JP6325093B2 - Colored composition, cured film, color filter, pattern forming method, color filter manufacturing method, solid-state imaging device, and image display device - Google Patents

Description

  The present invention relates to a colored composition, a cured film, a color filter, a pattern forming method, a method for producing a color filter, a solid-state imaging device, and an image display device.

  A solid-state imaging device is a precision semiconductor product in which many fine members are incorporated. For example, in an image sensor as a solid-state image sensor, a plurality of pixels that convert incident light into an electrical signal, a CMOS (Complementary Metal-Oxide Semiconductor) sensor that selectively reads each pixel, and readout from each pixel through a silicon substrate There is a charge-coupled device (CCD) that transfers the signal charges. The image sensor has integrated semiconductor devices that read out pixel signals and has a dense and complicated internal structure. In general color image sensors, color filters composed of three colors of red (R), green (G), and blue (B) are formed, and these are arranged in an array called a Bayer pattern. With this configuration, incident light is spatially color-separated and the incident light accurately reaches the sensor.

Various materials and manufacturing methods have been proposed in order to manufacture a device having a structure as designed by precisely arranging a large number of members as described above. For example, there has been proposed a technique that enables dry etching of the color filter pixel portion by providing a planarizing film below the color filter and forming the planarizing film with a metal oxide (Patent Document 1). Further, although not limited to a color image sensor, a method of patterning and etching a silicon resin film applied to an interlayer insulating film with a resist mask is disclosed (Patent Document 2).
Moreover, forming a pattern using a siloxane-based resin composition is disclosed (Patent Documents 3 to 5).

JP 2009-103746 A Japanese Patent Laid-Open No. 06-77176 JP 2012-36385 A JP 2012-87316 A JP 2010-85579 A

Here, when patterning is performed by etching using the color filter color layer as a mask, it is necessary to remove the resist on the color layer after the etching. When removing the resist, the colored layer under the resist is preferably not removed as much as possible.
An object of the present invention is to provide a colored composition capable of forming a colored layer that is difficult to be removed together with a resist. Moreover, it aims at providing the pattern formation method, the manufacturing method of a color filter, a solid-state image sensor, and an image display apparatus.

式（１Ａ）中、「−」は結合子を表す。
＜５＞シロキサン樹脂が、下記式（１）で表される部分構造を有するシロキサン樹脂を含む、＜３＞に記載の着色組成物；

式（１）中、Ｒ¹およびＲ²はそれぞれ独立に炭素数１〜４のアルキル基、炭素数１または２のアルコキシル基または水素原子を表し、＊は結合子を表し、ｎは正の整数を表す。
＜６＞シロキサン樹脂が、アルコキシシラン化合物を加水分解縮合して得られたシロキサン樹脂である、＜１＞〜＜５＞のいずれかに記載の着色組成物。
＜７＞有機色材が、有機顔料および有機染料の少なくとも１種を含む、＜１＞〜＜６＞のいずれかに記載の着色組成物。
＜８＞＜１＞〜＜７＞のいずれかに記載の着色組成物を硬化してなる硬化膜。
＜９＞＜１＞〜＜７＞のいずれかに記載の着色組成物を用いた着色層を有するカラーフィルタ。
＜１０＞＜１＞〜＜７＞のいずれかに記載の着色組成物を用いて基板上に着色層を形成する工程と、着色層上にレジスト層を形成し、パターニングする工程と、パターニングされたレジスト層をマスクとして、エッチングする工程とを含む、パターン形成方法。
＜１１＞エッチングする工程が、ハロゲン系ガスを含むエッチングガスを用いてドライエッチングすることを含む、＜１０＞に記載のパターン形成方法。
＜１２＞エッチングガスがフッ素系ガスと酸素ガスとアルゴンガスとを含み、フッ素系ガスと酸素ガスとの混合比率が単位時間における体積比で１：１〜１：４であり、エッチングガス中におけるアルゴンガスの流量が９０体積％以下である、＜１１＞に記載のパターン形成方法。
＜１３＞エッチングガスがアルゴンガスとＣ₄Ｆ₆と酸素ガスとを含む、＜１１＞または＜１２＞に記載のパターン形成方法。
＜１４＞ドライエッチング後に残存するレジスト層をアッシング処理する工程をさら含み、アッシング処理が、灰化処理、プラズマ処理または光励起処理である、＜１１＞〜＜１３＞のいずれかに記載のパターン形成方法。
＜１５＞＜１０＞〜＜１４＞のいずれかに記載のパターン形成方法を含む、カラーフィルタの製造方法。
＜１６＞基板上に、＜１＞〜＜７＞のいずれかに記載の着色組成物をドライエッチング処理およびアッシング処理して第１の着色画素を形成した後、第１の着色画素と異なる色調の着色画素を順次形成することを含む、＜１５＞に記載のカラーフィルタの製造方法。
＜１７＞＜９＞に記載のカラーフィルタ、または、＜１５＞もしくは＜１６＞に記載のカラーフィルタの製造方法により得られたカラーフィルタを有する固体撮像素子。
＜１８＞＜９＞に記載のカラーフィルタ、または、＜１５＞もしくは＜１６＞に記載のカラーフィルタの製造方法により得られたカラーフィルタを有する画像表示装置。
＜１９＞基板上に、第１の着色画素を形成する工程と、第１の着色画素が形成された基板上に、第１の着色画素とは色調の異なる第２の着色画素を形成する工程と、を含み、第１の着色画素を形成する工程は、＜１＞〜＜７＞のいずれかに記載の着色組成物を用いて基板上に第１の着色層を形成する工程と、第１の着色層上にレジスト層を形成し、レジスト層をパターニングする工程と、パターニングされたレジスト層をマスクとして、ハロゲン系ガスを含むエッチングガスを用いてドライエッチングする工程と、ドライエッチングする工程後に残存するレジスト層を、アッシング処理する工程と、含むカラーフィルタの製造方法。Under such circumstances, as a result of intensive studies by the present inventors, the coloring composition contains a siloxane resin and an organic coloring material, and the content of the organic coloring material in the total solid content of the coloring composition is 20 By setting the content of the resin component in the total solid content of the colored composition to 10 to 80% by mass and the content of the siloxane resin to 80% to 100% by mass with respect to the total mass of the resin component, The present inventors have found that the above problems can be solved and have completed the present invention.
Specifically, the above problem has been solved by the following means <1>, preferably by means <2> to <18>.
<1> A colored composition comprising a resin component containing a siloxane resin and an organic colorant,
The content of the organic color material in the total solid content of the colored composition is 20 to 90% by mass, the content of the resin component in the total solid content of the colored composition is 10 to 80% by mass, The coloring composition whose content of siloxane resin is 80-100 mass% with respect to the total mass.
<2> The colored composition according to <1>, wherein the total content of the organic color material and the siloxane resin is 80 to 100% by mass with respect to the total solid content in the colored composition.
<3> The colored composition according to <1> or <2>, wherein an organic color material is dispersed by a siloxane resin.
<4> The colored composition according to any one of <1> to <3>, wherein the siloxane resin includes a siloxane resin having a partial structure represented by the following formula (1A);

In formula (1A), “-” represents a connector.
<5> The colored composition according to <3>, wherein the siloxane resin includes a siloxane resin having a partial structure represented by the following formula (1);

In formula (1), R ¹ and R ² each independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 or 2 carbon atoms, or a hydrogen atom, * represents a bond, and n is a positive integer. Represents.
<6> The colored composition according to any one of <1> to <5>, wherein the siloxane resin is a siloxane resin obtained by hydrolytic condensation of an alkoxysilane compound.
<7> The colored composition according to any one of <1> to <6>, wherein the organic color material includes at least one of an organic pigment and an organic dye.
<8> A cured film obtained by curing the colored composition according to any one of <1> to <7>.
<9> A color filter having a colored layer using the colored composition according to any one of <1> to <7>.
<10> A step of forming a colored layer on the substrate using the colored composition according to any one of <1> to <7>, a step of forming a resist layer on the colored layer, and patterning; And a step of etching using the resist layer as a mask.
<11> The pattern forming method according to <10>, wherein the etching step includes dry etching using an etching gas containing a halogen-based gas.
<12> The etching gas contains a fluorine-based gas, an oxygen gas, and an argon gas, and the mixing ratio of the fluorine-based gas and the oxygen gas is 1: 1 to 1: 4 by volume ratio per unit time. The pattern forming method according to <11>, wherein the flow rate of the argon gas is 90% by volume or less.
<13> The pattern forming method according to <11> or <12>, wherein the etching gas contains argon gas, C ₄ F _6, and oxygen gas.
<14> The pattern formation according to any one of <11> to <13>, further including a step of ashing the resist layer remaining after dry etching, wherein the ashing process is an ashing process, a plasma process, or a photoexcitation process Method.
<15> A method for producing a color filter, comprising the pattern forming method according to any one of <10> to <14>.
<16> On the substrate, after forming the first colored pixel by dry etching and ashing the colored composition according to any one of <1> to <7>, a color tone different from that of the first colored pixel The method for producing a color filter according to <15>, comprising sequentially forming the colored pixels.
<17> A solid-state imaging device having the color filter according to <9> or the color filter obtained by the method for producing a color filter according to <15> or <16>.
<18> An image display device having the color filter according to <9> or the color filter obtained by the method for producing a color filter according to <15> or <16>.
<19> A step of forming a first colored pixel on a substrate, and a step of forming a second colored pixel having a color tone different from that of the first colored pixel on a substrate on which the first colored pixel is formed. And forming the first colored pixel includes forming a first colored layer on the substrate using the colored composition according to any one of <1> to <7>, and A step of forming a resist layer on one colored layer and patterning the resist layer; a step of performing dry etching using an etching gas containing a halogen-based gas using the patterned resist layer as a mask; and a step of performing dry etching A step of ashing the remaining resist layer; and a method of manufacturing a color filter.

  ADVANTAGE OF THE INVENTION According to this invention, it became possible to provide the coloring composition which can form the colored layer which is hard to be removed with a resist. Further, it has become possible to provide a cured film, a color filter, a pattern forming method, a color filter manufacturing method, a solid-state imaging device, and an image display device.

It is a schematic sectional drawing of a 1st colored layer. It is a schematic sectional drawing which shows the state in which the photoresist layer was formed on the 1st colored layer. It is a schematic sectional drawing which shows the state in which the resist pattern was formed on the 1st colored layer. It is a schematic sectional drawing which shows the state in which the 1st coloring pattern was formed by providing the removal part group in the 1st coloring layer by etching. It is a schematic sectional drawing which shows the state from which the resist pattern in FIG. 4 was removed. It is a schematic sectional drawing which shows the state in which the 2nd coloring pixel and the 2nd coloring layer were formed. It is a schematic sectional drawing which shows the state from which the 2nd colored layer in FIG. 6 and a part of 2nd colored pixel were removed. It is a schematic sectional drawing which shows the state in which the 3rd coloring pixel and the 3rd coloring layer were formed. It is a schematic sectional drawing which shows the state from which the 3rd colored layer in FIG. 8 was removed.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

In the notation of a group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes a group (atomic group) having a substituent together with a group (atomic group) having no substituent. To do. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. “Light” means actinic rays or radiation.
Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl and “(meth) acrylic” ) "Acryloyl" represents both and / or acryloyl and methacryloyl.
In the present specification, “monomer” and “monomer” are synonymous.
The monomer in this specification 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 this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
The weight average molecular weight refers to that measured by gel permeation chromatography (GPC) unless otherwise specified. GPC was isolated by removing the solvent from the obtained polymer, and the obtained solid content was diluted to 0.1% by mass with tetrahydrofuran, and HLC-8020 GPC (manufactured by Tosoh Corporation) was used. It is possible to measure by using three TSKgel Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) connected in series as a column. Conditions can be set using a RI detector with a sample concentration of 0.35 mass%, a flow rate of 0.35 ml / min, a sample injection amount of 10 μL, and a measurement temperature of 40 ° C.
In this specification, the total solid content refers to the total mass of the components excluding the solvent from the total composition of the composition. The solid content in the present invention is a solid content at 25 ° C.

