JP2011069817A - Method for manufacturing substrate for microarray, composition for forming bulkhead, bulkhead of substrate for microarray, method for manufacturing biochip, and biochip - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing substrate for microarray, composition for forming bulkhead, bulkhead, method for manufacturing biochip, and biochip, in which both adhesion of bulkhead with substrate and water resistance of bulkhead are improved. <P>SOLUTION: The method for manufacturing the substrate for microarray 100, equipped with a substrate 10, a bulkhead 20 partitioning surface of the substrate 10 and an area 30 partitioned by the bulkhead, includes the process to form the first film by using the composition containing compound (A) such as C.I. pigment red 254, and the process to form the bulkhead through patterning of the first film. These composition and bulkhead are provided for the processes. Also it includes the process to form the bulkhead 20 by using the method for manufacturing substrate for microarray, the process to arrange anchoring material for fixing target matter in the area 30, and the process to fix the target matter in the anchoring material. The biochip is thus obtained. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a microarray substrate, a partition wall forming composition, a partition wall for a microarray substrate, a method for producing a biochip, and a biochip. More specifically, the present invention relates to a method for producing a substrate for microarray used in a microarray such as a biochip used for DNA sequencing, a composition for forming a partition, a partition for a substrate for microarray, a method for producing a biochip, and a biochip.

In recent years, substances such as nucleic acids, proteins, peptides, sugar chains, low molecular weight compounds, cells, and tissues are mounted as probe molecules on a substrate, and the interaction with biological related substances that are target molecules is measured and reactions are performed. Microarrays are attracting attention as devices for use. In this microarray, a substrate (a substrate for microarray) having a plurality of partitioned reaction regions (cavities) for immobilizing probe molecules is used. Specifically, for example, biochips are known in which target materials such as DNA, proteins, sugar chains, and other biological materials are partitioned on the substrate surface and accumulated at high density. This biochip is attracting attention because it can process a large number of specimens simultaneously. Attempts have been made to increase the amount of accumulation in order to obtain more information through batch processing.
As a method of arranging a large number of target materials in an array on the substrate surface, two types of methods are mainly known. One is a method of arranging the target material by synthesizing on the substrate, and the other is a method of arranging the target material prepared in advance on the substrate surface via droplets or the like. Among these, the latter method employs, for example, a method in which a liquid in which a target material is dissolved is dropped and fixed on a predetermined region of the substrate.
The following patent documents 1 to 3 are known as techniques using such a technique.
Further, when such a biochip is used, it can be used as a substrate for a sequencing agent for detecting a base sequence such as a nucleic acid. A base material can be detected by amplifying an ecological substance on the biochip by polymerase chain reaction (PCR method) and using a fluorescent label emitted from the ecological substance (Patent Document 4 or 5).
Furthermore, as a method for detecting the interaction and reaction between the probe molecule and the target molecule, the fluorescence emitted during the interaction and reaction between the probe molecule and the target molecule can be used using a fluorescent labeling agent, if necessary. Techniques for detecting are known. That is, for example, in a reaction using a fluorescent label, a technique is known in which the entire microarray is irradiated with induced light, and fluorescence emitted from individual cavities is received by a measuring device to detect the presence or state of the reaction ( Patent Documents 1 to 5).

JP 2005-214889 A WO06 / 101229 JP 2001-343385 A JP 2006-320307 A WO07 / 048033

In the microarray such as the biochip, it is general to obtain information on the reaction from the fluorescence by using a fluorescent label for the reaction in each cavity partitioned by the partition walls. That is, for example, in a reaction using a fluorescent label, the entire biochip is irradiated with induced light, and fluorescence emitted from each cavity is received by a measuring device to detect the presence or state of the reaction.
However, as described above, as the density increases, color mixing of fluorescence emitted from each cavity becomes a problem. That is, there is a problem that the partition walls are narrowed due to high density and the light between the cavities cannot be sufficiently separated. On the other hand, the component that has an absorption band in the measurement light region (such as a light absorber) can be optically separated between the cavities, but the properties that are originally required for the partition are reduced by the addition of different components to the partition. There is a problem that can be.

  The present invention has been made in view of the above problems, and improves the adhesion between the partition wall and the substrate and the water resistance of the partition wall while ensuring optical separation between the cavities (that is, regions partitioned by the partition wall). It is an object of the present invention to provide a method for producing a microarray substrate, a composition for forming a partition, a partition for a microarray substrate, a method for producing a biochip, and a biochip.

