.0% by mass is more preferable.

<Filler>
The composition of the present invention may further contain a filler. Examples of the filler that can be used in the present invention include spherical silica surface-treated with a silane coupling agent.
When the composition of the present invention contains a filler, it is preferable in that a highly durable pattern can be obtained (especially when the wiring density of the metal wiring covered with the solder resist is high, more severe durability against the solder resist). The above effect is remarkable when the property is required).
By using spherical silica surface-treated with a silane coupling agent, the thermal cycle test resistance and storage stability of the composition are improved.For example, even after passing through a harsh atmosphere such as a thermal cycle test, It is possible to maintain a similar good shape.

The “spherical” in the spherical filler is not necessarily a needle shape, a columnar shape, or an indeterminate shape, but may be rounded and does not necessarily need to be “true spherical”. "Spherical" is mentioned as a mobile phone.
It can be confirmed that the filler is spherical by observing with a scanning electron microscope (SEM).

There is no restriction | limiting in particular in the volume average particle diameter of the primary particle of the said filler, Although it can select suitably according to the objective, 0.05 micrometer-3 micrometers are preferable, and 0.1 micrometer-1 micrometer are more preferable. When the volume average particle size of the primary particles of the filler is in the above range, the deterioration of processability due to the expression of thixotropic properties is suppressed, and the maximum particle size is not increased, so that foreign matter adheres to the obtained cured film. And the occurrence of defects due to non-uniformity of the coating film is suppressed, which is advantageous.
The volume average particle size of the primary particles of the filler can be measured by a dynamic light scattering particle size distribution measuring device.
The filler can be dispersed by using a dispersant or a binder. As described above, an alkali-soluble binder polymer having a crosslinkable group in the side chain is particularly preferable from the viewpoint of curability.

-Surface treatment-
Next, the surface treatment of the filler will be described. There is no restriction | limiting in particular as surface treatment of a filler, Although it can select suitably according to the objective, The process which coat | covers a silica with a silane coupling agent is preferable.

-Silane coupling agent-
There is no restriction | limiting in particular as a silane coupling agent used for the surface treatment of a filler, Although it can select suitably according to the objective, At least 1 sort (s) selected from an alkoxysilyl group, a chlorosilyl group, and an acetoxysilyl group A functional group (hereinafter also referred to as “first functional group”) and at least one functional group selected from a (meth) acryloyl group, an amino group and an epoxy group (hereinafter also referred to as “second functional group”). The second functional group is more preferably a (meth) acryloyl group or an amino group, the second functional group is more preferably a (meth) acryloyl group, and the second functional group is a (meth) acryloyl group. And advantageous in terms of storage stability and TCT resistance.

  Further, as described in JP-B-7-68256, the first functional group is at least one selected from an alkoxysilyl group, a chlorosilyl group, and an acetoxysilyl group, and the second functional group is an imidazole group or an alkyl group. Those having at least one selected from an imidazole group and a vinylimidazole group can also be preferably used.

  The silane coupling agent is not particularly limited. For example, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)- γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, JP 7- [Alpha]-[[3- (trimethoxysilyl) propoxy] methyl] -imidazole-1-ethanol, 2-ethyl-4-methyl- [alpha]-[[3- (trimethoxysilyl) propoxy] described in Japanese Patent No. 68256 Methyl] -imidazole-1-ethanol, 4-vinyl-α-[[3 (Trimethoxysilyl) propoxy] methyl] - imidazole-1-ethanol, 2-ethyl-4-methyl-imidazo-trimethoxysilane, and their salts, intramolecular condensates, intermolecular condensates, and the like preferably. These may be used individually by 1 type and may be used in combination of 2 or more types.

The surface treatment of the spherical silica with the silane coupling agent may be performed only on the spherical silica in advance (this case is also referred to as “pretreatment” hereinafter) or other fillers contained in the composition. You may carry out together with a part or all of.
The method for performing the pretreatment is not particularly limited, and examples thereof include a dry method, an aqueous solution method, an organic solvent method, and a spray method. The temperature at which the pretreatment is performed is not particularly limited, but is preferably from room temperature to 200 ° C.
It is also preferable to add a catalyst during the pretreatment. There is no restriction | limiting in particular as this catalyst, For example, an acid, a base, a metal compound, an organometallic compound etc. are mentioned.

  The amount of the silane coupling agent added in the pretreatment is not particularly limited, but is preferably in the range of 0.01 to 50 parts by mass with respect to 100 parts by mass of spherical silica, and 0.05 to The range of 50 parts by mass is more preferable. When the addition amount is in the above range, a surface treatment sufficient to exhibit the effect is performed, and a decrease in handleability due to aggregation of spherical silica after the treatment is suppressed.

  In the silane coupling agent, the first functional group reacts with the substrate surface, the spherical silica surface, and the active group of the binder, and the second functional group further includes a carboxyl group and an ethylenically unsaturated group of the binder. In order to react, there exists an effect | action which improves the adhesiveness of a board | substrate and a photosensitive layer. On the other hand, since the silane coupling agent is highly reactive, when it is added to the composition, the second functional group mainly reacts or deactivates during storage due to the diffusion action, and the shelf life And pot life may be shortened.

However, as described above, if the spherical silica pretreated with a silane coupling agent is used, the diffusion effect is suppressed, so that the shelf life and pot life problems are greatly improved. It is also possible to do. Furthermore, when pre-treating spherical silica, conditions such as stirring conditions, temperature conditions, and use of a catalyst can be freely selected, so that the silane coupling agent is compared with the case of adding without pre-treatment. The reaction rate between the first functional group and the active group in the spherical silica can be remarkably increased. Therefore, very good results can be obtained particularly in severe required characteristics such as electroless gold plating, electroless solder plating, and moisture resistance load test. Moreover, the amount of the silane coupling agent used can be reduced by performing the pretreatment, and the shelf life and pot life can be further improved.
Examples of the spherical silica surface-treated with a silane coupling agent that can be used in the present invention include, for example, Electrochemical Industry: FB, SFP series, Tatsumori: 1-FX, Toa Gosei: HSP series, Fuso Chemical Industries: SP series etc. are mentioned.

  The composition may or may not contain a filler, but when it is contained, the filler content with respect to the total solid mass of the composition is not particularly limited and can be appropriately selected according to the purpose. The total solid content is preferably 1% by mass to 40% by mass, more preferably 2 to 30% by mass, and even more preferably 3 to 20% by mass. When the addition amount is in the above range, a sufficient decrease in the coefficient of linear expansion is achieved, and embrittlement of the formed cured film is suppressed, and the function as a wiring protective film when a wiring is formed using a permanent pattern Is fully expressed.

<Dispersant>
In the present invention, when the tungsten compound is particularly tungsten fine particles, it may be dispersed by a known dispersant for the purpose of improving the dispersibility and dispersion stability of the tungsten compound in the composition.

Examples of the dispersant that can be used in the present invention include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (Meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate], and surfactants such as polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and alkanol amine.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

  Examples of the terminal-modified polymer having an anchor site to the surface include a polymer having a phosphate group at its terminal described in JP-A-3-112992, JP-T2003-533455, and the like. A polymer having a sulfonic acid group at its terminal described in JP-A-273191, a polymer having a partial skeleton or a heterocyclic ring of an organic dye described in JP-A-9-77994, or the like in JP-A-2008-29901 Examples thereof include a polymer produced by modifying an oligomer or polymer having a hydroxyl group or an amino group at one end and an acid anhydride. In addition, a high molecular weight terminal in which two or more anchor portions (acid groups, basic groups, organic dye partial skeletons, heterocycles, etc.) to the surface of the infrared shielding material are introduced at the polymer ends described in JP-A-2007-277514. Molecules are also preferred because of their excellent dispersion stability.

  Examples of the graft polymer having an anchor site to the surface include poly (lower alkyleneimine) described in JP-A No. 54-37082, JP-A No. 8-507960, JP-A No. 2009-258668, and the like. Reaction product of polyester and polyester, reaction product of polyallylamine and polyester described in JP-A-9-169821 and the like, amphoteric dispersion resin having basic group and acidic group described in JP-A-2009-203462, Copolymers of macromonomer and nitrogen atom monomer described in Kaihei 10-339949, JP-A-2004-37986, etc., JP-A-2003-238837, JP-A-2008-9426, JP-A-2008- JP-A-201032, a graft polymer having a partial skeleton of an organic dye or a heterocyclic ring, They include copolymers of macromonomer and acid group-containing monomers described in 6268 JP like.