[Coloring composition]
The colored composition of the present invention (hereinafter also referred to as the composition of the present invention) contains a siloxane resin and an organic color material, and the content of the organic color material in the total solid content of the colored composition is 20 to 90% by mass. The content of the resin component in the total solid content of the coloring composition is 10 to 80% by mass, and the content of the siloxane resin with respect to the total mass of the resin component is 80 to 100% by mass. To do.
ADVANTAGE OF THE INVENTION According to this invention, the coloring composition which can form the colored layer which is hard to be removed with a resist can be provided. Although this mechanism is not clear, it is presumed as follows. When the amount of the siloxane resin in all the resin components is 80% by mass or more, the surface of the formed colored layer is more effectively covered with the siloxane resin, and carbon atoms are less likely to be present on the surface of the colored layer. Therefore, in particular, when removing the resist on the colored layer after dry etching, it is possible to efficiently remove only the resist and to prevent the colored layer from being removed together.
The composition of the present invention preferably contains a dispersion in which an organic color material is dispersed with a siloxane resin. By adopting such a configuration, the effect of the present invention is more effectively exhibited.

<Organic color material>
As the organic color material, an organic pigment or an organic dye can be used, and an organic pigment is preferably included.
The organic pigment used in the composition of the present invention means an insoluble dye compound that is difficult to dissolve in a solvent. Typically, it is used in the state of being dispersed as particles in the composition. Here, an arbitrary solvent is mentioned with a solvent, For example, the solvent illustrated in the column of the solvent mentioned later is mentioned. The organic pigment used in the composition of the present invention preferably has a solubility at 25 ° C. of 0.001 g / 100 g Solvent or less with respect to, for example, both propylene glycol monomethyl ether acetate (PGMEA) and water.

Examples of organic pigments include azo pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, diketopyrrolopyrrole pigments, perylene pigments, phthalocyanine pigments, azomethine pigments, isoindoline pigments, and quinophthalone pigments.
A red pigment can be used as an anthraquinone pigment. Specifically, C.I. I. And CI Pigment Red 177.
As the quinacridone pigment, a red pigment and a blue pigment can be used. Specifically, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment violet 19, C.I. I. Pigment violet 42 and the like.
A purple pigment can be used as the dioxazine pigment. Specifically, C.I. I. And CI Pigment Violet 23.
A red pigment can be used as the diketopyrrolopyrrole pigment. Specifically, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 270, C.I. I. And CI Pigment Red 272.
As the perylene pigment, a red pigment can be used. Specifically, C.I. I. Pigment red 155, C.I. I. And CI Pigment Red 224.
As the phthalocyanine pigment, a green pigment and a blue pigment can be used. Specifically, C.I. I. Pigment green 7, 36, 58, C.I. I. Pigment blue 15: 6.
As an anthraquinone pigment, a red pigment and a purple pigment can be used. Specifically, C.I. I. Pigment red 177, C.I. I. Pigment red 182, C.I. I. Pigment red 216, C.I. I. Pigment violet 5: 1 and the like.
As the azomethine pigment, a red pigment and a yellow pigment can be used. Specifically, C.I. I. Pigment red 257, C.I. I. And CI Pigment Yellow 150.
A yellow pigment can be used as the isoindoline pigment. Specifically, C.I. I. Pigment yellow 139, 185 and the like.
A yellow pigment can be used as the quinophthalone pigment. Specifically, C.I. I. And CI Pigment Yellow 138.

Other organic pigments include the following.
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 147, 148, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179 180,181,182,187,188,193,194,199,213,214, etc.,
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. ,
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 166, 168, 169, 170, 171, 172, 175, 176, 178, 179, 184, 185, 187, 188, 190, 200, 208, 210, 220, 226, 242, 246, 279

C. I. Pigment Green 10, 37
C. I. Pigment Violet 1,27,32,37
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 16, 22, 60, 64, 66, 79, 80
C. I. Pigment Black 1
The organic pigments can be used alone or in various combinations in order to increase color purity.
The composition of the present invention preferably contains at least one of a phthalocyanine pigment and an azomethine pigment as the organic pigment. I. Pigment green 58 and C.I. I. More preferably, at least one pigment yellow 150 is contained.

When used for a color filter, the primary particle size of the organic pigment is preferably 200 nm or less from the viewpoint of color unevenness and contrast, and is preferably 5 nm or more from the viewpoint of dispersion stability. The primary particle size of the organic pigment is more preferably 5 to 150 nm, still more preferably 10 to 100 nm, and particularly preferably 20 to 80 nm.
The primary particle size of the organic pigment can be measured by a known method such as an electron microscope.

Examples of the organic dye include JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, Tokuho 2592207, and U.S. Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 505950, US Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-51115 The pigment | dye currently disclosed by 6-194828 gazette etc. can be used.
The chemical structure includes pyrazole azo, pyromethene, anilinoazo, xanthene, triphenylmethane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine. Organic dyes such as those can be used. In addition, a pigment multimer may be used as the organic dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A.

Content of the organic color material in the composition of this invention is 20 mass%-90 mass% with respect to the total solid of a coloring composition, and can also be 40-90 mass%, and 50-85 mass. % Or 60 to 85% by mass.
Moreover, it is preferable that the quantity of the organic pigment with respect to the total mass of the organic color material contained in the composition of this invention is 90 mass% or more of the total mass of the organic color material. In addition, the amount of the organic pigment relative to the total mass of the organic color material contained in the composition of the present invention can be 10% by mass or less, can be 5% by mass or less, and can be 1% by mass or less. It can also be 0 mass%. In particular, C.I. I. Pigment green 36 and C.I. I. The total amount of Pigment Yellow 150 is preferably 90% by mass or more of the total amount of the organic color material.
Only one organic colorant may be used, or two or more organic colorants may be used in combination. The content in the case of using two or more types preferably satisfies the above range.
Content of an inorganic color material can also be 5 mass% or less with respect to the total solid of a coloring composition, can also be 1 mass% or less, and can also be 0.5 mass% or less.
The organic color material is preferably dispersed with a siloxane resin. That is, a dispersion in which an organic color material is dispersed with a siloxane resin is preferably included in the composition.

式（１Ａ）中、「−」は結合子を表す。<Siloxane resin>
The composition of the present invention contains a siloxane resin. The siloxane resin preferably has a partial structure represented by the following formula (1A).

In formula (1A), “-” represents a connector.

In the present specification, unless otherwise specified, a silicon-containing polymer in which the main chain is constituted by a siloxane bond obtained through a hydrolysis reaction and a condensation reaction using an alkoxysilane raw material is referred to as a “siloxane resin”. The siloxane resin can be obtained through a hydrolysis reaction and a condensation reaction using an alkoxysilane raw material described later. A siloxane resin is a product in which a part or all of alkoxy groups of alkoxysilane are hydrolyzed to be converted into silanol groups, and at least part of the generated silanol groups are condensed to form Si—O—Si bonds. it can. Since silicon has four bonds, the basic structural unit of the siloxane resin is classified according to the number of organic groups represented by methyl groups and phenyl groups per silicon atom. It can be divided into two. Specifically, the siloxane resin is divided into the following M unit, D unit, T unit, and Q unit. In the following units, R represents an organic group, preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group, an ethyl group or a propyl group.

式（１）中、Ｒ¹およびＲ²はそれぞれ独立に炭素数１〜４のアルキル基、炭素数１または２のアルコキシル基または水素原子を表す。＊は結合子を表す。ｎは正の整数を表し、２〜３００であることが好ましく、１０〜２００であることがより好ましい。The siloxane resin is also preferably a siloxane resin including a partial structure represented by the following formula (1).

In formula (1), R ¹ and R ² each independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 or 2 carbon atoms, or a hydrogen atom. * Represents a connector. n represents a positive integer, preferably 2 to 300, and more preferably 10 to 200.

式（２）および（３）中、Ｒ³は（ｍ＋ｌ）価の有機連結基を表し、Ｒ⁴およびＲ⁵はそれぞれ独立に単結合または２価の連結基を表し、Ａ¹は顔料吸着部位または水素原子を表し、Ｐ¹は式（１）で表される部分構造を含む構造を表し、ｍは１〜８を表し、ｌは１〜１０を表す。Siloxane resin
A copolymer comprising at least a copolymer component having a partial structure represented by formula (1) and a copolymer component having a pigment adsorption site;
A structure represented by the following formula (2), or
The structure represented by following formula (3) may be sufficient.

In formulas (2) and (3), R ³ represents an (m + 1) -valent organic linking group, R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group, and A ¹ represents a pigment adsorption site. or represents a hydrogen atom, P ¹ represents a structure containing a partial structure represented by formula (1), m represents a 1 to 8, l represents 1 to 10.

In Formula (2) and Formula (3), A ¹ represents a pigment adsorption site or a hydrogen atom. In formula (2), l A ^{1 s} may be the same as or different from each other.

A ¹ may have one pigment adsorption site, or may have a plurality of pigment adsorption sites. When A ¹ has a plurality of pigment adsorption sites, they may be the same as or different from each other. Note that not represent pigment adsorption sites by A ¹ alone, a combination of and A ¹ and R ⁴ in formula (2), a combination of and A ¹ and R ³ in formula (2), A ¹ in the formula (3) And a combination of R ⁵ may be a pigment adsorption site. For example, when A ¹ is a hydrogen atom and R ⁴ is a sulfur atom, an embodiment in which the combination of A ¹ and R ⁴ represents a —SH group that is a pigment adsorption site can be exemplified.

A ¹ is, for example, a pigment adsorption site, 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to 100 oxygen atoms, 1 to 400 hydrogen atoms, and 0 A monovalent organic group formed by bonding an organic linking group composed of ˜40 sulfur atoms is preferable. When the pigment adsorption sites itself can constitute a monovalent organic group, of course it may be an organic group pigment adsorption sites itself is represented by A ^1.

  The siloxane resin has the above-described pigment adsorption site in which an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, a heterocyclic residue. It is preferable to include at least one site selected from a group, an amide group, an alkoxysilyl group, an epoxy group, an isocyanate group, a hydroxyl group, and a thiol group, an acidic group, a group having a basic nitrogen atom, a urea group, a coordination group It is more preferable to include at least one site selected from a group having a reactive oxygen atom, a heterocyclic residue, an amide group, an alkoxysilyl group, a hydroxyl group, and a thiol group, and a site selected from an acidic group, a hydroxyl group, and a thiol group It is particularly preferable that at least one kind is contained, and an acidic group, a hydroxyl group, and a thiol group are particularly preferable.

  Examples of acidic groups contained in the pigment adsorption site include carboxylic acid groups, sulfonic acid groups, monosulfate groups, phosphoric acid groups (phosphono groups, etc.), phosphonooxy groups, monophosphate groups, and boric acid groups. An acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a phosphonooxy group, and a monophosphate group are more preferable, and a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group are particularly preferable.