〔式（１）中、Ｒ^１及びＲ^２は各々独立に、水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のパーフルオロアルキル基、炭素数０〜５のアミノ基を表す。〕
〈２〉前記感放射線性組成物は、更に、重合体（Ｂ）、多官能性単量体（Ｃ）及び感放射線性重合開始剤（Ｄ）を含有し、且つ、
前記重合体（Ｂ）が、アルカリ可溶性重合体である前記〈１〉に記載のマイクロアレイ用基板の製造方法。
〈３〉基板と、前記基板表面を区画する隔壁と、前記隔壁により区画された基板上の領域と、を有するマイクロアレイ用基板における該隔壁を形成するための隔壁形成用組成物であって、
下記式（１）に示す化合物（Ａ）を含むことを特徴とする隔壁形成用組成物。

〔式（１）中、Ｒ^１及びＲ^２は各々独立に、水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のパーフルオロアルキル基、炭素数０〜５のアミノ基を表す。〕
〈４〉更に、重合体（Ｂ）、多官能性単量体（Ｃ）及び感放射線性重合開始剤（Ｄ）を含有し、且つ、
前記重合体（Ｂ）が、アルカリ可溶性重合体である前記〈３〉に記載の隔壁形成用組成物。
〈５〉前記〈３〉又は〈４〉に記載の隔壁形成用組成物を用いて得られたことを特徴とするマイクロアレイ用基板の隔壁。
〈６〉（ａ）前記〈１〉又は〈２〉に記載のマイクロアレイ用基板の製造方法を用いて、前記マイクロアレイ用基板を製造するマイクロアレイ用基板製造工程と、
（ｂ）前記領域にターゲット物質を固定するための固定用物質を配置する固定用物質配置工程と、
（ｃ）前記固定用物質にターゲット物質を固定する固定化工程と、を備えることを特徴とするバイオチップの製造方法。
〈７〉（ａ）前記〈１〉又は〈２〉に記載のマイクロアレイ用基板の製造方法を用いて、前記マイクロアレイ用基板を製造するマイクロアレイ用基板製造工程と、
（ｄ）前期領域に、表面にターゲット物質を有する担持物質を、配置する担持物質配置工程と、を備えることを特徴とするバイオチップの製造方法。
〈８〉前記固定用物質が、ポリリシン、コラーゲン、ラミニン、含シアル酸オリゴ糖、マンノース結合性レクチン、インテグリンファミリーリガンド、ペプチド、抗原又は抗体並びに核酸である前記〈６〉に記載のバイオチップの製造方法。
〈９〉前記ターゲット物質が、生体関連物質である前記〈７〉又は〈８〉に記載のバイオチップの製造方法。
〈１０〉前記〈７〉乃至〈９〉のうちのいずれかに記載のバイオチップの製造方法によって得られたことを特徴とするバイオチップ。な The present invention is as follows.
<1> In a method for manufacturing a microarray substrate, comprising: a substrate; a partition partitioning the surface of the substrate; and a region on the substrate partitioned by the partition.
A first film forming step of forming a first film on a substrate using a radiation-sensitive composition containing a compound (A) represented by the following formula (1);
And a partition wall forming step of forming the partition walls by patterning the first film by a lithography method.

[In Formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a perfluoroalkyl group having 1 to 10 carbon atoms, or an amino acid having 0 to 5 carbon atoms. Represents a group. ]
<2> The radiation-sensitive composition further contains a polymer (B), a polyfunctional monomer (C), and a radiation-sensitive polymerization initiator (D), and
The method for producing a microarray substrate according to <1>, wherein the polymer (B) is an alkali-soluble polymer.
<3> A partition forming composition for forming the partition in a microarray substrate having a substrate, a partition partitioning the substrate surface, and a region on the substrate partitioned by the partition,
A composition for forming a partition wall comprising a compound (A) represented by the following formula (1).

[In Formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a perfluoroalkyl group having 1 to 10 carbon atoms, or an amino acid having 0 to 5 carbon atoms. Represents a group. ]
<4> Furthermore, it contains a polymer (B), a polyfunctional monomer (C) and a radiation sensitive polymerization initiator (D), and
The partition-forming composition according to <3>, wherein the polymer (B) is an alkali-soluble polymer.
<5> A partition wall for a microarray substrate obtained by using the partition wall forming composition according to <3> or <4>.
<6> (a) A microarray substrate manufacturing process for manufacturing the microarray substrate using the method for manufacturing a microarray substrate according to <1> or <2>;
(B) a fixing substance arranging step of arranging a fixing substance for fixing the target substance in the region;
(C) An immobilization step of immobilizing a target material on the immobilization material, and a biochip manufacturing method comprising:
<7> (a) A microarray substrate manufacturing process for manufacturing the microarray substrate using the method for manufacturing a microarray substrate according to <1> or <2>;
(D) A biochip manufacturing method comprising: a support material disposing step of disposing a support material having a target material on a surface thereof in a first region.
<8> The biochip according to <6>, wherein the immobilizing substance is polylysine, collagen, laminin, sialic acid oligosaccharide, mannose-binding lectin, integrin family ligand, peptide, antigen or antibody, and nucleic acid. Method.
<9> The biochip manufacturing method according to <7> or <8>, wherein the target material is a biological material.
<10> A biochip obtained by the biochip manufacturing method according to any one of <7> to <9>. Na