  As a macromonomer used when producing a graft polymer having an anchor site on the surface by radical polymerization, a known macromonomer can be used. Macromonomer AA-6 (terminal group) manufactured by Toa Gosei Co., Ltd. Is a methacryloyl group polymethyl methacrylate), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (a copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 (terminal Polybutyl acrylate whose group is a methacryloyl group), Plaxel FM5 manufactured by Daicel Chemical Industries, Ltd. (2-hydroxyethyl methacrylate, ε-caprolactone 5 molar equivalent addition product), FA10L (ε of 2-hydroxyethyl acrylate) -Caprolactone 10 molar equivalent addition product), and JP-A-2-272009 Polyester macromonomer described in the publication No. and the like. Among these, the polyester-based macromonomer particularly excellent in flexibility and solvophilicity is particularly preferable from the viewpoints of dispersibility of the infrared shielding material in the composition, dispersion stability, and developability exhibited by the composition using the infrared shielding material. The polyester macromonomer represented by the polyester macromonomer described in JP-A-2-272009 is most preferable.

  As the block polymer having an anchor site to the surface, block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.

Moreover, a well-known dispersing agent and surfactant can be selected suitably, and can be used.
Specific examples include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide), 161, 162, and 163, manufactured by BYK Chemie. 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050-4010-4165 (polyurethane system), EFKA4330, manufactured by EFKA. -4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative) ", Ajinomoto Fan Techno "Ajispa" “PB821, PB822, PB880, PB881”, “Floren TG-710 (urethane oligomer)” manufactured by Kyoeisha Chemical Co., Ltd., “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon KS- manufactured by Enomoto Kasei Co., Ltd. 860, 873SN, 874, # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyether ester), DA-703-50, DA-705, DA-725 "," Demol RN, N (naphthalene) "manufactured by Kao Corporation Sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) ”,“ homogenol L-18 (polymer polycarboxylic acid) ”,“ Emulgen 920, 930, 935, 985 ” (Polyoxyethylene nonylphenyl ether) ”,“ Acetamine 86 (stearylamine) SETATE) ”, Nippon Lubrizol Co., Ltd.“ Solsperse 5000 (phthalocyanine derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the terminal), 24000, 28000, 32000, 38500 ( Graft type polymer) ", Nikko Chemical's" Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ", Kawaken Fine Chemical Co., Ltd. Hinoact T-8000E, Shin-Etsu Chemical Industry Co., Ltd., Organosiloxane Polymer KP341, Yusho Co., Ltd. “W001: Cationic Surfactant”, Polyoxyethylene Lauryl Ether, Polyoxyethylene Stearyl Ether, Polyoxyethylene Oleyl A , Polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, nonionic surfactants such as sorbitan fatty acid esters, anionic surfactants such as "W004, W005, W017" Agents, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450” manufactured by Morishita Sangyo Co., Ltd., “Disperse Aid 6, Disp. Polymer dispersing agents such as Perth Aid 8, Disperse Aid 15, Disperse Aid 9100, “Adeka Pluronic L31, F38, L42, L44, L61, L64, F68 manufactured by ADEKA Corporation , L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 ”,“ Ionet (trade name) S-20 ”manufactured by Sanyo Chemical Co., Ltd., and the like.

These dispersants may be used alone or in combination of two or more. The dispersant of the present invention may be used in combination with an alkali-soluble resin together with a terminal-modified polymer, a graft polymer, or a block polymer having an anchor site to the surface of the infrared shielding material. . Alkali-soluble resins include (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and carboxylic acid in the side chain. Examples of the acid cellulose derivative include a resin having a hydroxyl group modified with an acid anhydride, and a (meth) acrylic acid copolymer is particularly preferable. Further, N-substituted maleimide monomer copolymers described in JP-A-10-300902, ether dimer copolymers described in JP-A-2004-300204, and polymerizable groups described in JP-A-7-319161. An alkali-soluble resin containing is also preferred.
From the viewpoints of dispersibility, developability and sedimentation, the following resins described in JP-A 2010-106268 are preferred, and in particular, from the viewpoint of dispersibility, polymer dispersion having a polyester chain in the side chain An agent is preferable, and a resin having an acid group and a polyester chain is preferable from the viewpoint of dispersibility and resolution of a pattern formed by a photolithography method. As a preferable acid group in the dispersant, an acid group having a pKa of 6 or less is preferable from the viewpoint of adsorptivity, and carboxylic acid, sulfonic acid, and phosphoric acid are particularly preferable.

The dispersion resin described in JP 2010-106268 A, which is preferably used in the present invention, will be described below.
A preferred dispersant is a graft copolymer having a graft chain selected from a polyester structure, a polyether structure, and a polyacrylate structure, in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10,000 in the molecule. It is preferable that at least the structural unit represented by any one of the following formulas (1) to (4) is included, and at least the following formulas (1A), (2A), (3A), ( 3B) and the structural unit represented by any of the following (4) is more preferable.

In the formulas (1) to (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH, and an oxygen atom is particularly preferred.
In the formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. X ¹ , X ² , X ³ , X ⁴ and X ⁵ are preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms from the viewpoint of synthesis restrictions, and may be a hydrogen atom or a methyl group. Are more preferable, and a methyl group is particularly preferable.
In the formulas (1) to (4), Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a divalent linking group and are not particularly limited in structure. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ and Y ⁴ include the following (Y-1) to (Y-21) linking groups. In the following structures, A and B each represent a bond with the left terminal group and the right terminal group in formulas (1) to (4). Of the structures shown below, (Y-2) and (Y-13) are more preferable from the viewpoint of ease of synthesis.

In the formulas (1) to (4), Z ¹ , Z ² , Z ³ and Z ⁴ are each independently a monovalent organic group, and the structure is not particularly limited. Hydroxyl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthioether group, arylthioether group, heteroarylthioether group, amino group, and the like. Among these, the monovalent organic group represented by Z ¹ , Z ² , Z ³ and Z ⁴ preferably has a steric repulsion effect particularly from the viewpoint of improving dispersibility, and is represented by Z ^{1 to} Z ³ . As the organic group, each independently an alkyl group having 5 to 24 carbon atoms or an alkoxy group having 5 to 24 carbon atoms is preferable, and among them, particularly an alkoxy group having each independently a branched alkyl group having 5 to 24 carbon atoms. Or the alkoxy group which has a C5-C24 cyclic alkyl group is preferable. In addition, the organic group represented by Z ⁴ is preferably independently an alkyl group having 5 to 24 carbon atoms, and among them, each independently a branched alkyl group having 5 to 24 carbon atoms or a cyclic group having 5 to 24 carbon atoms. Alkyl groups are preferred.
In Formula (1)-Formula (4), n, m, p, and q are integers of 1 to 500, respectively.
Moreover, in Formula (1) and Formula (2), j and k represent the integer of 2-8 each independently. J and k in Formula (1) and Formula (2) are preferably integers of 4 to 6, and most preferably 5, from the viewpoints of dispersion stability and developability.

R ³ in the formula (3) represents a branched or straight chain alkylene group. R ³ in formula (3) is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms.
R ⁴ in the formula (4) represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure. R ⁴ in formula (4) is preferably a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R ⁴ in Formula (4) is an alkyl group, the alkyl group may be a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or 5 to 20 carbon atoms. Are preferable, a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable. In addition, as R ⁴ in formula (4), two or more types of R ⁴ having different structures may be mixed and used in the graft copolymer.

  In the graft copolymer, the structural unit represented by the formula (1) to the formula (4) is preferably contained in a range of 10% to 90% in terms of mass with respect to the total mass of the graft copolymer. More preferably, it is contained in the range of 30% to 70%. When the structural units represented by the formulas (1) to (4) are included within this range, the dispersibility of the pigment is high and the developability when forming the light-shielding film is good.

  Moreover, in the graft copolymer, the graft copolymer from which 2 or more types of structures differ can be contained.

The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of dispersion stability and developability.
The structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of dispersion stability and developability.

Wherein (1A), X ^1, Y ^1, Z ¹ and n are as defined X ^1, Y ^1, Z ¹ and n in Formula (1), and preferred ranges are also the same.
Wherein (2A), X ^2, Y ^2, Z ² and m are as defined X ^2, Y ^2, Z ² and m in the formula (2), and preferred ranges are also the same.
The structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or the following formula (3B) from the viewpoints of dispersion stability and developability.

Wherein (3A) or ^{(3B), X 3, Y} 3, Z 3 and p, the formula ^{(3) X 3, Y 3} , have the same meaning as Z ³ and p in, preferred ranges are also the same.

  The graft copolymer is more preferably one having a structural unit represented by the formula (1A).