Examples of the group having a basic nitrogen atom represented by the pigment adsorption site include an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , where R ⁸ , R ⁹ , and R ¹⁰ independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms), a guanidyl group, an amidinyl group, and the like.

Examples of urea groups contained in the pigment adsorption site include —NR ¹⁵ CONR ¹⁶ R ¹⁷ (wherein R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). And an aryl group having 6 or more carbon atoms and an aralkyl group having 7 or more carbon atoms), and —NR ¹⁵ CONHR ¹⁷ (wherein R ¹⁵ and R ¹⁷ are each independently a hydrogen atom or carbon An alkyl group having 1 to 10 atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms are more preferred, and —NHCONHR ¹⁷ (where R ¹⁷ is a hydrogen atom or a carbon atom) An alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms are particularly preferable.

Examples of the urethane group contained in the pigment adsorption site include —NHCOOR ¹⁸ , —NR ¹⁹ COOR ²⁰ , —OCONHR ²¹ , —OCONR ²² R ²³ (where R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and the like, and —NHCOOR ¹⁸ , —OCONHR ²¹ (Wherein R ¹⁸ and R ²¹ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms). —NHCOOR ¹⁸ , —OCONHR ²¹ (wherein R ¹⁸ and R ²¹ each independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms). .)etc Particularly preferred.

  Examples of the group having a coordinating oxygen atom contained in the pigment adsorption site include an acetylacetonate group and a crown ether group.

  Examples of the hydrocarbon group having 4 or more carbon atoms contained in the pigment adsorption site include an alkyl group having 4 or more carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and the like. An alkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and the like are more preferable, and an alkyl group having 4 to 15 carbon atoms (for example, an octyl group and a dodecyl group). Etc.), aryl groups having 6 to 15 carbon atoms (for example, phenyl group, naphthyl group and the like), aralkyl groups having 7 to 15 carbon atoms (for example, benzyl group and the like) and the like are particularly preferable.

Examples of the heterocyclic residue contained in the pigment adsorption site include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, Pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone And anthraquinone.
Examples of the amide group contained in the pigment adsorption site include -CONHR ²⁴ (wherein R ²⁴ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms. For example).
Examples of the alkoxysilyl group contained in the pigment adsorption site include a trimethoxysilyl group and a triethoxysilyl group.

The organic linking group bonded to the pigment adsorption site may be a single bond or 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms. And an organic linking group consisting of 0 to 20 sulfur atoms is preferred, and this organic linking group may be unsubstituted or may further have a substituent.
Specific examples of the organic linking group include the following structural units or groups constituted by combining the following structural units.

  When the organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. Group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group and other C1-C6 acyloxy groups, methoxy group, ethoxy group and other C1-C6 alkoxy groups Halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonic acid ester groups such as cyano group and t-butyl carbonate group, etc. Can be mentioned.

  The description of paragraph number 0016-0046 of Unexamined-Japanese-Patent No. 2013-43962 can be referred to for the example of the other possible aspect of the organic group which has a pigment adsorption site, The content is integrated in this-application specification.

In the above formulas (2) and (3), R ⁴ each independently represents a single bond or a divalent linking group. In the above formula (2), 1 R ⁴ may be the same as or different from each other.
Examples of the divalent organic linking group include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 atoms. Group consisting of the above sulfur atom is included, and may be unsubstituted or may further have a substituent.

Specific examples of the divalent organic linking group represented by R ⁴ include a structural unit selected from the following structural unit group G or a group constituted by combining these structural units.

R ⁴ is a single bond, or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 10 Preferred is a divalent organic linking group comprising 1 sulfur atom, a single bond, or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50. More preferable is a divalent organic linking group composed of 1 hydrogen atom and 0 to 7 sulfur atoms, a single bond, 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 A divalent organic linking group consisting of 10 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms is particularly preferred.

That is, a preferred example of the structure represented by the formula (2) includes a structure represented by the following formula (2) ′.
_{^{(A 1 -R 4A -S) l}} -R 3 - (R 5 -P 1) m (2) '
In formula (2) ′, A ¹ , R ⁴ , R ⁵ , P ¹ , l and m are the same as those in formula (2), respectively, and the preferred ranges are also the same. S represents a sulfur atom, and R ^4A represents a single bond or a divalent organic linking group. n R ^4A may be the same or different. As the divalent organic linking group represented by R ^4A , the same as those mentioned as the divalent organic linking group represented by R ⁴ in formula (2) can be used, and the preferred embodiments are also the same. It is.

R ^4A is a single bond, a structural unit selected from the structural unit group G or a combination of these structural units, “1 to 10 carbon atoms, 0 to 5 nitrogen atoms, A divalent organic linking group (which may have a substituent, comprising 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms). Is, for example, an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group or a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, C1-C6 acyloxy groups such as N-sulfonylamide group and acetoxy group, C1-C6 alkoxy groups such as methoxy group and ethoxy group, halogen atoms such as chlorine and bromine, methoxycarbonyl group, ethoxy Carbonyl group, an alkoxycarbonyl group having 2 to 7 carbon atoms such as cyclohexyl oxycarbonyl group, a cyano group, carbonate group, such as t- butyl carbonate group, and the like.) And is preferably.

In the above formulas (2) and (3), R ³ represents an (m + 1) -valent organic linking group. m + 1 preferably satisfies 3 to 10.
The (m + 1) -valent organic linking group represented by R ³ includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200 hydrogen atoms. A group consisting of atoms and 0 to 20 sulfur atoms is included, and may be unsubstituted or may further have a substituent.

  Specific examples of the (m + 1) -valent organic linking group include the following structural units or groups formed by combining these structural units (which may form a ring structure).

  Examples of the (m + 1) -valent organic linking group include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, and 0 to Groups consisting of 10 sulfur atoms are preferred, 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to More preferred are groups consisting of 7 sulfur atoms, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, 1 to 80 hydrogen atoms, and 0. Groups consisting of ˜5 sulfur atoms are particularly preferred.

  Among the above, when the (m + 1) -valent organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. Carbons such as aryl groups having 6 to 16 carbon atoms, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc., acyloxy groups having 1 to 6 carbon atoms, methoxy groups, ethoxy groups, etc. C1-C6 alkoxy groups, halogen atoms such as chlorine and bromine, methoxycarbonyl groups, ethoxycarbonyl groups, cyclohexyloxycarbonyl groups and other C2-C7 alkoxycarbonyl groups, cyano groups, t-butyl carbonate groups And the like, and the like.

Paragraph numbers 0060 to 0063 of JP 2013-43962 A can be referred to for specific examples of the (m + 1) -valent organic linking group represented by R ³ , the contents of which are incorporated herein. However, the present invention is not limited to these.

In the above formulas (2) and (3), R ⁵ each independently represents a single bond or a divalent linking group. In the above formula (2), m R ^{5 s} may be the same as or different from each other.
Examples of the divalent linking group represented by R ⁵ include examples of the divalent linking group represented by R ⁴ . R ⁵ is preferably a single bond or S-.

In the above formulas (2) and (3), P ¹ represents a structure including the partial structure represented by the above formula (1).
The structure including the partial structure represented by the formula (1) can be selected from various polymer skeletons according to the purpose and the like. The m P ^{1 s} may be the same as or different from each other. P ¹ includes at least one structural unit. Two or more structural units may be included, and in that case, at least one is a partial structure represented by the formula (1).

P ¹ includes a partial structure represented by the formula (1). The partial structure represented by the formula (1) is preferably a structural unit derived from a silicone monomer, and the silicone monomer may be a silicone macromer. In the present specification, “macromer (also referred to as macromonomer)” is a general term for an oligomer having a polymerizable functional group (degree of polymerization of about 2 or more and about 300 or less) or a polymer. ) And both properties. The structural unit is derived from a silicone macromer having a weight average molecular weight of 1,000 to 50,000 (more preferably 1,000 to 10,000, and still more preferably 1,000 to 5,000). It is preferably a structural unit.

The structure including the partial structure represented by the formula (1) is not particularly limited. For example, methyl straight silicone resin, acrylic resin-modified silicone resin, polyester resin-modified silicone resin, epoxy resin-modified silicone resin, alkyd resin Modified silicone resins and rubber-based silicone resins can be used.
More preferred are methyl straight silicone resins and acrylic resin-modified silicone resins, and more preferred are methyl straight silicone resins.

  Examples of the structure including the partial structure represented by the formula (1) include X-22-174ASX, X-22-174BX, KF-2012, X-22-173BXX-22-3710 manufactured by Shin-Etsu Chemical Co., Ltd. And so on.

  In the above formulas (2) and (3), l represents 1 to 10, preferably 1 to 5, more preferably 1 to 4, and particularly preferably 1 to 3.

  In the above formulas (2) and (3), m represents 1 to 8, preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.

<Manufacture of siloxane resin>
The siloxane resin can be obtained by hydrolytic condensation of an alkoxysilane compound (through a hydrolysis reaction and a condensation reaction).

<< tetraalkoxysilane >>
In order to produce a siloxane resin, an alkoxysilane raw material containing tetraalkoxysilane can be used as a starting material. The alkoxysilane raw material means a starting raw material composed of alkoxysilane (a silicon compound having an alkoxy group).
Tetraalkoxysilane is an organosilicon compound in which four alkoxy groups are bonded to a silicon atom, and can be represented by the following formula (3).
Formula (3): Si (OR ⁴ ) ₄
(In formula (3), each R ⁴ independently represents an alkyl group.)

The alkoxy group of tetraalkoxysilane is not particularly limited, and examples thereof include a methoxy group and an ethoxy group. More specifically, R ⁴ in Formula (3) is preferably a linear or branched alkyl group having 1 to 20 carbon atoms. The number of carbon atoms of R ⁴ in the formula (3) is 1 to 10 preferably 1 to 4 is more preferred. In particular, from the viewpoint of easy control of the hydrolysis rate, it is preferable that R ⁴ in formula (3) is an ethyl group, that is, OR ⁴ in formula (3) is an ethoxy group.

Specific examples of tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, and tetra-tert-butoxysilane. Tetramethoxysilane and tetraethoxysilane are preferred.
In addition, tetraalkoxysilane may use only 1 type and may use 2 or more types together.

  In the total amount of alkoxysilane that is a raw material for the siloxane resin, the content of tetraalkoxysilane is preferably 0.1% by mass or more, more preferably 10 to 100% by mass, and further preferably 50 to 100% by mass. By setting it as such a structure, the surface can be smooth and the cured film excellent in transparency can be formed. Moreover, the adhesiveness with respect to a base material can also be made more favorable.

<< Alkyltrialkoxysilane >>
In addition to tetraalkoxysilane, other alkoxysilanes can be used as the alkoxysilane as a raw material for the siloxane resin. As another alkoxysilane, alkyltrialkoxysilane is preferable.
An alkyltrialkoxysilane is an organosilicon compound in which one alkyl group and three alkoxy groups are bonded to a silicon atom, and can be represented by the following formula (2).
Formula (2): R ² Si (OR ³ ) ₃
(R ² and R ³ each independently represents an alkyl group.)