According to the method for manufacturing a microchip substrate of the present invention, it is possible to improve the adhesion between the partition wall and the substrate and the water resistance of the partition wall while ensuring optical separation between the regions partitioned by the partition wall. .
In the method for producing a microchip substrate, the radiation-sensitive composition further contains a polyfunctional monomer (C) and a radiation-sensitive polymerization initiator (D), and the polymer (B) In the case of an alkali-soluble polymer, excellent properties in adhesion and water resistance can be exhibited.
According to the partition wall forming composition of the present invention, the optical separation between the partitioned regions is ensured, and the adhesion to the substrate (the base substrate constituting the microchip substrate) and the water resistance are excellent. A partition wall of a microchip substrate (which can also be used for biochip applications) can be obtained.
When the partition wall forming composition further contains a polyfunctional monomer (C) and a radiation sensitive polymerization initiator (D), and the polymer (B) is an alkali-soluble polymer, Excellent properties in water resistance and water resistance.
According to the partition wall of the microchip substrate of the present invention (which can also be used for biochips), the substrate (element substrate constituting the microchip substrate) while ensuring optical separation between the partitioned regions. It can be set as the partition wall excellent in adhesiveness and water resistance.
According to the biochip manufacturing method of the present invention, a biochip with improved adhesion between the partition wall and the substrate and water resistance of the partition wall while ensuring optical separation between the regions partitioned by the partition wall is manufactured. it can.
According to the biochip of the present invention, the optical separation between regions partitioned by the partition walls is ensured, and the adhesion between the partition walls and the substrate and the water resistance of the partition walls are excellent.

1 is a perspective view schematically illustrating a microchip substrate (pre-biochip) according to the present invention. 1 is a plan view schematically illustrating a microchip substrate (pre-biochip) according to the present invention. It is explanatory drawing which illustrates typically the manufacturing method of the board | substrate for microchips which concerns on this invention. It is explanatory drawing which illustrates typically the manufacturing method of the 1st biochip which concerns on this invention. It is explanatory drawing which illustrates typically the manufacturing method of the 2nd biochip which concerns on this invention.

  Hereinafter, the present invention will be described in detail. In the present specification, “(meth) acryl” means acryl and methacryl, and “(meth) acrylate” means acrylate and methacrylate.

[1] Method for Producing Microchip Substrate The method for producing a microchip substrate according to the present invention comprises a substrate (a substrate constituting the microchip substrate, hereinafter also simply referred to as “element substrate”), and a surface of the substrate. In the manufacturing method of the substrate for microarrays having a partition wall to be partitioned and a region on the substrate partitioned by the partition wall,
A first film forming step of forming a first film on a substrate using a radiation-sensitive composition containing the compound (A);
And a partition wall forming step of forming the partition walls by patterning the first film by a lithography method.

  In the microarray substrate of the present invention, by forming the partition wall 20 using the compound of the above formula (1), the partition wall 20 can efficiently shield light having a target wavelength (550 nm). Therefore, excellent optical separation of the region (cavity) 30 separated by the partition wall 20 can be obtained. In addition, the compound represented by the above formula (1) can exhibit a high shielding effect when added in a small amount. For this reason, the compounding quantity to the radiation sensitive composition of the compound of said Formula (1) can be restrained small, and adhesiveness with the base substrate 10 can fully be exhibited. In particular, since more resin components that contribute to the adhesion of the partition wall 20 to the substrate 10 can be blended, it is possible to contribute to the improvement of adhesion.

The partition 20 formed by this method partitions the surface of the raw substrate 10 as illustrated in FIGS. A region partitioned by the partition wall 20 becomes a cavity 30 surrounded by the partition wall 20.
In addition, the biochip 100 referred to in the present method includes at least the base substrate 10 and the partition wall 20 (without the fixing material and the target material), and the microarray substrate (that is, the pre-biochip) 101, the fixing material and A support material 53 is placed on a chip 100a (FIG. 4) on which a target material is disposed, and a microarray substrate (that is, a pre-biochip) 101 having at least a base substrate 10 and partition walls 20 (without a support material). It is the chip | tip 100b (FIG. 5) arrange | positioned. The microarray substrate (ie, pre-biochip) 101 is a chip that is used by a user introducing a target material. Details of other biochips and partition walls will be described later.