  Specific examples include the following compounds. In addition, in the following exemplary compounds, the numerical value written together with each structural unit (the numerical value written together with the main chain repeating unit) represents the content of the structural unit [described as mass%: (wt%)]. The numerical value written together with the repeating part of the side chain indicates the number of repetitions of the repeating part.

  As the dispersant in the present invention, a compound having a polyester chain as exemplified Compound 72 is preferable.

  As content of the dispersing agent at the time of preparing the pigment dispersion in this invention, it is 1 mass%-with respect to the total solid content mass of the coloring agent (a black pigment and another coloring agent are included) in a pigment dispersion. 90 mass% is preferable and 3 mass%-70 mass% is more preferable.

When using a dispersant, first, a dispersion composition is prepared with a tungsten compound (and other infrared shielding materials as described above), a dispersant, and an appropriate solvent, and then blended into the composition of the present invention. It is preferable to improve dispersibility.
The composition of the present invention may or may not contain a dispersant, but when it is contained, the content of the dispersant in the dispersion composition is the total solid mass of the infrared shielding particles in the dispersion composition. 1% by mass to 90% by mass is preferable, and 3% by mass to 70% by mass is more preferable.
1-30 mass% is preferable with respect to the total solid, and, as for the compounding quantity of this dispersant composition in case the soldering resist composition of this invention contains a dispersant composition, 2-10 mass% is more preferable.

<Organic carboxylic acid, organic carboxylic anhydride>
The composition of the present invention may contain an organic carboxylic acid having a molecular weight of 1000 or less and / or an organic carboxylic acid anhydride.
Specific examples of the organic carboxylic acid compound include aliphatic carboxylic acids and aromatic carboxylic acids. Examples of aliphatic carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, methacrylic acid, oxalic acid, malonic acid, succinic acid, Examples thereof include dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, and tricarboxylic acids such as tricarbaric acid and aconitic acid. Examples of the aromatic carboxylic acid include carboxylic acids in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid and phthalic acid, and carboxylic acids in which a carboxyl group is bonded to the phenyl group through a carbon bond. Among these, those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically maleic acid, malonic acid, succinic acid, and itaconic acid are preferred.

  Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specific examples include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, and tetrahydrophthalic anhydride. Succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. An aliphatic carboxylic acid anhydride is mentioned. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Among these, those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferable.

When these organic carboxylic acids and / or organic carboxylic acid anhydrides are included, the amount added is usually 0.01 to 10% by weight, preferably 0.03 to 5% by weight, more preferably 0% in the total solid content. The range is from 0.05 to 3% by weight.
By adding these organic carboxylic acids and / or organic carboxylic anhydrides having a molecular weight of 1000 or less, it is possible to further reduce the remaining undissolved material of the composition while maintaining high pattern adhesion.

The crosslinking agent is described in detail, for example, in paragraphs [0166] to [0182] of JP2012-003225A, the contents of which are incorporated herein.
The curing accelerator is described in detail, for example, in paragraph [0241] of JP2012-003225A, the contents of which are incorporated herein.
The elastomer is described in detail in, for example, paragraphs [0242] to [0254] of JP2012-003225A, the contents of which are incorporated herein.
The thermal polymerization inhibitor is described in detail, for example, in paragraph numbers [0101] to [0102] of JP-A-2008-250074, the contents of which are incorporated herein.
The plasticizer is described in detail in paragraph numbers [0103] to [0104] of Japanese Patent Application Laid-Open No. 2008-250074, for example, the contents of which are incorporated herein.
The colorant is described in detail, for example, in paragraph numbers [0105] to [0106] of JP-A-2008-250074 and paragraph numbers [0038] and [0039] of JP-A-2009-205029. This content is incorporated herein.
The adhesion promoter is described in detail, for example, in paragraphs [0107] to [0109] of JP-A-2008-250074, the contents of which are incorporated herein.
Any of the additives described in these publications can be used in the composition of the present invention.

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. For example, fluorine resins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) (including high density and ultra high molecular weight), etc. Filter. Among these materials, polypropylene (including high density polypropylene) is preferable.
The filter has a pore diameter of about 0.01 to 7.0 μm, preferably about 0.01 to 2.5 μm, and more preferably about 0.01 to 1.5 μm. By setting it as this range, it becomes possible to remove reliably the fine foreign material which is mixed in the melted composition and inhibits the preparation of a uniform and smooth composition in a subsequent process.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent pore sizes are larger than the pore size of the first filtering. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here 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. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
As the second filter, a filter formed of the same material as the first filter described above can be used. The pore size of the second filter is suitably about 0.5 to 7.0 μm, preferably about 2.5 to 7.0 μm, more preferably about 4.5 to 6.0 μm. By setting the amount within this range, the component particles contained in the mixed solution remain mixed and are mixed in the mixed solution, and foreign matters that hinder the preparation of a uniform and smooth composition are removed in a later step. be able to.
For example, the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.

The use of the composition of the present invention is not particularly limited, and examples thereof include a solder resist, a light shielding film for a back surface of a silicon substrate in a solid-state imaging device, a light shielding film for a wafer level lens, and the like. It is preferable.
When the composition of the present invention is used for a solder resist, the solid content concentration is preferably 30% by mass or more and 80% by mass or less, more preferably 35% by mass, in order to form a relatively thick coating film. % To 70% by mass, most preferably 40% to 60% by mass.
The viscosity of the composition of the present invention is preferably in the range of 1 mPa · s to 3000 mPa · s, more preferably in the range of 10 mPa · s to 2000 mPa · s, most preferably 100 mPa · s. The range is from s to 1500 mPa · s.
When the composition of the present invention is used for a solder resist, it is preferably in the range of 10 mPa · s or more and 3000 mPa · s or less, more preferably 500 mPa · s or more, from the viewpoint of thick film formation and uniform coatability. The range is 1500 mPa · s or less, and most preferably 700 mPa · s or more and 1400 mPa · s or less.

The present invention also relates to a cured film (preferably a photosensitive layer) formed from the above-described composition of the present invention. Since such a photosensitive layer is formed from the composition of the present invention, the light-shielding property in the infrared region is high, the light-transmitting property in the visible light region is high, and it has a desired shape and is durable. It is a photosensitive layer capable of forming a pattern excellent in durability against high temperature and high humidity and adhesion to a substrate.
The present invention also relates to a permanent pattern formed from the above-described composition of the present invention. The permanent pattern of the present invention is obtained by performing exposure and alkali development on a photosensitive layer formed from the composition of the present invention. By using the composition of the present invention, a red pattern is obtained. Highly light-shielding in the outer region, high light-transmitting property in the visible light region, has a desired shape, and has excellent durability (durability against high temperature and high humidity, adhesion to the substrate, etc.) is there.
Furthermore, this invention includes the process of applying the soldering resist composition of this invention on a board | substrate, and the process of carrying out pattern exposure of this soldering resist composition. More specifically, a step of forming a photosensitive layer using the composition of the present invention, a step of pattern-exposing the photosensitive layer to cure an exposed portion, and an unexposed portion removed by alkali development to obtain a permanent pattern And a step of forming a pattern in this order.

  Hereinafter, a method for forming a permanent pattern using the composition of the present invention as an example will be described in detail. However, the following description regarding the type and amount of the solvent for preparing the coating liquid, the coating liquid coating method, the thickness of the photosensitive layer, the exposure process, and other processes is not limited to the solder resist application. Here, a case where a photosensitive layer (composition layer) is formed using the composition will be described as an example.

-Photosensitive layer-
In order to form a patterned solder resist (solder resist pattern), first, a photosensitive layer is formed from the composition of the present invention. The photosensitive layer is not particularly limited as long as it is a layer formed containing the composition, and the film thickness, the laminated structure, and the like can be appropriately selected according to the purpose.
As the method for forming the photosensitive layer, a coating solution prepared by dissolving, emulsifying or dispersing the composition of the present invention in water or a solvent is prepared on a substrate, and the coating solution is directly applied and dried. The method of forming by is mentioned.

  The solvent for preparing the coating solution is not particularly limited, and can be appropriately selected depending on the purpose as long as it can uniformly dissolve or disperse each component of the composition of the present invention. For example, methanol Alcohols such as ethanol, normal-propanol, isopropanol, normal-butanol, secondary butanol, normal-hexanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, cyclohexanone, cyclopentanone; ethyl acetate, Esters such as butyl acetate, acetic acid-normal-amyl, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, propylene glycol monomethyl ether acetate, and methoxypropyl acetate; Aromatic hydrocarbons such as len, benzene and ethylbenzene; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride and monochlorobenzene; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl Ethers such as ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol, propylene glycol monomethyl ether; dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane and the like. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

The method for applying the coating liquid on the substrate is not particularly limited and can be appropriately selected depending on the purpose.For example, using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, etc. The method of apply | coating is mentioned.
In addition, the drying conditions of the coating film vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 seconds to 150 ° C. for about 30 seconds to 15 minutes.