The number of carbon atoms of R ² in the formula (2) is preferably 1 to 12, more preferably 1 to 6, 1 to 3 is more preferable. Specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group. A methyl group or an ethyl group is preferable, and a methyl group is more preferable.
Examples of the alkoxy group possessed by the alkyltrialkoxysilane include a methoxy group and an ethoxy group. More specifically, R ³ in the formula (2) is preferably a linear or branched alkyl group having 1 to 20 carbon atoms. The number of carbon atoms of R ³ is 1 to 10 preferably 1 to 4 is more preferred. In particular, from the viewpoint of easy control of the hydrolysis rate, it is preferable that R ³ in formula (2) is an ethyl group, that is, OR ³ in formula (2) represents an ethoxy group.

Specific examples of the alkyltrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, and propyltriethoxysilane. Of these, methyltriethoxysilane or ethyltriethoxysilane is preferable, and methyltriethoxysilane is more preferable.
Only one type of alkyltrialkoxysilane may be used, or two or more types may be used in combination.
When using alkyltrialkoxysilane as a raw material for the siloxane resin, the content of alkyltrialkoxysilane is preferably 1 to 10 parts by mass with respect to 100 parts by mass of tetraalkoxysilane.

  Known methods can be used for the hydrolysis reaction and condensation reaction for obtaining the siloxane resin, and a catalyst may be used if necessary.

<< Catalyst >>
Examples of the catalyst used for the hydrolysis reaction and the condensation reaction include metal oxides, acids, alkalis, boron compounds, and the like containing at least one of Al, Zn, Ti, and Sn.
Examples of the metal oxide containing at least one of Al, Zn, Ti, and Sn include aluminum isopropoxide.
Examples of the acid (organic acid, inorganic acid) include nitric acid, oxalic acid, acetic acid, formic acid, hydrochloric acid, boric acid and the like.
Examples of the alkali include ammonia, triethylamine, ethylenediamine, and the like.
Examples of the boron compound include alkoxyborane (trialkoxyborane and the like).
Although the usage-amount of a catalyst is not specifically limited, 0.1-10 mass parts is preferable with respect to 100 mass parts of alkoxysilane raw materials.
Only 1 type may be used for a catalyst and it may use 2 or more types together.

You may add a solvent to the reaction system of a hydrolysis reaction and a condensation reaction as needed. Although it will not restrict | limit especially if a hydrolysis reaction and a condensation reaction can be implemented as a solvent, For example, it is preferable to use water or the organic solvent mentioned later.
Optimum conditions for the hydrolysis reaction and condensation reaction (temperature, time, amount of solvent) are appropriately selected according to the type of material used.

  A copolymer comprising at least a copolymer component having a partial structure represented by the above formula (1) and a copolymer component having a pigment adsorption site, a structure represented by the formula (2), or a formula (3) For example, paragraph numbers 0110 to 0134 of JP2013-43962A can be referred to as a method for producing a pigment dispersant having a structure represented by the formula, the contents of which are incorporated herein.

  The weight average molecular weight of the siloxane resin is preferably 3000 or more, more preferably 5000 or more, and particularly preferably 8000 or more. As an upper limit, 50000 or less is preferable, 30000 or less is more preferable, and 20000 or less is especially preferable.

Content of the resin component in the composition of this invention is 10-80 mass% with respect to the total solid of the composition of this invention, 15-80 mass% is preferable, and 20-80 mass% is more preferable. . Here, the resin component includes a resin other than the siloxane resin used in the present invention.
Moreover, in the composition of this invention, content of the siloxane resin with respect to the total mass of a resin component is 80-100 mass%, 85-100 mass% is preferable, 90-100 mass% is more preferable, 95-100 More preferred is mass%.
The total content of the organic color material and the siloxane resin with respect to the total solid content in the composition of the present invention is preferably 80 to 100% by mass, and more preferably 84 to 100% by mass.
8-80 mass% is preferable and, as for the total amount of siloxane resin with respect to the total solid in the composition of this invention, 16-80 mass% is more preferable.

<Other ingredients>
The composition of the present invention includes a solvent, a resin other than the siloxane resin (hereinafter also referred to as other resin), a polymerizable compound, a polymerization initiator, a surfactant, and the like as components other than the siloxane resin and the organic colorant. May be contained.

<< Solvent >>
The composition of the present invention may further contain a solvent. The solvent is not particularly limited as long as the solubility of each component and the coating property of the coloring composition are satisfied.
Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl 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- Xylpropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy) Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 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, γ-butyrolactone, etc.
Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME) , Propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate,
Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
As aromatic hydrocarbons, for example, toluene, xylene, and
Preferable examples of alcohols include 3-methyl-3-methoxybutanol.
The content of the solvent in the composition of the present invention is preferably such that the total solid concentration of the composition of the present invention is 5% by mass to 80% by mass from the viewpoint of applicability. The amount of 60% by mass is more preferable, and the amount of 10% by mass to 50% by mass is particularly preferable.
The composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Other resins >>
<<< Other dispersant >>>
In the composition of the present invention, a siloxane resin may be used as a dispersant, or only a dispersant other than the siloxane resin (hereinafter also referred to as other dispersant) may be used as the dispersant.
Other dispersants include polymer dispersants [eg, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) Acrylic copolymer, naphthalenesulfonic acid formalin condensate]; surfactants such as polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines; and pigment derivatives; 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.
As for other dispersants, for example, the description in paragraphs 0216 to 0222 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
When the composition of the present invention contains another dispersant, the total content of the other dispersant is 1 part by weight to 80 parts by weight with respect to 100 parts by weight of the organic colorant in the composition of the present invention. It can also be 5 mass parts-70 mass parts, and it can also be 10 mass parts-60 mass parts.
When the composition of the present invention contains substantially no other dispersant, the content of the other dispersant is 5 parts by mass or less with respect to 100 parts by mass of the organic colorant in the composition of the present invention. It can also be 1 mass part or less, and can also be 0 mass part.
The composition of the present invention may contain only one type of other dispersant, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
Further, a silane coupling agent may be contained in order to compensate for dispersion with siloxane. An example of the silane coupling agent (manufactured by Shin-Etsu Silicone Co., Ltd., product name: KBM-573 (the following structure)) can be mentioned.

<<<< Other Binder >>>>
In the composition of the present invention, since the above-described siloxane resin also functions as a binder, a binder other than the siloxane resin (hereinafter also referred to as other binder) may not be substantially contained. Furthermore, you may contain.
An organic resin can also be used as a binder other than the siloxane resin.
The composition of the present invention may contain only one type of other binder, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
When the composition of the present invention further contains another binder, the total content of the other binder is preferably 50% by mass or less based on the total solid content in the composition of the present invention, and 20 The content is more preferably at most mass%, particularly preferably from 2 to 10 mass%.
Specific examples of other binders include alkali-soluble resins described in paragraphs 0179 to 0209 of JP2013-77009A, the contents of which are incorporated herein.

<< polymerizable compound >>
The composition of the present invention may not substantially contain a polymerizable compound, but may further contain a polymerizable compound.
As for the polymerizable compound, for example, the description of paragraphs 0129 to 0136 of JP2011-137125A can be referred to, and the contents thereof are incorporated in the present specification.
When the composition of this invention contains a polymeric compound, content of a polymeric compound can be 1-10 mass% with respect to the total solid of the composition of this invention, 0.1-3 It can also be made into the mass%.
When the composition of the present invention does not substantially contain a polymerizable compound, the content of the polymerizable compound can be 1% by mass or less based on the total solid content of the composition of the present invention. It can also be made into the mass% or less, and can also be 0 mass%.
The composition of this invention may contain only 1 type of polymeric compounds, and may contain 2 or more types. When two or more types are included, the total amount is preferably within the above range.

<< Polymerization initiator >>
Although the composition of this invention may contain a polymerization initiator, it does not need to contain a polymerization initiator substantially. In particular, when the composition of the present invention is used in a dry etching process, it is preferable that the photopolymerization initiator is not substantially contained.
As a polymerization initiator, it can select suitably from well-known photoinitiators, for example. Only one type of photopolymerization initiator may be used, or two or more types may be used in combination.
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, etc. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, and the like.
Examples of the oxime compound include those represented by the formula (OX-1) or (OX-2) after paragraph 0513 of JP2012-208494A (corresponding to <0632> of US Patent Application Publication No. 2012/235099). The description of the compound represented by can be referred to, and the contents thereof are incorporated in the present specification.
Moreover, as polymerization initiators, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD) Commercial products such as can also be used. Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (manufactured by ADEKA) can also be used.
When the composition of this invention contains a polymerization initiator, content of a polymerization initiator can be 1-5 mass% with respect to the total solid of the composition of this invention. It can also be 1 mass%.
When the composition of the present invention does not substantially contain a polymerization initiator, the content of the polymerization initiator can be 1% by mass or less based on the total solid content of the composition of the present invention. It can also be made into the mass% or less, and can also be 0 mass%.
The composition of the present invention may contain only one type of polymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Surfactant >>
The composition of the present invention may further contain various surfactants from the viewpoint of further improving applicability.
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, the composition of the present invention can further improve liquid properties (particularly fluidity) when it is prepared as a coating liquid by containing a fluorosurfactant, and can improve the uniformity of coating thickness and saving. Liquidity can be further improved.
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, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (above, manufactured by Asahi Glass Co., Ltd.).

  Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol 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), Rusupasu 20000 (Lubrizol Japan Co., Ltd.), 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 Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by Big Chemie.
When the composition of this invention contains surfactant, 0.001 mass%-2.0 mass% are preferable with respect to the total mass of the composition of this invention, More preferably Is 0.005% by mass to 1.0% by mass.
The composition of the present invention may contain only one type of surfactant or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Other ingredients >>
In addition to the above, the composition of the present invention can contain various additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like as necessary. Examples of these additives include those described in paragraphs 0155 to 0156 of JP-A No. 2004-295116, the contents of which are incorporated herein.
The composition of the present invention may contain a sensitizer and a light stabilizer described in paragraph 0078 of JP-A No. 2004-295116, and a thermal polymerization inhibitor described in paragraph 0081 of the publication.

<Curing film, pattern forming method, color filter, and color filter manufacturing method>
Next, a cured film, a pattern formation method, and a color filter which are one embodiment of the present invention will be described in detail through a manufacturing method thereof. In addition, a method for manufacturing a color filter using a pattern forming method, which is one embodiment of the present invention, will be described.
The cured film is formed by curing the composition of the present invention. Such a cured film is preferably used for a color filter.

In the pattern forming method, the composition of the present invention is applied on a support to form a colored layer, and unnecessary portions are removed to form a colored pattern.
The pattern forming method can be suitably applied to the formation of a colored pattern (pixel) included in the color filter.
The composition of the present invention may form a pattern by a dry etching method, or may produce a color filter by pattern formation by a so-called photolithography method.
That is, as a first embodiment of the pattern forming method, a step of applying a colored composition on a support to form a coating film and curing the coating film to form a colored layer, a resist layer on the colored layer A pattern forming method including a step of forming a resist layer by patterning the resist layer by exposure and development, and a step of dry etching the colored layer using the resist pattern as an etching mask is exemplified. The pattern forming method includes a step of forming a colored layer on a substrate using the composition of the present invention, a step of forming a resist layer on the colored layer, and an etching gas containing a halogen-based gas using the resist layer as a mask. It is preferable to include a step of dry etching using.
Further, as a second embodiment of the pattern forming method, a step of forming a colored layer on a support using a colored composition, a step of exposing the colored layer in a pattern, and developing and removing an unexposed portion A pattern forming method including a step of forming a colored pattern.
Such a pattern forming method is used for manufacturing a colored layer of a color filter. That is, this specification also discloses a color filter manufacturing method including a pattern forming method, which is one embodiment of the present invention.
These details will be described below.