The “first film forming step” is a step of forming the first film 21 on the base substrate 10 using a radiation-sensitive composition containing the compound (A) represented by the formula (1) (see FIG. 3). ).
In the present invention, by using the radiation-sensitive composition containing the compound (A), the cavities can be optically separated, and the partition wall and the base substrate (or another layer laminated on the base substrate surface) Adhesion can be improved. In addition, when the partition wall is brought into contact with water or a liquid containing water, the swelling of the partition wall can be suppressed, thereby preventing the partition wall from being peeled off from the surface of the base substrate and the adhesion being deteriorated.

The “radiation sensitive composition” is a composition containing the compound (A). About this radiation sensitive composition and compound (A), each in the composition for partition formation mentioned later can be applied as it is.
The radiation-sensitive composition may be formed into a film in any way, but usually, the liquid radiation-sensitive composition is applied to the target surface (for example, the surface of the base substrate or another layer laminated on the base substrate). Formed on the surface). The coating method is not particularly limited, and various methods such as spin coating, cast coating, roll coating, and printing can be used.

  Further, when the radiation-sensitive composition contains a solvent, the coating film obtained by applying the radiation-sensitive composition was included in the coating film by pre-baking (PB), if necessary. A solvent etc. can be volatilized. Although the heating conditions at the time of prebaking are suitably selected according to the characteristic of a radiation sensitive composition, heating temperature can be 30-240 degreeC, for example, Preferably it can be 50-180 degreeC. Furthermore, the heating time can be 30 to 1800 seconds, and preferably 60 to 600 seconds.

  The thickness of the first film is not particularly limited, but can be 0.01 to 500 μm, for example. Preferably it can be 1-100 micrometers, More preferably, it can be 10-70 micrometers. In this range, the height of the partition wall suitable for the biochip can be ensured.

The kind of the “substrate (substrate)” is not particularly limited, and may be made of an inorganic material, an organic material, or a composite material thereof. The base substrate 10 may be made of different materials on the front side and the other side. Examples of the material constituting the base substrate include inorganic materials mainly containing silicon such as silicon, silicon dioxide, and glass (including borosilicate glass, surface-modified glass, and quartz glass). Further, organic materials such as polypropylene and polyacrylamide (including polyacrylamide whose surface is activated by acrylamide) can be used. In addition, a base substrate having a reactive site (for example, an active amino group) suitable for further improving the adhesion with the first film can be used as appropriate.
In addition, as the base substrate 10, a base substrate having a light receiving element such as a solid-state image sensor (such as a CMOS image sensor) can be used. When an element substrate having a light receiving element is used, the element substrate itself can receive the fluorescence emitted during the interaction and reaction between the probe molecule and the target molecule.

The “partition wall forming step” is a step of patterning the first film 21 by a lithography method to form the partition wall 20 (see FIG. 3).
The “lithography method” is a method of patterning the first film 21 by exposing through the pattern mask 40 so that a desired pattern is obtained, and then developing to reveal the pattern. That is, the partition wall forming step usually includes an exposure step of exposing the first film 21 through the pattern mask 40 and a developing step of removing unnecessary portions with a developer after the exposure.
In addition, FIG. 3 is a case where a negative type radiation sensitive composition is used, and also when a positive type radiation sensitive composition is used, a partition can be formed with the same method.

In the exposure step, the type of radiation used for exposure is not particularly limited, and the spectrum of a mercury lamp (wavelength: 300 to 600 nm), LED lamp, ultraviolet light (including g-line, h-line, i-line, etc.), deep ultraviolet ray {KrF excimer laser (Including wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), EUV (wavelength 13 nm, etc.), X-rays such as synchrotron radiation, charged particle beams such as electron beams, γ Examples thereof include a line, a molecular beam, and an ion beam. These may use only 1 type and may use 2 or more types together. The exposure conditions are appropriately selected according to the composition of the radiation-sensitive composition, the type of additive, and the like.

  The developing step is a step of removing a portion soluble in the developer after the exposure step. As the developer, various known alkaline developers are usually used. The solubility in the developer means that there is a difference in solubility in the developer relative to the exposed part and the unexposed part. When the film is immersed in the developer at 23 ° C. for 1 minute, the initial state of the film The property of being dissolved exceeding 1% of the film thickness.

  Examples of the developer include alkali metal hydroxide, aqueous ammonia, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, and 1,8-diazabicyclo [5.4.0]. Examples thereof include liquids in which alkaline compounds such as -7-undecene and 1,5-diazabicyclo [4.3.0] -5-nonene are dissolved. Although the density | concentration of the said alkaline compound is not specifically limited, 10 mass% or less is preferable, 1-10 mass% is more preferable, and 2-5 mass% is still more preferable.