  There is no restriction | limiting in particular as thickness of the said photosensitive layer, Although it can select suitably according to the objective, For example, 1 micrometer-100 micrometers are preferable, 2 micrometers-50 micrometers are more preferable, and 4 micrometers-30 micrometers are especially preferable.

(Solder resist pattern formation method)
The method of forming a pattern cured film using the solder resist composition of the present invention includes at least a pattern exposure step, and usually, a development step in which conditions are appropriately selected as necessary, and other steps. Including. In the present invention, “exposure” is used to include not only light of various wavelengths but also irradiation of an electron beam, an X-ray or the like.

<Exposure process>
In the exposure step, the photosensitive layer formed by the composition layer is exposed through a mask, and only the region irradiated with light is cured by this step.
The exposure is preferably performed by irradiation of radiation, and as the radiation that can be used for the exposure, ultraviolet rays such as electron beams, KrF, ArF, g rays, h rays, i rays and visible light are particularly preferably used. Preferably, KrF, g line, h line, and i line are preferable.
As an exposure method. Examples include stepper exposure and exposure with a high-pressure mercury lamp.
Exposure is more preferably 5mJ / cm ² ~3000mJ / cm ² is preferably ^{10mJ / cm 2 ~2000mJ / cm 2} , 50mJ / cm 2 ~1000mJ / cm 2 being most preferred.

<Other processes>
There is no restriction | limiting in particular as said other process, According to the objective, it can select suitably, For example, the surface treatment process of a board | substrate, a image development process, a hardening process process, a post exposure process etc. are mentioned.

<Development process>
Subsequent to the exposure step, an alkali development treatment (development step) is performed, and the light non-irradiated part in the exposure step is eluted in an alkaline aqueous solution. Thereby, only the photocured part remains and the solder resist which has pattern-shaped light-shielding property is formed.
As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 ° C. to 40 ° C., and the development time is 10 seconds to 180 seconds.

  Examples of the alkali used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0. ] An alkaline aqueous solution obtained by diluting an organic alkaline compound such as -7-undecene with pure water so that the concentration is generally 0.001 to 10% by mass, preferably 0.01 to 1% by mass is used. . In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

<Curing process>
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed pattern after the development step, if necessary. By performing this treatment, the mechanical strength of the permanent pattern is obtained. Will improve.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminated body having the patterned photosensitive layer formed after the development step. Through the entire surface exposure, the curing of the polymerization component in the composition forming the photosensitive layer is accelerated, the curing of the permanent pattern further proceeds, and the mechanical strength and durability are improved.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

Moreover, as a method of the entire surface heat treatment, a method of heating the entire surface of the laminate having the formed patterned photosensitive layer after the development step can be mentioned. By heating the entire surface, the film strength of the pattern is increased.
120 to 250 degreeC is preferable and the heating temperature in a whole surface heating has more preferable 120 to 250 degreeC. When the heating temperature is 120 ° C. or higher, the film strength is improved by heat treatment, and when the heating temperature is 250 ° C. or lower, the resin in the composition is decomposed to prevent the film quality from being weak and brittle.
The heating time in the entire surface heating is preferably 3 minutes to 180 minutes, and more preferably 5 minutes to 120 minutes.
There is no restriction | limiting in particular as an apparatus which performs whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

  Since the patterned resist thus formed has excellent infrared shielding properties, its application range is wide. Since the composition of the present invention is excellent in shielding properties in the infrared region and light transmittance in the ultraviolet region to the visible region, a pattern having an excellent shape is formed, and the formed pattern (cured film) is excellent. In addition, since it has an infrared shielding property, it is useful for forming a solder resist for a device having a photo diode having sensitivity to the infrared region, particularly for a solid-state imaging device.

  As described above, the composition of the present invention is useful not only for forming a solder resist, but also for forming a light-shielding film on the back surface of a silicon substrate in a solid-state imaging device and a light-shielding film on a wafer level lens.

  Thus, the present invention also relates to a solid-state imaging device having a permanent pattern formed from the composition of the present invention.

Hereinafter, although the solid-state image sensor which concerns on embodiment of this invention is demonstrated, referring FIG.1 and FIG.2, this invention is not limited by the following specific examples.
Throughout FIGS. 1 and 2, common portions are denoted by common reference numerals.
In the description, “upper”, “upper”, and “upper” refer to the side far from the silicon substrate 10, and “lower”, “lower”, and “lower” are the sides closer to the silicon substrate 10. Point to.

FIG. 1 is a schematic cross-sectional view illustrating a configuration of a camera module including a solid-state imaging device according to a specific example of the embodiment.
A camera module 200 shown in FIG. 1 is connected to a circuit board 70 that is a mounting board via solder balls 60 that are connection members.
Specifically, the camera module 200 includes a solid-state image sensor substrate 100 having an image sensor section on a first main surface of a silicon substrate, and a glass substrate disposed above the first main surface side of the solid-state image sensor substrate 100. 30 (light transmissive substrate), an infrared cut filter 42 disposed above the glass substrate 30, a lens holder 50 disposed above the glass substrate 30 and the infrared cut filter 42 and having the imaging lens 40 in the internal space, The solid-state image pickup device substrate 100 and the glass substrate 30 are configured to include a light shielding / electromagnetic shield 44 disposed so as to surround the periphery. Each member is bonded by adhesives 20, 41, 43, 45.
In the camera module 200, incident light hν from outside passes through the imaging lens 40, the infrared cut filter 42, and the glass substrate 30 in order, and then reaches the imaging element portion of the solid-state imaging element substrate 100.
The camera module 200 is connected to the circuit board 70 via a solder ball 60 (connection material) on the second main surface side of the solid-state imaging device substrate 100.

FIG. 2 is an enlarged cross-sectional view of the solid-state imaging device substrate 100 in FIG.
The solid-state image sensor substrate 100 includes a silicon substrate 10 as a base, an image sensor 12, an interlayer insulating film 13, a base layer 14, a red color filter 15R, a green color filter 15G, a blue color filter 15B, an overcoat 16, a micro The lens 17, the light shielding film 18, the insulating film 22, the metal electrode 23, the solder resist layer 24, the internal electrode 26, and the element surface electrode 27 are configured.
However, the solder resist layer 24 may be omitted.

First, the configuration on the first main surface side of the solid-state imaging device substrate 100 will be mainly described.
As shown in FIG. 2, an imaging element unit in which a plurality of imaging elements 12 such as CCDs and CMOSs are two-dimensionally arranged is provided on the first main surface side of the silicon substrate 10 that is a base of the solid-state imaging element substrate 100. ing.
An interlayer insulating film 13 is formed on the image sensor 12 in the image sensor section, and a base layer 14 is formed on the interlayer insulating film 13. Furthermore, on the base layer 14, a red color filter 15 R, a green color filter 15 G, and a blue color filter 15 B (hereinafter collectively referred to as “color filter 15”) corresponding to the image sensor 12. ) Are arranged.
A light shielding film (not shown) may be provided around the boundary between the red color filter 15R, the green color filter 15G, and the blue color filter 15B, and the periphery of the imaging element unit. This light shielding film can be produced using, for example, a known black color resist.
An overcoat 16 is formed on the color filter 15, and a microlens 17 is formed on the overcoat 16 so as to correspond to the imaging element 12 (color filter 15).

In addition, a peripheral circuit (not shown) and an internal electrode 26 are provided in the periphery of the image sensor section on the first main surface side, and the internal electrode 26 is electrically connected to the image sensor 12 via the peripheral circuit. Has been.
Furthermore, an element surface electrode 27 is formed on the internal electrode 26 with the interlayer insulating film 13 interposed therebetween. In the interlayer insulating film 13 between the internal electrode 26 and the element surface electrode 27, a contact plug (not shown) for electrically connecting these electrodes is formed. The element surface electrode 27 is used for applying a voltage and reading a signal through the contact plug and the internal electrode 26.
A base layer 14 is formed on the element surface electrode 27. An overcoat 16 is formed on the base layer 14. The base layer 14 and the overcoat 16 formed on the element surface electrode 27 are opened to form a pad opening, and a part of the element surface electrode 27 is exposed.

The above is the configuration on the first main surface side of the solid-state imaging device substrate 100.
On the first main surface side of the solid-state image sensor substrate 100, an adhesive 20 is provided around the image sensor section, and the solid-state image sensor substrate 100 and the glass substrate 30 are bonded via the adhesive 20.