Hereinafter, although each process in a pattern formation method is demonstrated in detail through the manufacturing method of the color filter for solid-state image sensors, this invention is not limited to this method. Hereinafter, the color filter for the solid-state imaging device may be simply referred to as “color filter”.
A method for producing a color filter includes a step of forming a colored layer on a substrate using the composition of the present invention, a step of forming a resist layer on the colored layer and patterning, and a halogen-based gas using the patterned resist layer as a mask. It is preferable to include a step of dry etching using an etching gas containing.
Further, the color filter manufacturing method includes forming a first colored pixel on the substrate by dry etching and ashing the colored composition, and then forming a second colored pixel having a color tone different from that of the first colored pixel. It may include forming the third colored pixels sequentially. The composition of the present invention can be preferably used as a composition for forming colored pixels by dry etching. Therefore, the composition of the present invention can be preferably used as the first colored composition for forming the first colored pixel.
Hereinafter, the manufacturing method of the color filter will be described with reference to FIGS.

<<< Step of Forming First Colored Pixel >>>
In the step of forming the first colored pixel (first colored pattern 12), it is preferable to form the first colored pixel by dry etching.
In the color filter manufacturing method, first, as shown in the schematic cross-sectional view of FIG. 1, the first colored layer 11 is formed using the first colored composition (step (A)). The first colored layer 11 is preferably a green transmission layer. By making the first colored layer 11 a green transmissive layer, color sensitivity can be further improved. That is, the first coloring composition is preferably for forming a green transmission layer.

The first colored layer 11 is formed by, for example, applying a colored composition on a support by a coating method such as spin coating, slit coating, spray coating, spin coating, casting coating, roll coating, and the like, and drying the layer. It can be formed by forming. In particular, it is preferable to apply by spin coating.
The support is not particularly limited as long as it is used for a color filter in addition to a silicon substrate. For example, soda glass, borosilicate glass, quartz glass, and a transparent conductive film attached to these are used for liquid crystal display elements. And a photoelectric conversion element substrate used for a solid-state imaging device, such as an oxide film or silicon nitride. Further, an intermediate layer or the like may be provided between the support and the color filter as long as the effects of the present invention are not impaired.
As thickness of the 1st colored layer 11 after drying, the range of 0.3-2.0 micrometers is preferable, The range of 0.35-1.5 micrometers is more preferable, The range of 0.35-1.2 micrometers is more preferable.

The first colored layer 11 is preferably cured by heating with a heating device such as a hot plate or an oven. The heating temperature is preferably 90 ° C to 250 ° C, and more preferably 100 ° C to 230 ° C. The heating time varies depending on the heating means, but is usually about 2 to 30 minutes when heated on a hot plate, and is usually about 30 to 90 minutes when heated in an oven.
The first colored layer 11 is preferably further subjected to heat treatment (post-bake). The post-baking heating temperature is preferably 150 ° C to 350 ° C, more preferably 200 ° C to 250 ° C. The heating time varies depending on the heating means, but is usually about 3 to 90 minutes.

  Next, patterning is performed by dry etching so that the removed portion group is formed in the first colored layer 11 (step (B)). Thereby, the first colored pattern 12 is formed. According to this technique, the first colored layer is formed with the first colored composition, and a desired shape (particularly, compared with the case where the removal portion group is provided by exposing and developing the first colored layer). The (rectangular) removal portion group can be provided more reliably.

  Dry etching can be performed using an etching gas using the patterned photoresist layer as a mask. For example, as shown in the schematic sectional view of FIG. 2, first, a photoresist layer 51 is formed on the first colored layer 11.

  Specifically, a photoresist layer 51 is formed by applying a positive or negative photoresist on the first colored layer 11 and drying it. In forming the photoresist layer 51, it is preferable to further perform a pre-bake treatment. In particular, as a process for forming a photoresist, a mode in which a heat treatment after exposure (PEB: Post Exposure Bake) and a heat treatment after development (post-bake treatment) are desirable.

As the photoresist, for example, a positive type photoresist is used. This positive photoresist is sensitive to radiation such as ultraviolet rays (g-rays, h-rays, i-rays), near-ultraviolet rays (eg KrF rays) including excimer lasers, far-ultraviolet rays, electron beams, ion beams and X-rays. A positive resist composition suitable for a positive photoresist can be used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is particularly preferable.
Specifically, the positive photoresist is preferably a composition containing a quinonediazide compound and an alkali-soluble resin. Examples of the quinonediazide compound include a naphthoquinonediazide compound.
The thickness of the photoresist layer 51 after drying is preferably 0.1 to 3 μm, preferably 0.2 to 2.5 μm, and more preferably 0.3 to 2 μm. Note that the application of the photoresist layer 51 can be suitably performed using the same application method as that for the first colored layer 11.

Next, as shown in the schematic cross-sectional view of FIG. 3, the photoresist layer 51 is exposed and developed to form a resist pattern (patterned photoresist layer) 52 provided with a resist removal portion group 51A.
The formation of the resist pattern 52 is not particularly limited, and a conventionally known photolithography technique can be used. By providing the resist removal unit group 51 </ b> A in the photoresist layer 51 by exposure and development, a resist pattern 52 as an etching mask used in the next dry etching is provided on the first colored layer 11.
The exposure of the photoresist layer 51 can be performed by exposing a positive or negative photoresist to g-line, h-line, i-line, etc., preferably i-line, through a predetermined mask pattern. . After the exposure, the photoresist is removed in accordance with a region where a colored pattern is to be formed by developing with a developer.
Any developer can be used as long as it dissolves the exposed portion of the positive resist and the uncured portion of the negative resist without affecting the first colored layer 11 containing the colorant. A combination of various organic solvents or an alkaline aqueous solution can be used.
As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving an alkaline compound so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 5% by mass is suitable. Alkaline compounds include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropyl Ammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like can be mentioned. In addition, when alkaline aqueous solution is used as a developing solution, generally a washing process is performed with water after development.

Next, as shown in the schematic cross-sectional view of FIG. 4, the resist pattern 52 is used as an etching mask, and patterning is performed by dry etching so that the removal portion group 120 is formed in the first colored layer 11. Thereby, the 1st coloring pattern 12 is formed. Here, the removal unit group 120 includes a first removal unit group 121 and a second removal unit group 122.
The removal unit group 120 is provided on the first colored layer 11 in a checkered pattern. Therefore, the 1st coloring pattern 12 in which the removal part group 120 is provided in the 1st coloring layer 11 has a some square 1st coloring pixel in checkered form.
Specifically, in the dry etching, the first colored layer 11 is dry etched using the resist pattern 52 as an etching mask. Representative examples of dry etching include JP-A-59-126506, JP-A-59-46628, JP-A-58-9108, JP-A-58-2809, JP-A-57-148706, JP-A-61-41102, and the like. And the contents thereof are incorporated herein by reference.

Dry etching is preferably performed in the following manner from the viewpoint of forming a pattern cross section closer to a rectangle and reducing damage to the support.
The etching gas preferably contains a halogen-based gas. The halogen-based gas is preferably a fluorine-based gas, and preferably contains a fluorine-based gas and an oxygen gas (O ₂ ). In the etching gas, the mixing ratio of fluorine-based gas and O ₂ (fluorine-based gas / O ₂ ) is preferably 1: 1 to 1: 4 in flow rate ratio. A known gas can be used as the fluorine compound gas, but a gas represented by the following formula (I) is preferable.
C _n H _m F _l Formula (I)
[In formula (I), n represents 1-6, m represents 0-13, and l represents 1-14. ]

As the fluorine-based gas represented by the above formula (I), perfluorogas is preferable. Specific examples of the fluorine-based gas are selected from the group of CF ₄ , C ₂ F ₆ , C ₃ F ₈ , C ₂ F ₄ , C ₄ F ₈ , C ₄ F ₆ , C ₅ F ₈ , and CHF _3. It is preferably at least one, more preferably at least one selected from the group consisting of C ₄ F ₆ , C ₅ F ₈ , C ₄ F ₈ , and CHF ₃ , C ₄ F ₆ , C ₅ One or more selected from the group of F ₈ is more preferable, and C ₄ F ₆ is particularly preferable. As the fluorine-based gas, one kind of gas can be selected from the above group, and two or more kinds may be included in the mixed gas.
In addition, when C _n F _l gas (n represents 1 to 6 and l represents 1 to 14) is dissociated, C becomes a factor that suppresses the progress of etching of the Si or SiN substrate. In order to suppress the progress of the etching, H ₂ , CO ₂ or the like may be further added.

From the viewpoint of maintaining the partial pressure control stability of the etching plasma and the perpendicularity of the etching shape, the etching gas is further made of helium (He), neon (Ne), argon (Ar) in addition to the fluorine-based gas and O _2. , Krypton (Kr), and a rare gas such as xenon (Xe) are preferably selected and mixed. As other gases that may be mixed, one kind of gas may be selected from the above group, and two or more kinds may be included in the mixed gas. In particular, argon gas is preferable.
The mixing ratio of other gases that may be mixed is preferably greater than 0 and 25 or less, more preferably 10 or more and 20 or less, and more preferably 16 when O ₂ is 1 as a flow ratio. preferable.

1-100 degreeC is preferable, as for the temperature of etching gas, 10-80 degreeC is more preferable, and 15-50 degreeC is further more preferable.
The gas flow rate of the etching gas is preferably 1500 ml / min or less, more preferably 500 to 1200 ml / min.
The flow rate of the halogen-based gas in the etching gas is preferably 10 to 400 ml / min, and more preferably 15 to 300 ml / min. The flow rate of oxygen gas in the etching gas is preferably 10 to 200 ml / min, and more preferably 20 to 100 ml / min. The ratio of the molar amount of carbon atoms and hydrogen atoms in the etching gas to the molar amount of fluorine atoms in the etching gas ((carbon atom + hydrogen atom) / fluorine atom) is 0.5 to 0.7. Is preferable, and it is more preferable that it is 0.6-0.7.
The flow rate of the argon gas in the etching gas is preferably 90% by volume or less with respect to the total amount of the etching gas. By setting the flow rate of the argon gas in the etching gas in such a range, it can be more effectively suppressed that the argon gas becomes an impurity and inhibits etching.

The internal pressure of the chamber in which dry etching is performed is preferably 0.5 to 6.0 Pa, and more preferably 1 to 5 Pa. The rectangularity of the etching pattern can be improved under conditions that satisfy the mixing ratio of the mixed gas and the internal pressure of the chamber.
The high frequency can be selected from 400 kHz, 60 MHz, 13.56 MHz, 2.45 GHz, and the like, and can be processed with an RF power of 50 to 2000 W, preferably 100 to 1000 W.
In the chamber for performing dry etching, the upper bias value is preferably 100 to 500 W, and more preferably 100 to 200 W. In the chamber where dry etching is performed, the electrode bias value is preferably 0 to 500 W, and more preferably 100 to 200 W.
200-1200W is preferable and the source power in the case of an etching process has more preferable 400-1000W.
1-100 degreeC is preferable and the processing temperature of an etching has more preferable 10-80 degreeC.
The etching processing time, that is, the time from the start to the end of etching is preferably 1 to 200 seconds, and more preferably 20 to 150 seconds.