The kind of the solvent constituting the developer is not particularly limited, and examples thereof include water and / or an organic solvent. Organic solvents include ketones such as acetone; alcohols such as ethyl alcohol; ethers such as tetrahydrofuran; esters such as ethyl acetate; aromatic hydrocarbons such as toluene; phenol, acetonyl acetone, dimethylformamide, etc. Is mentioned. These organic solvents may use only 1 type and may use 2 or more types together.
Further, a surfactant or the like can be added to the developer. Thereby, the wettability of the developer with respect to the first film can be improved.

In the manufacturing method of the substrate for microarrays of this invention, other processes can be provided besides the first film forming process and the partition forming process. As another process, a heat treatment {that is, a PEB (Post Exposure Bake)} performed after the exposure is given. The apparent sensitivity of the first film can be improved by performing PEB. The heating conditions for PEB are appropriately selected according to the composition of the radiation-sensitive composition, the type of additive, and the like, but are preferably 30 to 200 ° C, more preferably 50 to 150 ° C. Further, after the development, a water washing step of washing the first film (partition) after development can be performed.
Furthermore, as another process, the heat processing performed after image development are mentioned. The heating conditions for the heat treatment performed after development are appropriately selected according to the composition of the radiation-sensitive composition, the type of additives, etc., but are usually 30 to 300 ° C., preferably 50 to 250 ° C., and the heating time. Is usually 1 minute to 5 hours.

[2] Partition wall forming composition The partition wall forming composition of the present invention is a microarray substrate having a base substrate, partition walls partitioning the surface of the base substrate, and regions on the substrate partitioned by the partition walls. A partition wall forming composition for forming the partition wall,
Compound (A) is contained.

The barrier rib-forming composition of the present invention is a radiation-sensitive composition in the method for producing a microarray substrate. That is, the partition wall forming composition has radiation sensitivity.
The partition wall forming composition of the present invention contains the compound (A). This compound (A) is an organic pigment, and each has a specific absorption band. As will be described later, the partition wall forming composition contains this compound (A) regardless of the negative type and the positive type.

〔式（１）中、Ｒ^１及びＲ^２は各々独立に、水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のパーフルオロアルキル基、炭素数０〜５のアミノ基を表す。〕 The “compound (A)” is a compound represented by the following formula (1).

[In Formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a perfluoroalkyl group having 1 to 10 carbon atoms, or an amino acid having 0 to 5 carbon atoms. Represents a group. ]

Examples of the alkyl group having 1 to 10 carbon atoms in the formula (1) include a methyl group, an ethyl group, a propyl group (n-, i-), a butyl group (n-, i-, sec-, t-), and the like. Is mentioned.
Examples of the perfluoroalkyl group having 1 to 10 carbon atoms in the formula (1) include groups in which all of the hydrogen atoms of the alkyl group having 1 to 10 carbon atoms in the formula (1) are replaced by fluorine atoms.

The amino group having 0 to 5 carbon atoms in the formula (1) is a group represented by —NR ³ R ⁴ . R ³ and R ⁴ of this amino group each independently represent a hydrogen atom, a linear or branched chain hydrocarbon group having 1 to 10 carbon atoms, or a cyclic hydrocarbon group having 3 to 10 carbon atoms. . Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group (n-, i-), and a butyl group (n-, i-, sec-, t-). On the other hand, as the cyclic hydrocarbon group, an alicyclic group such as cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group; phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, Aromatic groups such as 4-t-butylphenyl group, 1-naphthyl group and benzyl group can be mentioned.

Among these, R ¹ and R ² in the formula (1) are preferably a halogen atom, a phenyl group or a hydrogen atom, and more preferably a chlorine atom or a phenyl group. In addition, R ¹ and R ² in the formula (1) are preferably bonded to the 4-position carbon of the benzene ring included in the formula (1).

  Specific examples of the component (A) include C.I. I. Pigment red 254, 264 and 255, and C.I. I. Pigment Orange 71 and 73 are listed. Among these, C.I. I. Pigment Red 254, 264 and 255 are preferable. Two or more of these components (A) can be used in combination.

  Although content of the said compound (A) is not specifically limited, 0.01-300 mass parts is preferable with respect to 100 mass parts of polymers (B), 0.1-100 mass parts is more preferable, 100 parts by mass is more preferable. In this range, particularly excellent adhesion and water resistance can be obtained.

  Other pigments can be used in combination with the compound (A) in the partition wall forming composition of the present invention. The type of other pigments is not particularly limited. For example, various compounds classified as pigments (hereinafter simply referred to as “pigment compounds”) in the color index (CI; issued by The Society of Dyer's and Colorists). Can be used.