  The silicon substrate 10 has a through hole that penetrates the silicon substrate 10, and a through electrode that is a part of the metal electrode 23 is provided in the through hole. The imaging element portion and the circuit board 70 are electrically connected by the through electrode.

Next, the configuration on the second main surface side of the solid-state imaging device substrate 100 will be mainly described.
On the second main surface side, an insulating film 22 is formed from the second main surface to the inner wall of the through hole.
On the insulating film 22, a metal electrode 23 patterned so as to extend from a region on the second main surface of the silicon substrate 10 to the inside of the through hole is provided. The metal electrode 23 is an electrode for connecting the image pickup element portion in the solid-state image pickup element substrate 100 and the circuit board 70.
The through electrode is a portion of the metal electrode 23 formed inside the through hole. The through electrode penetrates part of the silicon substrate 10 and the interlayer insulating film, reaches the lower side of the internal electrode 26, and is electrically connected to the internal electrode 26.

Further, a solder resist layer 24 (protective layer) that covers the second main surface on which the metal electrode 23 is formed and has an opening that exposes a part of the metal electrode 23 on the second main surface side. Insulating film).
Further, on the second main surface side, a light shielding film 18 is provided which covers the second main surface on which the solder resist layer 24 is formed and has an opening through which a part of the metal electrode 23 is exposed. It has been.
In this configuration, (1) the light-shielding solder resist layer in which the light-shielding film 18 and the solder resist layer 24 become a single layer may be formed from the composition of the present invention, or (2) the light-shielding film 18. And the solder resist layer 24 are separate layers, and the light shielding film 18 may be formed from the composition of the present invention (in this case, the solder resist layer may be formed from a known solder resist composition).
In FIG. 2, the light shielding film 18 is patterned so as to cover a part of the metal electrode 23 and expose the remaining part, but may be patterned so as to expose the entire metal electrode 23. (The same applies to the patterning of the solder resist layer 24).
The solder resist layer 24 may be omitted, and the light shielding film 18 may be directly formed on the second main surface on which the metal electrode 23 is formed.

  A solder ball 60 as a connection member is provided on the exposed metal electrode 23, and the metal electrode 23 of the solid-state imaging device substrate 100 and a connection electrode (not shown) of the circuit board 70 are connected via the solder ball 60. , Are electrically connected.

Although the configuration of the solid-state image sensor substrate 100 has been described above, each part of the solid-state image sensor substrate 100 other than the light-shielding film 18 is described in paragraphs 0033 to 0068 in Japanese Patent Laid-Open No. 2009-158863. It can be formed by a known method such as the method described in Paragraph Nos. 0036 to 0065 in JP-A-2009-99591.
The light shielding film 18 can be formed by the above-described manufacturing method of the light shielding film of the present invention.
The interlayer insulating film 13 is formed as a SiO ₂ film or a SiN film, for example, by sputtering, CVD (Chemical Vapor Deposition) or the like.
The color filter 15 is formed by photolithography using a known color resist, for example.
The overcoat 16 and the base layer 14 are formed, for example, by photolithography using a known organic interlayer film forming resist.
The microlens 17 is formed by using styrene resin or the like, for example, by photolithography.
In the case where the solder resist layer 24 is combined with the light shielding film 18 to form a single light shielding solder resist layer, the layer is preferably formed of the composition of the present invention.
On the other hand, when the solder resist layer 24 is a separate layer from the light shielding film 18, the solder resist layer 24 is formed by photolithography using, for example, a known solder resist containing a phenol resin, a polyimide resin, or an amine resin. Preferably it is formed.
The solder ball 60 is formed using, for example, Sn—Ag, Sn—Cu, Sn—Ag—Cu as Sn—Pb (eutectic), 95Pb—Sn (high lead high melting point solder), and Pb free solder. . The solder ball 60 is formed in a spherical shape having a diameter of 100 μm to 1000 μm (preferably a diameter of 150 μm to 700 μm), for example.
The internal electrode 26 and the element surface electrode 27 are formed as a metal electrode such as Cu by CMP (Chemical Mechanical Polishing) or photolithography and etching, for example.
The metal electrode 23 is formed as a metal electrode such as Cu, Au, Al, Ni, W, Pt, Mo, Cu compound, W compound, and Mo compound by sputtering, photolithography, etching, and electrolytic plating, for example. The metal electrode 23 may have a single layer configuration or a stacked configuration including two or more layers. The film thickness of the metal electrode 23 is, for example, 0.1 μm to 20 μm (preferably 0.1 μm to 10 μm). The silicon substrate 10 is not particularly limited, but a silicon substrate that is thinned by scraping the back surface of the substrate can be used. Although the thickness of the substrate is not limited, for example, a silicon wafer having a thickness of 20 μm to 200 μm (preferably 30 to 150 μm) is used.
The through hole of the silicon substrate 10 is formed by, for example, photolithography and RIE (Reactive Ion Etching).

  As described above, the solid-state imaging device substrate 100 which is a specific example of the embodiment has been described with reference to FIGS. 1 and 2. However, the embodiment is not limited to the embodiment of FIGS. If it is the structure which has an electrode and a light shielding film, there will be no limitation in the structure in particular.

  Next, an example in which a permanent pattern obtained from the composition of the present invention is applied to a light shielding film of a wafer level lens will be described with reference to the drawings.

FIG. 7 is a plan view showing an example of the configuration of a wafer level lens array having a plurality of wafer level lenses.
As shown in FIG. 7, the wafer level lens array includes a substrate 410 and lenses 412 arranged on the substrate 410. Here, in FIG. 7, the plurality of lenses 412 are arranged two-dimensionally with respect to the substrate 410, but may be arranged one-dimensionally.
8 is a cross-sectional view taken along line AA shown in FIG.
As shown in FIG. 8, in the wafer level lens array, a light shielding film 414 for preventing light transmission from a portion other than the lens 412 is provided between the plurality of lenses 412 arranged on the substrate 410.
The wafer level lens is configured by one lens 412 existing on the substrate 410 and a light shielding film 414 provided on the peripheral edge thereof. The composition of the present invention is used for forming the light shielding film 414.

  Hereinafter, a configuration of a wafer level lens array in which a plurality of lenses 412 are two-dimensionally arranged on the substrate 410 as shown in FIG. 7 will be described as an example.

  The lens 412 is generally made of the same material as the substrate 410, and is molded integrally on the substrate 410 or formed as a separate structure and fixed on the substrate. is there. Although an example is given here, the wafer level lens of the present invention is not limited to this mode, and can take various modes such as a multi-layer structure and a lens module separated by dicing.

  As a material for forming the lens 412, for example, glass can be used. There are many types of glass, and a glass having a high refractive index can be selected. Therefore, the glass is suitable for a lens material that requires a large power. Further, glass has excellent heat resistance, and has an advantage of withstanding reflow mounting on an imaging unit or the like.

  As another material for forming the lens 412, a resin can be used. Resin is excellent in processability and is suitable for forming a lens surface easily and inexpensively with a mold or the like.

In that case, it is preferable to use an energy curable resin for forming the lens 412. The energy curable resin may be either a resin curable by heat or a resin curable by irradiation with active energy rays (for example, heat, ultraviolet rays, or electron beam irradiation).
Any known energy curable resin can be used, but considering reflow mounting of the imaging unit, a resin having a relatively high softening point such as 200 ° C. or higher is preferable. A resin having a softening point of 250 ° C. or higher is more preferable.

  Hereinafter, with reference to FIGS. 9 to 14, the form and production of the wafer level lens will be described in detail by taking an example of a production method of the wafer level lens array.

[Wafer Level Lens Form and Fabrication (1)]
-Lens formation-
First, a method for forming the lens 412 on the substrate 410 will be described with reference to FIGS. 9 and 10A to 10C.
Here, FIG. 9 is a diagram showing a state in which a molding material (described as M in FIG. 9), which is a resin composition for lens formation, is supplied to the substrate 410.
FIGS. 10A to 10C are diagrams showing a procedure for forming the lens 412 on the substrate 410 with the mold 460. FIG.

  As shown in FIG. 9, the molding material M is dropped onto the portion of the substrate 410 where the lens 412 is molded using the dispenser 450. Here, an amount of the molding material M corresponding to one lens 412 is supplied to one part to be supplied.

After the molding material M is supplied to the substrate 410, a mold 460 for molding the lens 412 is disposed on the surface of the substrate 410 to which the molding material M is supplied, as shown in FIG.
Here, the mold 460 is provided with recesses 462 for transferring the shape of the lens 412 in accordance with the number of desired lenses 412.