  Further, the etching may be just a Just etching process or may include an over-etching process. Just etching refers to an operation in which etching is performed until the substrate is exposed. The Just etching time can be calculated by a method of detecting a difference in the intensity of secondary electrons generated when the base material is exposed by a detector or an etching rate. The over-etching process refers to performing an etching process in addition to just etching. Overetching is performed, for example, when an in-plane distribution exists after etching or to further remove residues. The overetching process is preferably performed by setting an overetching ratio. Moreover, it is preferable to calculate the overetching ratio from the etching process time to be performed first. The over-etching ratio can be arbitrarily set, but it is preferably 30% or less of the etching processing time in the etching process, and 5 to 25% in terms of maintaining the etching resistance of the photoresist and the rectangularity of the pattern to be etched. Is more preferable.

Next, as shown in the schematic cross-sectional view of FIG. 5, the resist pattern 52 remaining after the etching is removed.
It is preferable to remove the resist pattern remaining after etching by ashing. As the ashing treatment, ashing treatment, plasma treatment in which gas is excited by high frequency or the like (plasma ashing), or photoexcitation treatment (photoexcitation ashing) performed by irradiation of gas and ultraviolet rays is preferable. In particular, photoexcited ashing performed by gas and ultraviolet irradiation is preferable. By performing such an ashing process, it is possible to surely remove the resist pattern and more effectively suppress the removal of the first colored pattern 12 together with the resist pattern.
In photoexcited ashing, light such as ultraviolet rays is irradiated into a chamber into which a reactive gas is introduced. This removes the resist while promoting the chemical reaction between the reactive gas and the resist. By irradiating with ultraviolet rays, organic bonds in the resist can be broken. When ultraviolet rays are absorbed by ozone, excited oxygen atoms are generated. Excited oxygen atoms have a strong oxidizing power and react with the broken bond photoresist to volatilize and remove the resist.
In plasma ashing, oxygen gas is turned into plasma with non-ionizing radiation such as visible light or microwaves. When the resist is placed in oxygen plasma, it is combined with oxygen radicals in the plasma, becomes carbon dioxide and water, and is evaporated and peeled off. In a chamber into which a gas such as ozone is introduced, light such as ultraviolet rays is irradiated and the resist is peeled off using a chemical reaction between the gas and the resist.

1-50 Pa is preferable and the processing pressure in the case of an ashing process has more preferable 2-30 Pa.
1-100 degreeC is preferable and the process temperature in the case of an ashing process has more preferable 10-80 degreeC.
200-1200W is preferable and the source power in the case of an ashing process has more preferable 400-1000W.
The processing time of the ashing process, that is, the time from the start to the end of ashing is preferably 1 to 200 seconds, and more preferably 20 to 100 seconds.
In the chamber for performing the ashing treatment, the upper bias value is preferably 100 to 500 W, and more preferably 100 to 200 W. Moreover, in the chamber which performs an ashing process, 0-500W is preferable and, as for an electrode bias value, 100-200W is more preferable.

The gas used for the ashing treatment is not particularly limited, but is preferably Ar, fluorine-based gas, O ₂ , O ₃ , N ₂ , H ₂ , or a mixed gas thereof, and more preferably O _2. . As an example of the fluorine-based gas, the fluorine-based gas mentioned in the above-described etching gas can be used.
1-100 degreeC is preferable, as for the temperature of the gas used for an ashing process, 10-80 degreeC is more preferable, and 15-50 degreeC is further more preferable.
The gas flow rate used for the ashing treatment is preferably 1200 ml / min or less, more preferably 100 to 1000 ml / min.
The flow rate of the halogen-based gas in the gas used for the ashing treatment is preferably 0 to 20 ml / min, and more preferably 0 to 10 ml / min.
The flow rate of oxygen gas in the gas used for the ashing treatment is preferably 50 to 1000 ml / min, more preferably 80 to 800 ml / min. The flow rate of oxygen gas in the gas used for the ashing treatment is preferably 90% by volume or more with respect to the total amount of gas used for the ashing treatment.
The flow rate of argon gas in the gas used for the ashing treatment is preferably 0 to 1000 ml / min, more preferably 0 to 800 ml / min.

<<< Step of Forming Second Colored Pixel >>>
In the step of forming the second colored pixel, it is adjacent to the first colored pattern 12 in the same manner as the first colored pattern 12, except that the second colored composition is used instead of the first colored composition. The second colored pixel to be formed may be formed by dry etching, or the second colored pixel may be formed by photolithography. By forming the second colored pixel by photolithography, the number of steps can be reduced as compared with the case where all steps are performed by dry etching. Hereinafter, an example in which the second colored pixel is formed by photolithography will be described. The second colored composition is for forming a colored layer having a color tone different from that of the first colored composition.

In the step of forming the second colored pixels, as shown in the schematic cross-sectional view of FIG. 6, the second colored composition is embedded in the first removed portion group 121 and the second removed portion group 122. The second colored layer 21 is laminated with the second colored composition on the first colored layer 11 (that is, the first colored pattern 12 in which the removed portion group 120 is formed on the first colored layer 11). (Step (C)). Thereby, the 2nd coloring pattern 22 which has a some 2nd coloring pixel in the removal part group 120 is formed. Here, the second colored pixel is preferably a square pixel. The second colored layer 21 can be formed in the same manner as the method for forming the first colored layer 11.
The thickness of the second colored layer 21 after post-baking is preferably 0.1 to 1.5 μm, and more preferably 0.1 to 1.0 μm.

Then, the second colored layer 21 and each removed portion of the second removed portion group 122 are exposed and developed at a position 21A corresponding to the first removed portion group 121 of the second colored layer 21. Are removed (step (D)) (see the schematic cross-sectional view of FIG. 7).
The developer is synonymous with the developer described in the step of forming the first colored pixels described above.
As a development method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) The paddle method is particularly preferable.
The development time is not particularly limited as long as the second colored layer 21 and the second colored pixel 22R in the unexposed area are sufficiently dissolved, and is usually 10 seconds to 300 seconds. Preferably, it is 20 seconds to 120 seconds.
The temperature of the developer is preferably from 0 ° C to 50 ° C, more preferably from 15 ° C to 35 ° C.

<<< Step of Forming Third Colored Pixel >>>
The method for manufacturing a color filter may further include a step of forming a third colored pixel after the step of forming the second colored pixel.
In the step of forming the third colored pixel, the third colored pixel is dry-etched in the same manner as the first colored pixel except that the third colored composition is used instead of the first colored composition. Alternatively, the third colored pixel may be formed by photolithography. Hereinafter, an example in which the third colored pixel is formed by photolithography will be described. The third colored composition is for forming a colored layer having a color tone different from that of the first colored composition and the second colored composition.
In the step of forming the third colored pixel, as shown in the schematic cross-sectional view of FIG. 8, the third colored composition is embedded in the second removal portion group 122 to form a plurality of third colored pixels. The third colored composition is formed on the first colored layer (that is, the first colored pattern 12 in which the second colored pattern 22 is formed in the first removed portion group 121). The 3rd colored layer 31 which is a coloring composition is formed with a thing (process (E)). As a result, the third colored pattern 32 having a plurality of third colored pixels is formed in the second removal portion group 122. Here, the third colored pixel is preferably a square pixel. The third colored layer 31 can be formed in the same manner as the step of forming the first colored layer 11.
As thickness of the 3rd colored layer 31 after post-baking, the range of 0.1-1 micrometer is preferable, The range of 0.2-0.8 micrometer is more preferable, The range of 0.3-0.6 micrometer is more preferable .

  Then, the third colored layer 31 is removed by exposing and developing the position 31A of the third colored layer 31 corresponding to the second removal portion group 122. Thereby, as shown in the schematic sectional view of FIG. 9, the color filter 100 having the first colored pattern 12, the second colored pattern 22, and the third colored pattern 32 is manufactured (step (F) )).

  The 2nd coloring composition mentioned above and the 3rd coloring composition contain a coloring agent, respectively. Examples of the colorant include those described above in the coloring composition of the present invention, but one of the second colored pixel and the third colored pixel is a blue transmissive portion, and the other is a red transmissive portion. It is preferable. Examples of the colorant contained in the coloring composition for forming the blue transmitting part include C.I. I. Pigment violet 1, 19, 23, 27, 32, 37, 42, and C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80 or more It is done. The colorant contained in the coloring composition for forming the red transmitting part is preferably at least one selected from those described in paragraph numbers 0037 and 0039 of JP2012-172003A, Is incorporated herein by reference.

  In each of the second coloring composition and the third coloring composition, the content of the coloring agent with respect to the total solid content of the coloring composition is preferably 30% by mass or more, and 35% by mass or more. It is more preferable, and it is still more preferable that it is 40 mass% or more. Moreover, content of the coloring agent with respect to the total solid of a coloring composition is 90 mass% or less normally, and it is preferable that it is 80 mass% or less.

Moreover, it is preferable that a negative radiation sensitive composition is respectively used for the 2nd coloring composition and the 3rd coloring composition. This negative radiation sensitive composition includes negative radiation sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), deep ultraviolet rays including excimer laser, electron beams, ion beams and X rays. Sex compositions can be used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is particularly preferable.
Irradiation dose (exposure dose) is more preferably 30mJ / cm ² ~3000mJ / cm ² is preferably ^{50mJ / cm 2 ~2500mJ / cm 2} , 100mJ / cm 2 ~500mJ / cm 2 is particularly preferred.

  Specifically, the negative radiation-sensitive composition is preferably a composition containing a photopolymerization initiator, a polymerization component (polymerizable compound), a binder resin (alkali-soluble resin or the like), and the like. Examples described in paragraph Nos. 0017 to 0064 of Kaikai 2005-326453 may be mentioned, the contents of which are incorporated herein. Such a negative radiation sensitive composition utilizes the fact that the photopolymerization initiator initiates the polymerization reaction of the polymerizable compound upon irradiation with radiation, and as a result, the alkali soluble state becomes alkali insoluble. To do.

In the above description, an example in which the first colored pixel is formed by dry etching has been described, but a wet etching method may be used instead of dry etching. An example of a method for forming a pattern by the wet etching method is shown below.
On the substrate, a colored composition is applied to form a colored layer.
As the substrate, soda glass, alkali-free glass, borosilicate glass, quartz glass, or the like can be usually used. For the coating, methods such as spinner, spray coating, dipping, roll coating, bar coating, and die coating are used. The applied colored composition is preferably dried at a temperature of 50 to 180 ° C. for several seconds to several hours using an oven, a hot plate, infrared rays or the like.
A photoresist for pattern formation is applied on the colored layer to form a photoresist layer. The thickness of the photoresist layer is preferably 0.1 to 3 μm, preferably 0.2 to 2.5 μm, and more preferably 0.3 to 2 μm.
Subsequently, using an exposure apparatus, a mask is placed on the photoresist layer, irradiated with actinic radiation, and exposed. Examples of actinic rays include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays and visible rays are preferable. In the case where a positive photoresist is used, after the exposure, development of the photoresist layer and etching of the colored layer are simultaneously performed using a developer for positive photoresist. HF (BHF) can also be used for etching the colored layer. Next, the photoresist layer which becomes unnecessary after etching is peeled off. Usually, a solvent such as acetone or cellosolve, a mixed solvent of NMP (N-methyl-2-pyrrolidone) / MEA (monoethanolamine) / ultra pure water (Deionized water), or the like is used for peeling. The colored film is heat-treated to finish the patterning of the colored film. The heat treatment is carried out for 5 minutes to 5 hours while selecting the temperature and raising the temperature stepwise or selecting a certain temperature range and continuously raising the temperature. The heat treatment temperature is preferably 180 to 400 ° C, and more preferably 180 to 350 ° C. For example, heat treatment is performed at 130 ° C., 200 ° C., and 300 ° C. for 30 minutes. Further, the temperature may be increased linearly from room temperature to 300 ° C. over 2 hours.