  Examples of the pigment compound include those having the following color index (CI) numbers. That is, C.I. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, 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 red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 272;

  C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 211;

  C. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 72, C.I. I. Pigment orange 74;

  C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38; C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment blue 80; C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58; C.I. I. Pigment brown 23, C.I. I. Pigment brown 25; C.I. I. Pigment black 1, C.I. I. Pigment Black 7.

  These above-mentioned various pigment compounds may use only 1 type, and may use 2 or more types together. Furthermore, not only the above-mentioned organic pigment but also an inorganic pigment can be used as necessary. Examples of inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean {red iron oxide (III)}, cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, Examples include amber, titanium black, synthetic iron black, and carbon black. These inorganic pigments may be used alone or in combination of two or more. In addition, one or more dyes or natural pigments can be used.

  When other pigments other than these compounds (A) are used in combination, the content is not particularly limited, but is usually preferably 100 parts by mass or less with respect to 100 parts by mass of the polymer (B). 0.00001-50 mass parts is more preferable, and 0.00001-10 mass parts is still more preferable.

  Moreover, the composition for partition formation of this invention contains a polymer (B) normally. Various polymers can be used for the polymer (B) contained in the partition wall forming composition depending on its form. That is, the present composition may be a negative radiation sensitive composition or a positive radiation sensitive composition. Further, the polymer (B) may be an organic polymer (carbon skeleton polymer), and an inorganic polymer {a polymer having an element other than carbon (for example, Si and Si and O) as a skeleton. }. That is, the partition wall forming composition may be a partition wall forming composition having an organic polymer as the polymer (B) and having negative characteristics (hereinafter, also simply referred to as “organic negative composition”), The polymer (B) may be a barrier rib-forming composition (hereinafter also simply referred to as “inorganic negative composition”) containing an inorganic polymer, and the polymer (B) may be an organic polymer. It may be a composition for forming barrier ribs containing positive characteristics (hereinafter also simply referred to as “organic positive composition”), and forming barrier ribs having positive characteristics containing an inorganic polymer as the polymer (B). Composition (hereinafter also simply referred to as “inorganic positive composition”).

  In the partition wall forming composition, when the organic polymer is a main component, the organic polymer is contained in an amount of 51% by mass or more (may be 100% by mass) when the entire composition is 100% by mass. Is done. That is, the inorganic polymer is not included, or even if included, it is less than 51% by mass. Similarly, when the main component is an inorganic polymer, the inorganic polymer is contained in an amount of 51% by mass or more (or 100% by mass) when the entire composition is 100% by mass. That is, the organic polymer is not included, or even if included, it is less than 51% by mass.

(1) Negative-type radiation-sensitive composition mainly composed of an organic polymer When the organic negative-type composition (1) is used as the partition-forming composition, examples of the organic negative-type composition include, for example, Disclosed in 2007-293306, JP2003-215802, JP2004-10660, JP2003-258422, JP2004-10660, JP2004-171026, and the like. Compositions can be used.

Among these, it is preferable to use the composition disclosed in JP 2007-293306 A. That is, the polymer (B) contains an alkali-soluble organic polymer (B1) (that is, the alkali-soluble polymer). Furthermore, it is preferable to contain a polyfunctional monomer (C1) and a radiation sensitive polymerization initiator (D1).
Further, when the alkali-soluble organic polymer (B1) as the polymer (B) has a reactive group, it has a group capable of reacting with the reactive group and a compound having a polymerizable group (polymerizable). A polymerizable group can be introduced into the alkali-soluble organic polymer (B1) using a group introduction component). That is, the alkali-soluble organic polymer into which a polymerizable group has been introduced by reacting the reactive group of the alkali-soluble organic polymer (B1) of the polymerizable group-introducing component with a group capable of reacting with the reactive group. (B1) can be used. Thereby, the water resistance of the partition 20 formed from a polymer (B1) and the adhesiveness (waterproof adhesiveness) with respect to the base substrate 10 of the partition 20 can be improved. The polymerizable group-introducing component and the alkali-soluble organic polymer (B1) having the polymerizable group introduced will be described later.

  The alkali-soluble organic polymer (hereinafter also simply referred to as “polymer (B1)”) as the polymer (B) is a structural unit represented by the following formula (2) (hereinafter simply referred to as “structural unit (B11)”). ]))) Or a polymer containing a structural unit represented by the following formula (3) (hereinafter also simply referred to as “structural unit (B12)”) is preferable.