  As shown in FIG. 10B, the mold 460 is pressed against the molding material M on the substrate 410, and the molding material M is deformed following the shape of the recess 462. When the mold 460 is pressed against the molding material M and the molding material M is a thermosetting resin or an ultraviolet curable resin, heat or ultraviolet rays are irradiated from the outside of the mold 460 to cure the molding material M. Let

  After the molding material M is cured, the substrate 410 and the lens 412 are released from the mold 460 as shown in FIG.

-Formation of light shielding film-
Next, with reference to FIGS. 11A to 11C, a method for forming the light shielding film 414 on the periphery of the lens 412 will be described.
Here, FIGS. 11A to 11C are schematic cross-sectional views showing a process of providing the light-shielding film 414 on the substrate 410 on which the lens 412 is molded.

  The light-shielding film 414 is formed by a light-shielding coating layer forming step (see FIG. 11A) in which the composition of the present invention is applied to the substrate 410 to form the light-shielding coating layer 414A. An exposure process (see FIG. 11B) in which the coating layer 414A is subjected to pattern exposure through the mask 470, and the exposed light-shielding coating layer 414A is developed to remove uncured portions, thereby forming a patterned light-shielding film. And a developing step for forming 414 (see FIG. 11C).

Note that the light shielding film 414 can be formed arbitrarily before or after the lens 412 is fabricated, but here, a method after the lens 412 is fabricated will be described in detail.
Hereinafter, each process in the formation method of the light shielding film 414 is demonstrated.

<Light-shielding coating layer forming step>
In the light-shielding coating layer forming step, as shown in FIG. 11A, a composition is coated on the substrate 410 to form a light-shielding coating layer 414A made of the composition and having a low light reflectance. At this time, the light-shielding coating layer 414A is formed so as to cover the entire surface of the substrate 410 and the surfaces of the lens surface 412a and the lens edge portion 412b of the lens 412.

There is no restriction | limiting in particular as the board | substrate 410 which can be used for this process. Examples include soda glass, alkali-free glass, Pyrex (registered trademark) glass, quartz glass, and transparent resin.
In addition, the board | substrate 410 said here says the form containing both the lens 412 and the board | substrate 410 in the aspect which forms the lens 412 and the board | substrate 410 integrally.
In addition, an undercoat layer may be provided on these substrates 410 as necessary in order to improve adhesion with an upper layer, prevent diffusion of substances, or flatten the surface of the substrate 10.

As a method of applying the composition on the substrate 410 and the lens 412, various application methods such as slit coating, spray coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be applied. it can.
The film thickness immediately after application of the composition is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 5 μm, from the viewpoint of film thickness uniformity of the coating film and ease of drying of the coating solvent. 2 μm to 3 μm is more preferable.

  The light-shielding coating layer 414A applied on the substrate 410 can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds using a hot plate, an oven, or the like.

  The coating film thickness after drying of the composition (hereinafter referred to as “dry film thickness” as appropriate) can be arbitrarily selected from the desired performance such as light-shielding properties, and is generally in the range of 0.1 μm to less than 50 μm. is there.

<Exposure process>
In the exposure step, the light-shielding coating layer 414A formed in the light-shielding coating layer forming step is exposed in a pattern. The pattern exposure may be scanning exposure, but as shown in FIG. 11B, a mode in which exposure is performed through a mask 70 having a predetermined mask pattern is preferable.

  In the exposure in this step, pattern exposure of the light-shielding coating layer 414A is performed through a predetermined mask pattern, and only the portion irradiated with light in the light-shielding coating layer 414A is cured by this exposure. Here, a mask pattern for irradiating light onto the surface of the lens edge 412b and the surface of the substrate 410 between the lenses 412 is used. By doing so, only the light-shielding coating layer 414A in the region excluding the lens surface 412a is cured by light irradiation, and this cured region forms the light-shielding film 414.

  As radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are particularly preferably used. This radiation may be a light source having a single wavelength, or a light source including all wavelengths such as a high-pressure mercury lamp may be used.

<Development process>
Next, by performing an alkali development process (development process), the light non-irradiated portion in exposure, that is, the uncured region of the light-shielding coating layer 414A is eluted into the alkaline aqueous solution, and only the region cured by light irradiation is left.
Specifically, the light-shielding coating layer 414A exposed as shown in FIG. 11B is developed to form a light-shielding coating formed on the lens surface 12a as shown in FIG. 11C. Only the layer 414A is removed, and a cured light shielding film 414 is formed in the other region.

As the alkali agent contained in the developer (alkaline aqueous solution) used in the development step, any of organic or inorganic alkali agents and combinations thereof can be used. In the formation of the light-shielding film in the present invention, it is desirable to use an organic alkali agent from the viewpoint of hardly damaging surrounding circuits.
Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0] -7-undecene and other organic alkaline compounds (organic alkaline agents), and inorganic compounds (inorganic alkaline agents) such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like. An alkaline aqueous solution diluted with pure water so that the concentration is 0.001 to 10% by mass, preferably 0.01 to 1% by mass, is preferably used as the developer.

  The development temperature is usually 20 ° C. to 30 ° C., and the development time is in the range of 20 seconds to 90 seconds.

  When a developer composed of such an alkaline aqueous solution is used, the unexposed portion of the coating film is generally removed with a developer and then washed (rinsed) with pure water. That is, after the development process, the excess developer is sufficiently washed and removed with pure water and further subjected to a drying step.

  In addition, after performing the light-shielding coating layer forming step, the exposure step, and the development step described above, the formed light-shielding film (light-shielding pattern) is cured by heating (post-baking) and / or exposure as necessary. A curing step may be included.

Post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 100 ° C. to 250 ° C. is performed. Conditions such as the post-baking temperature and time can be appropriately set depending on the material of the substrate 410 or the lens 412. For example, when the substrate 412 is glass, 180 ° C. to 240 ° C. is preferably used in the above temperature range.
In this post-bake treatment, the light-shielding film 414 formed after development is continuously or batch-wise used by a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so as to satisfy the above conditions. It can be done with a formula.

  In the above procedure, the case where the shape of the lens 412 is concave has been described as an example, but the shape is not particularly limited, and may be a convex shape or an aspherical shape. In the above procedure, a wafer level lens in which a plurality of lenses 412 are molded on one surface of the substrate 410 has been described as an example. However, a configuration in which a plurality of lenses 412 are molded on both surfaces of the substrate 410 may be used. In that case, a patterned light shielding film 414 is formed on both surfaces in a region excluding the lens surface.

[Wafer Level Lens Form and Fabrication (2)]
FIG. 12 is a diagram illustrating another configuration example of the wafer level lens array. The wafer level lens shown in FIG. 12 has a configuration (monolithic type) in which the substrate 410 and the lens 412 are simultaneously molded with the same molding material.
When producing such a wafer level lens, the same molding material as described above can be used. In this example, a plurality of concave lenses 412 are formed on one surface (the upper surface in the drawing) of the substrate 410, and a convex shape is formed on the other surface (the lower surface in the drawing). A plurality of lenses 420 are formed. Further, a patterned light-shielding film 414 is formed on a region of the substrate 410 excluding the lens surface 412a, that is, on the surface of the substrate 410 and the surface of the lens edge portion 412b. As a patterning method for forming the light shielding film 414, the above-described procedure can be applied.

[Wafer Level Lens Form and Fabrication (3)]
Next, with reference to FIGS. 13A to 13C and FIGS. 14A to 14C, still another configuration example of the wafer level lens array and a procedure for manufacturing the same will be described.
Here, FIGS. 13A to 13C are schematic views showing other processes for forming the patterned light-shielding film 414.
14A to 14C are schematic views showing a process of forming a lens 412 after forming a patterned light-shielding film 414 first.

  In the example of the wafer level lens array shown in FIGS. 9 to 12, the patterned light shielding film 414 is formed on the substrate 410 provided with the lens 412. However, in the procedure described below, first, the substrate 410 is formed. This is a procedure for forming the lens 412 on the substrate 410 after forming the patterned light-shielding film 414 on the substrate 410.

-Formation of light shielding film-
First, as shown in FIG. 13A, a light-shielding coating layer forming step of forming a light-shielding coating layer 414A by applying a composition onto a substrate 410 is performed.

  Thereafter, the light-shielding coating layer 414A applied on the substrate 410 is dried at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds using a hot plate, oven, or the like. The dry film thickness of the composition can be arbitrarily selected from performance such as desired light shielding properties, and is generally in the range of 0.1 μm or more and less than 50 μm.