  In the above description, the method of dry etching using the patterned resist layer as a mask and ashing to obtain the first colored pixel has been described. However, the colored layer is patterned by photolithography to form the first colored layer. Pixels may be obtained. For details of the photolithography method, reference can be made to paragraph numbers 0173 to 0185 of JP2013-227497A, the contents of which are incorporated herein.

In the above description, the manufacturing method assuming a general color filter array is shown, but the present invention is not limited to this. It can also be suitably used as a manufacturing method of a color filter for forming an n-color (n = 2 or more) color filter or a color filter whose shape is not square (for example, a line shape, a rectangular shape, etc.).
Alternatively, the first colored pixel that is the first color pixel can be formed by dry etching and ashing, and the second and subsequent color pixels can be formed by a method using a photolithography method.

  The color filter can be suitably used for a solid-state imaging device such as a CCD or CMOS, and is particularly suitable for a CCD or CMOS having a high resolution exceeding 1 million pixels. The solid-state image sensor color filter can be used, for example, as a color filter disposed between a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.

The film thickness of the colored pattern (colored pixel) in the color filter is preferably 0.1 to 1.0 μm, and more preferably 0.1 to 0.8 μm.
In addition, the size (pattern width) of the colored pattern (colored pixel) can be 2.5 μm or less, can be 2.0 μm or less, and can be 0.9 to 1.4 μm. In particular, by using a dry etching method, a colored pattern having the above size can be efficiently produced.

<Solid-state imaging device>
A solid-state image sensor which is one embodiment of the present invention includes a color filter for a solid-state image sensor. The configuration of the solid-state imaging device is a configuration provided with the color filter that is one embodiment of the present invention as the color filter for the solid-state imaging device, and is not particularly limited as long as the configuration functions as a solid-state imaging device. The following configurations are listed.

The solid-state imaging device has a plurality of photodiodes and polysilicon transfer electrodes constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) on a support, A device protective film made of silicon nitride or the like, which has a light shielding film made of tungsten or the like opened only on the light receiving part of the photodiode on the transfer electrode, and is formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving part. And having a color filter for a solid-state image sensor on the device protective film.
Further, a configuration having a light condensing means (for example, a microlens, etc., the same applies hereinafter) on the device protective film and under the color filter for the solid-state image sensor (on the side close to the support), The structure etc. which have a condensing means on may be sufficient.

<Image display device>
The color filter can be used not only for the solid-state imaging device but also for an image display device such as a liquid crystal display device or an organic EL display device, and is particularly suitable for use in a liquid crystal display device. A liquid crystal display device including a color filter which is one embodiment of the present invention can display a high-quality image with excellent display characteristics and hue of a display image.

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

The color filter may be used in a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the color filter can be applied to liquid crystal display devices with a wide viewing angle, such as horizontal electric field drive methods such as IPS and pixel division methods such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
The color filter can also be used in a bright and high-definition COA (Color-filter On Array) system. In the case of a COA type liquid crystal display device, the required characteristics for the color filter layer require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the stripping solution, in addition to the normal required characteristics as described above. Sometimes. In the color filter which is one embodiment of the present invention, since a dye having an excellent hue is used, the color purity, light transmittance, and the like are excellent, and the color pattern (pixel) is excellent in color, so the resolution is high and long-term durability is achieved. An excellent COA liquid crystal display device can be provided. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trends in the market (issued by Toray Research Center Research Division 2001)".

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

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

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

(Synthesis example of siloxane resin A)
In PGMEA, X-22-174ASX (manufactured by Shin-Etsu Chemical Co., Ltd.), methacrylic acid, and methyl methacrylate were dissolved in a mass ratio of 50:30:20, and a polymerization initiator (dimethyl- 2,2′-azobis (2-methylpropionate) “V-601”) was dissolved at a ratio of 0.3 mol% with respect to the total polymerization components, and polymerization was performed at 80 ° C. in a nitrogen atmosphere. On the way, 2 hours after the start of polymerization and 4 hours later, a polymerization initiator (V-601) was added in a ratio of 0.3 mol% (added later) in a ratio to the total polymerization components, and polymerization was performed for a total of 6 hours. After the polymerization, purification treatment and drying were performed to obtain siloxane resin A. The resulting siloxane resin A had a weight average molecular weight of about 10,000.
Siloxane resin A (Me represents a methyl group, n represents an integer, and R represents a substituent or a linking group)

化合物Ｄ

シロキサン樹脂Ｂ（ｎは０又は正の整数を表し、Ｒは置換基または連結基を表し、Ｚは下記構造を表す。）

シロキサン樹脂ＢのＺ部位

(Synthesis example of siloxane resin B)
X-22-174BX (manufactured by Shin-Etsu Chemical Co., Ltd.) and the following compound C are dissolved in PGMEA and a polymerization initiator (dimethyl-2,2′-azobis (2-methylpropionate) “V-601” is dissolved. )) Was dissolved in a ratio of 0.3 mol% with respect to the total polymerization components, and polymerization was performed at 80 ° C. in a nitrogen atmosphere. In the middle, after 2 hours from the start of polymerization, 0.3 mol% of a polymerization initiator (V-601) was added in a ratio to the total polymerization components, and polymerization was performed for 4 hours.
The obtained reaction solution and the following compound D are dissolved in PGMEA, and the polymerization initiator ((V-601) is dissolved in a ratio of 0.3 mol% with respect to the total polymerization components, and polymerization is performed at 80 ° C. in a nitrogen atmosphere. In the middle, after 2 hours from the start of polymerization, a polymerization initiator (V-601) was added in an amount of 0.3 mol% in a ratio to the total polymerization components, followed by polymerization for 4 hours. The weight average molecular weight of the siloxane resin B was about 8000. The X-22-174BX, the compound C, and the compound D were blended in a mass ratio of 90: 7: 3. did.
Compound C

Compound D

Siloxane resin B (n represents 0 or a positive integer, R represents a substituent or a linking group, and Z represents the following structure)

Z part of siloxane resin B

<Example 1>
(Preparation of coloring composition)
A coloring composition containing the following components was prepared by dispersing the following components with 0.5 mm beads for 30 minutes.
Organic colorant: A mixture of CI Pigment Green 58 (PG58) and CI Pigment Yellow 150 (PY150). 70% by mass with respect to the total solid content in the coloring composition (C.I. Pigment Green 58 is 38.5% by mass, CI Pigment Yellow 150 is 31.5% by mass)
-Siloxane resin A: 29.2% by mass with respect to the total solid content in the coloring composition
Triethoxyborane: 0.6% by mass with respect to the total solid content in the coloring composition
Aluminum isopropoxide: 0.1% by mass relative to the total solid content in the coloring composition
-PGMEA: The quantity from which the density | concentration of the solid content in a coloring composition will be 15.0 mass%

＜実施例３＞
実施例１の着色組成物において、シロキサン樹脂Ａ（着色組成物中の全固形分に対して２９．２質量％）を、上記シロキサン樹脂Ｂ（着色組成物中の全固形分に対して９．２質量％）と、シロキサン樹脂Ａ（着色組成物中の全固形分に対して２０質量％）とに変更し、さらに、ＰＧＭＥＡを、ＰＧＭＥＡとＰＧＭＥとの混合溶剤（質量比２０：８０）に変更したこと以外は実施例１と同様にして実施例３の着色組成物を調製した。
＜実施例４〜６＞
実施例１の着色組成物において、表１に示すように、その他成分のトリエトキシボラン及びアルミニウムイソプロポキシドのうち少なくともいずれかを配合しないこと以外は、実施例１と同様にして実施例４〜６の着色組成物を調製した。
＜実施例７＞
実施例１の着色組成物において、有機色材を、Ｃ.Ｉ.ピグメントレッド２５４（ＰＲ２５４）とＣ.Ｉ.ピグメントイエロー１３９（ＰＹ１３９）との混合物に変更したこと以外は実施例１と同様にして実施例７の着色組成物を調製した。なお、ＰＲ２５４が３８．５質量％、ＰＹ１３９が３１．５質量％とした。<Example 2>
In the colored composition of Example 1, the siloxane resin A (29.2% by mass with respect to the total solid content in the colored composition) was replaced with the resin X (with respect to the total solid content in the colored composition) having the following structure. %) And siloxane resin A (9.2% by mass with respect to the total solid content in the colored composition), and the colored composition of Example 2 was prepared in the same manner as Example 1. did.
Resin X (weight average molecular weight 25700, manufactured by FUJIFILM Fine Chemicals)

<Example 3>
In the colored composition of Example 1, siloxane resin A (29.2% by mass with respect to the total solid content in the colored composition) was changed to 9.9.9% with respect to the siloxane resin B (total solid content in the colored composition). 2 mass%) and siloxane resin A (20 mass% with respect to the total solid content in the colored composition), and further, PGMEA is changed to a mixed solvent of PGMEA and PGME (mass ratio 20:80). A colored composition of Example 3 was prepared in the same manner as Example 1 except for the change.
<Examples 4 to 6>
In the coloring composition of Example 1, as shown in Table 1, Examples 4 to 4 were carried out in the same manner as Example 1 except that at least one of triethoxyborane and aluminum isopropoxide as other components was not blended. 6 colored compositions were prepared.
<Example 7>
In the coloring composition of Example 1, the organic colorant was changed to a mixture of CI Pigment Red 254 (PR254) and CI Pigment Yellow 139 (PY139), and was the same as Example 1. Thus, a colored composition of Example 7 was prepared. In addition, PR254 was 38.5 mass% and PY139 was 31.5 mass%.

<Comparative Example 1>
In the coloring composition of Example 1, the siloxane resin A was changed to the resin X, and the coloring composition of Comparative Example 1 was prepared in the same manner as in Example 1 except that triethoxyborane and aluminum isopropoxide were not blended. Prepared.

<Comparative example 2>
In the coloring composition of Example 1, the siloxane resin A is changed to the resin X and the siloxane resin B so that the content of the siloxane resin B is 75% by mass with respect to the total mass of the resin components in the coloring composition. A colored composition of Comparative Example 2 was prepared in the same manner as Example 1 except that.

(Regarding pattern formation using a colored composition)
The colored composition of Example 1 obtained above was spin-coated at 2000 rpm on an 8-inch silicon wafer (substrate) using a spin coater ACT-8 manufactured by Tokyo Electron to obtain a coating film. The obtained coating film was heated on a hot plate at 100 ° C. for 2 minutes, and further heated at 220 ° C. for 5 minutes to form a colored layer (thickness 0.5 μm).

Subsequently, an adhesion treatment, a photoresist formation, and dry etching were performed to process the patterned colored layer. Specifically, pattern formation was performed according to the following procedure.
On the colored layer, a positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is applied with a spin coater and subjected to a heat treatment at 100 ° C. for 2 minutes to a thickness of 0.7 μm. A photoresist layer was formed so that Next, the corresponding region was subjected to pattern exposure at 300 mJ / cm ² using an i-line stepper (manufactured by Canon Inc., FPA3000i5 +), and heat treatment was performed at 110 ° C. for 1 minute. Then, after developing for 1 minute with a developer “FHD-5” (manufactured by FUJIFILM Electronics Materials Co., Ltd.), post-baking is performed at 100 ° C. for 1 minute to form a photoresist in the region where the array is to be formed. Removed. In this way, a Bayer pattern having a size of 1.2 μm × 1.2 μm was formed. Next, the colored layer was processed under the following dry etching conditions (1-1). Thereafter, the photoresist was removed under the following ashing conditions (2-1).