〔式（２）中、Ｒ^１は水素原子又はメチル基を表し、Ｒ^２は炭素数６〜１２の直鎖状、環状もしくは芳香族の炭化水素基を表し、Ｒ^４は−（Ｃ_ｎＨ_２ｎ）−基を表わし、ｍは１〜１０の整数であり、ｎは２〜４の整数である。〕

[In Formula (2), R ¹ represents a hydrogen atom or a methyl group, R ² represents a linear, cyclic or aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ⁴ represents — (C _n H _2n ) -group, m is an integer of 1-10, and n is an integer of 2-4. ]

〔式（３）中、Ｒ^３は水素原子又はメチル基を表す。〕

[In formula (3), R ³ represents a hydrogen atom or a methyl group. ]

Examples of the linear hydrocarbon group having 6 to 12 carbon atoms in the structural unit (B11) represented by the formula (2) include a hexyl group, a heptyl group, an octyl group, and a nonyl group. Examples of the cyclic hydrocarbon group having 6 to 12 carbon atoms include cycloalkyl groups such as cyclohexyl group, cycloheptyl group, and cyclooctyl group; isobornane, adamantane, bicyclo [2.2.1] heptane, tetracyclo [6.2. 1.1 ^{3, 6} . Groups derived from bridged hydrocarbons such as 0 ^2,7 ] dodecane, tricyclo [5.2.1.0 ^2,6 ] decane (that is, for example, isobornyl group, tricyclodecanyl group, adamantyl group, etc. ); Furthermore, examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include phenyl group, tolyl group (o-, m-, p-), 4-t-butylphenyl group, 1-naphthyl group, benzyl group and the like. Is mentioned.
In these linear hydrocarbon group, cyclic hydrocarbon group and aromatic hydrocarbon group, at least one hydrogen atom may be substituted with a hydrocarbon group such as a methyl group or an ethyl group.

〔式（４）中、Ｒ^１は水素原子又はメチル基を表し、Ｒ^２は炭素数６〜１２の直鎖状、環状もしくは芳香族の炭化水素基、又はこれらの基の少なくとも１つの水素原子が炭化水素基に置換された置換炭化水素基を表し、Ｒ^４は−（Ｃ_ｎＨ_２ｎ）−基を表わし、ｍは１〜１０の整数であり、ｎは２〜４の整数である。〕 This structural unit (B11) is usually obtained by polymerizing the polymer (B1) using the monomer (Bm1) represented by the following formula (4).

[In Formula (4), R ¹ represents a hydrogen atom or a methyl group, R ² represents a linear, cyclic or aromatic hydrocarbon group having 6 to 12 carbon atoms, or at least one hydrogen atom of these groups Represents a substituted hydrocarbon group substituted with a hydrocarbon group, R ⁴ represents a — (C _n H _2n ) — group, m is an integer of 1 to 10, and n is an integer of 2 to 4. ]

As the monomer (Bm1), phenoxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxydipropylene glycol (meth) acrylate, phenoxytripropylene glycol (meth) Acrylate, Phenoxytetrapropylene glycol (meth) acrylate, Lauroxydiethylene glycol (meth) acrylate, Lauroxytriethylene glycol (meth) acrylate, Lauroxytetraethylene glycol (meth) acrylate, Lauroxydipropylene glycol (meth) acrylate, Lauroxy Tripropylene glycol (meth) acrylate, Lauroxytetrapropylene glycol ( Data) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6]} decanyl (meth) acrylate, and the like.
These monomers may be used alone or in combination of two or more.

Among these monomers (Bm1), from the viewpoint of improving adhesion and water resistance, phenoxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxydi Propylene glycol (meth) acrylate, phenoxytripropylene glycol (meth) acrylate, phenoxytetrapropylene glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decanyl (meth) acrylate Preferably, phenoxydiethylene glycol acrylate, phenoxytriethylene glycol acrylate, phenoxytetraethylene glycol acrylate, isobornyl ( Data) acrylate, tricyclo [5.2.1.0 ^{2, 6]} decanyl (meth) acrylate are more preferred.

〔式（５）中、Ｒ^３は水素原子又はメチル基を表す。〕 On the other hand, the structural unit (B12) represented by the formula (3) is usually obtained by polymerizing the polymer (B1) using the monomer (Bm2) represented by the following formula (5). .

Wherein (5), R ³ represents a hydrogen atom or a methyl group. ]

Examples of the monomer (Bm2) include hydroxyl group-containing aromatic vinyl compounds such as hydroxystyrene (o-, p-, m-) and p-isopropenylphenol. These monomers (Bm2) may use only 1 type and may use 2 or more types together.
Among these, from the viewpoint of improving adhesion and water resistance, p-hydroxystyrene and p-isopropenylphenol are preferable, and p-isopropenylphenol is more preferable.