Next, as illustrated in FIG. 13B, an exposure process is performed in which the light-shielding coating layer 414 </ b> A formed in the light-shielding coating layer forming process is exposed in a pattern through a mask 470. Mask 470 has a predetermined mask pattern.
In the exposure in this step, the light-shielding coating layer 414 is subjected to pattern exposure to cure only the light-irradiated portion of the light-shielding coating layer 414A. Here, a mask pattern that irradiates light only to the light-shielding coating layer 414 </ b> A in a region excluding a portion that becomes the lens opening 414 a of the lens 412 when the lens 412 is molded in a later process is used. By this method, only the light-shielding coating layer 414A in the region excluding the portion that becomes the lens opening 414a of the lens 412 is cured by light irradiation. As radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are preferably used as in the procedure described above.

Next, by performing alkali development processing (development process), only the light-shielding coating layer 414A in the region corresponding to the lens opening 414a of the lens 412 which is an uncured region of the light-shielding coating layer 414A in the pattern exposure is converted into an alkaline aqueous solution. Is eluted. At this time, as shown in FIG. 13C, the light-cured light-shielding coating layer 414A except for the region of the lens opening 414a of the lens 412 remains on the substrate 410 to form a light-shielding film 414.
Here, as the alkaline agent in the alkaline aqueous solution as the developer, the same procedure as described above can be used. After the development process, the excess developer is then washed away and dried.

  Also in this embodiment, after performing the light-shielding coating layer forming step, the exposure step, and the development step, the curing step of curing the formed light-shielding film by the above-described post-baking and / or exposure as necessary. You may give it.

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

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

-Lens formation-
Next, a process of forming the lens 412 after forming the light shielding film 414 will be described.
As shown in FIG. 14A, a molding material M constituting the lens 412 is dropped by a dispenser 450 on a substrate 410 on which a patterned light-shielding film 414 is formed. The molding material M is supplied so as to partially include an end portion of the light shielding film 414 adjacent to the opening so as to cover a region corresponding to the lens opening 414 a of the lens 412.

  After the molding material M is supplied to the substrate 410, a mold 480 for molding a lens is disposed on the surface side of the substrate 410 to which the molding material M is supplied, as shown in FIG. 14B. The mold 480 is provided with concave portions 482 for transferring the shape of the lens 412 according to the number of desired lenses 412.

  The mold 480 is pressed against the molding material M on the substrate 410, and the molding material M is deformed following the shape of the recess. When the mold 480 is pressed against the molding material M and the molding material M is a thermosetting resin or an ultraviolet curable resin, the molding material M is cured by irradiating heat or ultraviolet rays from the outside of the mold. .

  After the molding material M is cured, the substrate 410 and the lens 412 are released from the mold 480 to obtain a wafer level lens including a patterned light-shielding film 414 on the substrate 410 as shown in FIG.

  As described above, the patterned light shielding film 414 provided in the wafer level lens is not only provided in the region excluding the lens surface 412a of the lens 412 as shown in FIG. 11, but also as shown in FIG. In addition, the light shielding film 414 may be provided in a region of the lens 412 excluding the lens opening 414a.

  The wafer level lens has sufficient light shielding in a region other than the lens surface 412a of the lens 412 or the lens opening 414a by a light shielding film 414 having a low light reflectance formed on a pattern on at least one surface of the substrate 410. Generation of reflected light can be suppressed. For this reason, when applied to an imaging module having a solid-state imaging device, it is possible to prevent the occurrence of problems such as ghosts and flares associated with reflected light during imaging.

  Further, since the light shielding film 414 is provided on the surface of the substrate, it is not necessary to attach another light shielding member or the like to the wafer level lens, and an increase in manufacturing cost can be suppressed.

  Note that in the case where a structure having an uneven surface is provided around the lens, there is a concern that light incident on the structure may be reflected or diverged, which may cause problems such as ghosts. Therefore, as shown in FIG. 11, if the light shielding film 414 patterned in the region excluding the lens surface 412a of the lens 412 is provided, light can be shielded except the lens surface 412a, and the optical performance can be improved. .

  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” and “%” are based on mass.

<Preparation of filler dispersion 1>
6.8 parts by mass of silica filler (manufactured by Nippon Aerosil Co., Ltd., Aerosil 50 particle size 30 nm), alkali-soluble resin (ACA230AA, Daicel Cytec Co., Ltd.), weight average molecular weight 14000 (polystyrene converted value by GPC method), After mixing 92.9 parts by mass of solid content 50% by mass, solvent: propylene glycol monomethyl ether acetate (PGME) and 0.3 part by mass of melamine, the motor mill M-50 (manufactured by Eiger Corp.) 1.0 mm zirconia beads were used and dispersed for 1.5 hours at a peripheral speed of 9 m / s. Filtration was performed using Nippon Pall Profile Star (polypropylene filtration accuracy 1.5 μm) to prepare filler dispersion 1.

<Preparation of solder resist composition>
(Example 1)
The following composition was mixed and filtered using Nippon Pole HDCII (high-density polypropylene filtration accuracy: 6.0 μm) to obtain the composition of Example 1. The solid content concentration of the composition of Example 1 was 47% by mass. The viscosity was 300 mPa · s.
Infrared light shielding particles YMF-02 (18.5 mass% dispersion of cesium tungsten oxide (Cs _0.33 WO ₃ , particle size showing maximum value in particle size distribution: 20 nm) manufactured by Sumitomo Metal Mining Co., Ltd.) 13 parts by mass / polymerizable compound Compound D: diglycerin EO-modified (meth) acrylate (manufactured by Toagosei Co., Ltd., M-460) 4.63 parts by mass / polymerization initiator α-aminoketone polymerization initiator (compound A), IRGACURE369 (BASF) (Made by company)
1.10 parts by mass / sensitizer Kayacure DETX-S (thioxanthone compound manufactured by Nippon Kayaku Co., Ltd.)
0.38 parts by mass UV absorber DPO (manufactured by Fujifilm Fine Chemical) 0.07 parts by mass Silane coupling agent KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.) 2.10 parts by mass Surfactant MegaFuck F-780 (Manufactured by DIC Corporation) 0.10 parts by mass-Filler dispersion 1 58.39 parts by mass-Solvent PGMEA 14.10 parts by mass

(Examples 2-3)
Except having replaced the photoinitiator (compound A) with the said compounds B and C, it was set as the composition similar to Example 1, and the composition of Example 2, 3 was obtained, respectively. The solid content concentrations of the compositions of Examples 2 and 3 were 47% by mass, respectively. The viscosity of the composition of Example 2 was (200) mPa · s, and that of Example 3 was 200 mPa · s.
Compound B Oxime polymerization initiator, IRGACUREOXE01 (manufactured by BASF)
Compound C Triazine polymerization initiator (synthesized according to a known method)

(Comparative Examples 1-4)
The composition of Comparative Examples 1-4 was obtained by setting it as the composition similar to Example 1 except having replaced the compound D of Example 1 with compound EH, respectively. The solid content concentrations of the compositions of Comparative Examples 1 to 4 were 47% by mass, respectively.
Compound E Dipentaerythritol hexaacrylate (synthesized according to a known method)
Compound F KAYARAD DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku
Compound G Nippon Kayaku, KAYARAD PR-1040
Compound H Shin-Nakamura Chemical A-DPH-12E (EO-modified dipentaerythritol hexaacrylate)

(Comparative Example 5)
The infrared ray shielding particles (YMF-02) of Example 1 were replaced with the following carbon black dispersion H, the input amount was changed from 19.13 parts by mass to 30.27 parts by mass, and the solvent (PGMEA) input amount was 14. A composition of Comparative Example 5 was obtained by using the same composition as in Example 1 except that 10 parts by mass was replaced by 2.96 parts by mass. The solid content concentration of the composition of Comparative Example 5 was 47% by mass.

(Preparation of carbon black dispersion H)
The following composition I was subjected to a high viscosity dispersion treatment with two rolls to obtain a dispersion. Then, the mixture of the following composition II was added to this dispersion, and it stirred for 3 hours using the homogenizer on 3000 rpm conditions. The obtained mixed solution was subjected to fine dispersion treatment for 4 hours with a disperser (trade name: Dispermat, manufactured by GETZMANN) using zirconia beads having a particle size of 0.3 mm to obtain a carbon black dispersion (solid content concentration of 18 0.0 mass%) was prepared.