<Dry etching conditions (1-1)>
Equipment used: U-621 manufactured by Hitachi High-Technologies Corporation
(Single wafer dry etching, ashing equipment)
Process parameters for using dry etching chamber
Pressure: 2.0Pa
Gas used: Ar / C ₄ F ₆ / O ₂ = 600/20/50 ml / min
Processing temperature: 20 ° C
Source power: 500W
Upper bias / electrode bias = 500/1000 W
Processing time: Just etching + 10% overetching In addition to Just etching, overetching was performed for 10% of the etching time of Just etching. The Just etching time was determined from an end point detector (detector).

<Ashing condition (2-1)>
Equipment used: U-621 manufactured by Hitachi High-Technologies Corporation
(Single wafer dry etching, ashing equipment)
Use of dry etching chamber Process parameters
Pressure: 2.0Pa
Gas used: O ₂ = 300 ml / min
Processing temperature: 20 ° C
Source power: 1000W
Upper bias / electrode bias = 100 / 100W
Processing time: Until there is no photoresist residue (up to 300 seconds)

  A pattern was formed in the same manner as in Example 1 except that the colored composition of Example 1 was replaced with the colored compositions of Examples 2 to 7 and Comparative Examples 1 and 2.

  It was found that when the colored compositions of Examples 1 to 7 were used, the pattern shape was good and the remaining resist was small. On the other hand, it was found that when the colored compositions of Comparative Examples 1 and 2 were used, it was difficult to achieve both good pattern shape and less resist residue.

<Surface condition of colored layer>
The surface state after forming the colored layer was evaluated under the following conditions.
A: The surface of the colored layer is not rough or cracked.
B: Surface roughness of the colored layer is observed.
C: Cracks on the surface of the colored layer are observed.
D: Both surface roughness and cracks of the colored layer are observed.
<Formability of photoresist>
The formability of the photoresist was evaluated under the following conditions.
A: Photoresist can be formed vertically, and no bottom is seen at the bottom.
B: Photoresist is formed vertically, but some pattern hems are seen at the bottom.
C: The shape of the photoresist is slightly tapered.
D: The shape of the photoresist is poor and the pattern separation property is poor.
<Etching pattern shape>
The pattern shape after etching was evaluated under the following conditions.
A: The pattern after etching is formed vertically.
B: The pattern after etching is slightly tapered, but is processed linearly.
C: The pattern after etching is processed in a non-linear state.
D: Etching is difficult.

<Etching rate>
The etching rate was evaluated under the following conditions.
A: Just etching time of 0.5 μm is 100 seconds or less.
B: Just etching time of 0.5 μm exceeds 100 seconds and is 200 seconds or less.
C: Just etching time of 0.5 μm exceeds 200 seconds.
D: Etching is difficult.

<Ashing resistance>
Ashing resistance was evaluated for the colored layer after ashing under the following conditions. The film thickness was measured with a cross-sectional SEM.
A: The amount of scraping is 0.02 μm or less from the original thickness of the colored layer, and there is no pinhole.
B: The scraping amount is more than 0.02 μm and less than 0.05 μm from the original thickness of the colored layer, and there is no pinhole.
C: The amount of scraping exceeds 0.05 μm from the original thickness of the colored layer, and there is no pinhole.
D: There is a lot of damage, the scraping amount exceeds 0.05 μm from the original film thickness of the colored layer, and there is a pinhole.

  From the above results, the content of the organic color material in the total solid content of the colored composition is 20 to 90% by mass, and the content of the resin component in the total solid content of the colored composition is 10 to 80% by mass. Yes, by using a colored composition in which the content of the siloxane resin is 80 to 100% by mass with respect to the total mass of the resin component, the surface state of the colored layer, the formability of the photoresist, the etching pattern shape, the etching rate and the ashing resistance Was also found to be good.

(About etching conditions)
In pattern formation using the colored composition of Example 1, the pattern was similarly changed except that the dry etching conditions (1-1) were changed to the conditions (1-2) to (1-4) shown in the following table. Formed.
<Evaluation of pattern shape>
The pattern shape was evaluated under the following conditions.
A: The etching shape is sharp, the substrate scraping is 0.01 μm or less, and there is no etching residue.
B: Although the etching shape is slightly rounded, the substrate is scraped to 0.01 μm or less and there is no etching residue.
C: Although the etching shape is good, the chipping of the substrate is 0.01 μm or more. There is no etching residue.
D: Etching residue is generated.

From the results of the above table, the etching gas contains fluorine-based gas, oxygen gas, and argon gas, and the mixing ratio of fluorine-based gas and oxygen gas is 1: 1 to 1: 4 in volume ratio per unit time. It was found that the condition where the flow rate of argon gas in the gas was 90% by volume or less was preferable.
In the case of the dry etching condition (1-2), the progress of the etching is mottled compared to the case of the dry etching condition (1-1), and the obtained pattern periphery may have spotted unevenness due to the etching residue. all right. In the case of the dry etching condition (1-3), as compared with the case of the dry etching condition (1-1), the photoresist selection ratio is lowered. As a result, the photoresist must be formed thick. It was found that the pattern after etching transfer was rounded due to the rounding of the shape. In the case of the dry etching condition (1-4), it was found that etching damage tends to occur in the silicon wafer as compared with the case of the dry etching condition (1-1).

(About ashing conditions)
In pattern formation using the colored composition of Example 1, the pattern was changed in the same manner except that the ashing condition (2-1) was changed to the conditions (2-2) to (2-8) shown in the following table. Formed.
<Evaluation of pattern shape>
The pattern shape was evaluated under the following conditions.
A: Etching pattern shaving is less than 0.02 μm B: Etching pattern shaving is 0.02 to 0.05 μm
C: Etching pattern scraping amount is 0.05 μm or more D: Etching pattern scraping amount is 0.05 μm or more, and there is no manufacturing suitability in determining the pattern shape

  From the result of the said table | surface, it turned out that a pattern shape can be made especially favorable by making ashing conditions into conditions (2-1) or conditions (2-7).

11 1st colored layer, 12 1st colored pattern,
21 a second colored layer, a position corresponding to 21A first removal unit group 121,
22 second colored pattern, 22R second colored pixel,
31 third colored layer 31, 31A position corresponding to the second removal portion group 122,
32 third colored pattern, 51 photoresist layer,
51A resist removal portion group, 52 resist pattern,
120 removal unit group, 121 first removal unit group, 122 second removal unit group

Claims (19)

A coloring composition comprising a resin component containing a siloxane resin and an organic colorant,
The content of the organic colorant in the total solid content of the coloring composition is 20 to 90% by mass,
The content of the resin component in the total solid content of the coloring composition is 10 to 80% by mass,
The content of the siloxane resin to the total weight of the resin component Ri 80 to 100% by mass,
The siloxane resin is a copolymer component having at least a partial structure represented by the formula (1) and derived from a silicone-based macromer containing the partial structure represented by the formula (1), and pigment adsorption The coloring composition which is a siloxane resin which is a copolymer containing a copolymer component having a moiety, a siloxane resin having a structure represented by the formula (2), or a siloxane resin having a structure represented by the formula (3) .

(In formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 or 2 carbon atoms, or a hydrogen atom, * represents a bond, and n represents a positive number. Represents an integer.)

(In Formula (2), R ³ represents an (m + 1) -valent organic linking group, R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group, and A ¹ represents a pigment adsorption site or a hydrogen atom. P ¹ is a structure including a partial structure represented by the formula (1), and represents a structure derived from a silicone-based macromer including a partial structure represented by the formula (1). 8 represents 1 and 1 represents 1 to 10.)

(In Formula (3), R ⁵ represents a single bond or a divalent linking group, A ¹ represents a pigment adsorption site or a hydrogen atom, and P ¹ is a structure including a partial structure represented by Formula (1). And represents a structure derived from a silicone-based macromer containing a partial structure represented by the formula (1).) Forming a colored layer on a substrate using a colored composition; forming a resist layer on the colored layer; patterning; and dry etching the colored layer using the patterned resist layer as a mask. And a step of ashing the resist layer remaining after the dry etching, and a coloring composition used in a pattern forming method,
The coloring composition, seen containing a resin component comprising a siloxane resin, and an organic colorant, a
The content of the organic colorant in the total solid content of the coloring composition is 20 to 90% by mass,
The content of the resin component in the total solid content of the coloring composition is 10 to 80% by mass,
The coloring composition whose content of the said siloxane resin with respect to the total mass of the said resin component is 80-100 mass%. The coloring composition according to claim 2 , wherein the siloxane resin includes a siloxane resin having a partial structure represented by the following formula (1A).

(In formula (1A), “-” represents a connector.) The coloring composition of Claim 3 in which the said siloxane resin contains the siloxane resin which has a partial structure represented by following formula (1).

(In formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 or 2 carbon atoms, or a hydrogen atom, * represents a bond, and n represents a positive number. Represents an integer.) The colored composition according to any one of claims 2 to 4 , wherein the siloxane resin is a siloxane resin obtained by hydrolytic condensation of an alkoxysilane compound. The coloring composition of any one of Claims 1-5 whose total content of the said organic color material and the said siloxane resin is 80-100 mass% with respect to the total solid in a coloring composition. The colored composition according to any one of claims 1 to 6 , wherein the organic color material is dispersed by the siloxane resin. The coloring composition according to any one of claims 1 to 7 , wherein the organic color material contains at least one of an organic pigment and an organic dye. The cured film formed by hardening | curing the coloring composition of any one of Claims 1-8 . The color filter which has a colored layer using the coloring composition of any one of Claims 1-8 . Forming a colored layer on a substrate using the colored composition according to any one of claims 1 to 8 ,
Forming a resist layer on the colored layer and patterning;
Using the patterned resist layer as a mask , dry etching the colored layer ;
Ashing the resist layer remaining after the dry etching;
A pattern forming method. The pattern forming method according to claim 11 , wherein the dry etching includes dry etching using an etching gas containing a halogen-based gas. The etching gas includes a fluorine-based gas, an oxygen gas, and an argon gas,
The mixing ratio of the fluorine-based gas and the oxygen gas is 1: 1 to 1: 4 by volume ratio in unit time,
The pattern formation method according to claim 12 , wherein a flow rate of the argon gas in the etching gas is 90% by volume or less. Said etching gas comprises argon gas and C ₄ F ₆ and oxygen gas, a pattern forming method according to claim 12 or 13. The ashing process, ashing, a plasma treatment or a photoexcitation process, a pattern forming method according to any one of claims 11 to 14. The manufacturing method of a color filter containing the pattern formation method of any one of Claims 11-15 . A solid-state imaging device having the color filter according to claim 10 . An image display device comprising the color filter according to claim 10 . Forming a first colored pixel on the substrate;
Forming a second colored pixel having a color tone different from that of the first colored pixel on a substrate on which the first colored pixel is formed;
Including
The step of forming the first colored pixel includes
Forming a first colored layer on the substrate using the colored composition according to any one of claims 1 to 8 ;
Forming a resist layer on the first colored layer and patterning the resist layer;
Using the patterned resist layer as a mask, dry etching using an etching gas containing a halogen-based gas; and
Ashing the resist layer remaining after the dry etching step;
A method for producing a color filter comprising:

Images