(Composition I)
-23 parts by mass of carbon black (Pigment Black 7) having a particle size of 15 nm showing the maximum value in the particle size distribution-45% by mass solution of PGMEA of benzyl methacrylate / methacrylic acid copolymer (copolymerization ratio of benzyl methacrylate / methacrylic acid = 67/33 (mol%), Mw: 28000)
22 parts by mass, Solsperse 5000 (manufactured by Nippon Lubrizol Co., Ltd.) 1.2 parts by mass

(Composition II)
45% by mass solution of PGMEA of benzyl methacrylate / methacrylic acid copolymer (benzyl methacrylate unit / methacrylic acid unit = 67/33 (mol%), Mw: 28000)
22 parts by mass / PGMEA 176 parts by mass

<Evaluation of solder resist composition>
(Infrared shielding)
A glass substrate is spin-coated under the above conditions to form a coating film of a photosensitive layer (solder resist composition layer) having a film thickness of 25 μm, and an ultraviolet visible near infrared spectrophotometer UV3600 (manufactured by Shimadzu Corporation) is used The transmittance of the coating film at a wavelength of 1200 nm was measured. The lower the transmittance, the better the infrared shielding property. Evaluation was performed based on the following evaluation criteria.
〔Evaluation criteria〕
5: The transmittance is 2% or less.
4: The transmittance is larger than 2% and not larger than 3%.
3: The transmittance is greater than 3% and 5% or less.
2: The transmittance is greater than 5% and 10% or less.
1: The transmittance is greater than 10%.

(Aging residue)
Each of the obtained infrared compositions was stored in a refrigerator (4 ° C.) for 6 months, and each was applied to a silicon wafer by spin coating so that the film thickness was 25 μm, and then 2 ° C. at 120 ° C. on a hot plate. A photosensitive layer was obtained by heating for a minute.
Then, the resulting photosensitive layer, using an i-line stepper, the exposure amount in the range of exposure amount 50~2000mJ / cm ² through a photomask having a pattern with a diameter of 300 [mu] m, is changed in steps of 50 mJ / cm ² And irradiated.
The exposed photosensitive layer was subjected to paddle development at 25 ° C. for 40 seconds using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide. Thereafter, it was rinsed with a spin shower and further washed with pure water to obtain an infrared shielding solder resist pattern. The inside of the 300 μm diameter circle pattern obtained when the development process was carried out for 60 seconds was observed with a scanning electron microscope, evaluated based on the evaluation criteria, and between 5 steps from 5 to 1 according to the following evaluation criteria Ranking was done by evaluation. Rank 3 or higher is a practical level.

〔Evaluation criteria〕
5: Level at which no roughness is seen on the silicon substrate surface and no residue is seen.
4: Level at which no roughness is seen on the silicon substrate surface and almost no residue is seen.
3: Some roughness is observed on the surface of the silicon substrate, but the residue is within an allowable level.
2: Roughness is observed on most of the surface of the silicon substrate, which is a rejected level.
1: Large roughness is observed on the entire surface of the silicon substrate, development is incomplete, and the level is unacceptable.

(Time exposure sensitivity)
Each of the obtained compositions was stored in a refrigerator (4 ° C.) for 6 months, and each was applied to a silicon wafer by spin coating to a film thickness of 25 μm, and then on a hot plate at 120 ° C. for 2 minutes. A photosensitive layer was obtained by heating.
Then, the resulting photosensitive layer, using an i-line stepper, the exposure amount in the range of exposure amount 50~2000mJ / cm ² through a photomask having a pattern with a diameter of 300 [mu] m, is changed in steps of 50 mJ / cm ² And irradiated.
The exposed photosensitive layer was subjected to paddle development at 25 ° C. for 40 seconds using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide. Thereafter, rinsing was performed with a spin shower, followed by washing with pure water to obtain an infrared shielding solder resist pattern. When the development process was carried out for 60 seconds, the minimum exposure amount (exposure sensitivity) at which a circular pattern having a diameter of 300 μm was obtained was measured (mJ / cm ² ). The smaller the numerical value, the better the pattern exposure sensitivity, which was evaluated based on the following evaluation criteria.

〔Evaluation criteria〕
5: Minimum exposure is 200 mJ / cm ² or less.
4: Minimum exposure amount greater than 200mJ / cm ² 250mJ / cm ² or less.
3: Minimum exposure amount greater than 250mJ / cm ² 300mJ / cm ² or less.
2: The minimum exposure amount is greater than 300 mJ / cm ² and 350 mJ / cm ² or less.
1: The minimum exposure amount is larger than 350 mJ / cm ² .

(Uniformity over time)
Each infrared composition is stored in a refrigerator (4 ° C.) for 6 months, applied onto a silicon wafer by spin coating at a rotation speed of 900 rpm for 25 seconds, and the resulting silicon wafer is placed on a hot plate at 120 ° C. Heated for 2 minutes.
The coating film obtained as described above was visually evaluated for coating uniformity, and was ranked according to the following evaluation criteria between 5 and 5 stages. Rank 3 or higher is a practical level.

〔Evaluation criteria〕
5: Roughness is not seen on the surface, and the coated surface is at a level where there is no problem.
4: Roughness is not seen on the surface, and the coated surface is at a level where there is almost no problem.
3: Roughness is observed on a part of the surface, and the coated surface is slightly bad, but is within an acceptable level.
2: Roughness is observed on most of the surface, the coated surface is poor, and the level is unacceptable.
1: Roughness was observed on the entire surface, the surface of the coated surface was considerably poor, and the level was unacceptable.

  As is clear from the above table, when the composition containing the compound represented by the general formula (1) and the infrared light shielding particles is used (Examples 1 to 3), the infrared light shielding properties are maintained and the change with time is not affected. It was found that adaptability was excellent. On the other hand, when a composition using a compound having a structure similar to that of the compound D used in the present invention such as the compounds E to H (Comparative Examples 1 to 4), the infrared light shielding property is maintained. It has been found that the change is remarkable with time, and the composition after the time has problems such as a tendency for the residue to drop, inferior sensitivity, and poor applicability.

2 Large pattern 3 Fine pattern 10 Silicon substrate 12 Image sensor 13 Interlayer insulating film 14 Base layer 15 Color filter 16 Overcoat 17 Micro lens 18 Light shielding film 20 Adhesive 22 Insulating film 23 Metal electrode 24 Solder resist layer 26 Internal electrode 27 Element surface Electrode 30 Glass substrate 40 Imaging lens 41 Adhesive 42 Infrared cut filter 43 Adhesive 44 Light shielding and electromagnetic shield 45 Adhesive 50 Lens holder 60 Solder ball 70 Circuit board 100 Solid-state imaging device substrate 200 Camera module 300 Silicon substrate 310 Circular metal electrode 320 Light-shielding film 330 Resist layer 340 Light-shielding film 410 Substrate 412 and 420 Lens 412a Lens surface 412b Lens edge 414 Light-shielding film 414A Light-shielding coating layer 414a Lens opening 450 Dispensers 460 and 48 Type 462 and 482 recess 470 mask

Claims (15)

A solder resist composition comprising a compound represented by the general formula (1) and infrared ray shielding particles.
General formula (1)

(In General Formula (1), each L is a group composed of a combination of an alkylene group and -O-, and each Ac is a (meth) acryloyloxy group.) The solder resist composition according to claim 1, wherein L in the general formula (1) is a group composed of a combination of —CH ₂ — and —O—. The solder resist composition according to claim 1, wherein the infrared light shielding particles include a tungsten compound. The solder resist composition according to claim 1, wherein the infrared light shielding particles are represented by the following general formula (2).
M _x W _y O _z (2)
M represents a metal, W represents tungsten, and O represents oxygen.
0.001 ≦ x / y ≦ 1.1
2.2 ≦ z / y ≦ 3.0 The soldering resist composition of Claim 4 whose M is an alkali metal in General formula (2). The soldering resist composition of Claim 4 whose M is cesium in General formula (2). In general formula (1), L is, -C ₂ H ₄ - to identify the group consisting of -O-, a solder resist composition according to any one of claims 1-6. Furthermore, the soldering resist composition of any one of Claims 1-7 containing a polymerization initiator. Furthermore, the soldering resist composition of any one of Claims 1-7 containing an (alpha) -amino ketone type | system | group polymerization initiator. Furthermore, the soldering resist composition of any one of Claims 1-9 containing an alkali-soluble binder. The soldering resist composition of any one of Claims 1-10 whose solid content concentration is 30-80 mass%. The cured film formed by hardening | curing the soldering resist composition of any one of Claims 1-11. A solid-state imaging device, a liquid crystal display device or an organic EL display device comprising the cured film according to claim 12. The manufacturing method of a pattern cured film including the process of applying the soldering resist composition of any one of Claims 1-11 on a board | substrate, and the process of carrying out pattern exposure of this soldering resist composition. A solid-state imaging device, a liquid crystal display device or an organic EL display device, comprising a step of applying the solder resist composition according to any one of claims 1 to 11 on a substrate, and a step of exposing the solder resist composition. Production method.

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