The amount of the structural unit (B11) in the polymer (B1) is not particularly limited, but is usually 1 to 80% by mass when the entire structural unit constituting the polymer (B1) is 100% by mass, 5-50 mass% is more preferable, and 5-40 mass% is still more preferable. In this range, particularly excellent adhesion can be exhibited.
The amount of the structural unit (B12) in the polymer (B1) is not particularly limited, but is usually 1 to 50% by mass when the entire structural unit constituting the polymer (B1) is 100 mol%. 5-40 mass% is more preferable, and 5-30 mass% is still more preferable. In this range, particularly excellent adhesion can be exhibited.

  The polymer (B1) can include another structural unit (B13) in addition to the structural unit (B11) and the structural unit (B12). Examples of the monomer that gives the structural unit (B13) include aromatic vinyl compounds such as styrene, methylstyrene (α-, p-), and p-methoxystyrene; heterogeneous compounds such as N-vinylpyrrolidone and N-vinylcaprolactam. Atom-containing alicyclic vinyl compounds; cyano group-containing vinyl compounds such as acrylonitrile and methacrylonitrile; conjugated diolefins such as 1.3-butadiene and isoprene; carboxyl group-containing vinyl compounds such as acrylic acid and methacrylic acid; (Meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) Acrylate, Polypropylene N-glycol mono (meth) acrylate, glycerol mono (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, and other (meth) acrylic acid esters; p-hydroxyphenyl (meth) acrylamide Etc. These other monomers may use only 1 type and may use 2 or more types together.

Among these other monomers, styrene, acrylic acid, methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl ( Preference is given to meth) acrylate, p-hydroxyphenyl (meth) acrylamide and the like.
The amount of the structural unit (B13) occupying the polymer (B1) is not particularly limited, but is usually 95% by mass or less when the entire structural unit constituting the polymer (B1) is 100 mol%. -90 mass% is more preferable, and 10-85 mass% is more preferable.

Furthermore, it is preferable that the polystyrene conversion weight average molecular weight by GPC of the said polymer (B1) is 1000-1 million, More preferably, it is 2000-400000, More preferably, it is 3000-300000.
Furthermore, the ratio of the polymer (B1) constituting the organic negative composition (1) is preferably 10 to 90% by mass, when the solid content in the organic negative composition is 100% by mass, preferably 30 to 80 mass% is more preferable, and 50-70 mass% is still more preferable.

  As described above, when the alkali-soluble organic polymer (B1) has a reactive group, the polymerizable group can be introduced into the alkali-soluble organic polymer (B1) using the polymerizable group-introducing component. . Thereby, the water resistance of the partition 20 formed from the alkali-soluble organic polymer (B1) and the adhesion (waterproof adhesion) of the partition 20 to the base substrate 10 can be improved. The polymerizable group-introducing component and the alkali-soluble organic polymer (B1) having the polymerizable group introduced will be described later.

Examples of the reactive group possessed by the alkali-soluble organic polymer (B1) include a phenolic hydroxyl group, a carboxyl group, and a sulfonic acid group. These groups may use only 1 type and may use 2 or more types together.
Moreover, an epoxy group, an isocyanate group, etc. are mentioned as a group which can react with the reactive group which alkali-soluble organic polymer (B1) has. These groups may use only 1 type and may use 2 or more types together.
Furthermore, examples of the polymerizable group include an ethylenically unsaturated group. These groups may use only 1 type and may use 2 or more types together.

  Among the combinations of the reactive group and the group reactive with the reactive group, (1) the reactive group is a carboxyl group, and the reactive group with the reactive group is an epoxy group. There are some cases. A method for introducing a polymerizable group into the alkali-soluble organic polymer (B1) by such a combination is disclosed in, for example, JP-A-2006-124664. Furthermore, (2) the case where the reactive group is a hydroxyl group and the group capable of reacting with the reactive group is an isocyanate group is exemplified. A method for introducing a polymerizable group into the alkali-soluble organic polymer (B1) by such a combination is disclosed in, for example, Japanese Patent Application Laid-Open No. 2007-241247.

In the case of (1) above, that is, when the alkali-soluble organic polymer (B1) has a carboxyl group as a reactive group and an epoxy group is used as a group capable of reacting with the carboxyl group, the epoxy group and the polymerizable group are polymerizable. A polymerizable group-introducing component having a group (polymerizable group-introducing compound) can be used. More specifically, a compound having an epoxy group as well as a (meth) acrylolyl group as the polymerizable group is exemplified. That is, for example, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, methyl glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether {4- (2,3-epoxy) butyl (meth) acrylate} and the like. These compounds may use only 1 type and may use 2 or more types together.
Although the compounding quantity of the said polymeric group introduction | transduction component can be made into an appropriate range according to conditions, For example, it is 5-90 by mole fraction with respect to the mole number of the carboxyl group in alkali-soluble organic polymer (B1). It is preferable to set it as mol%, and it is more preferable to set it as 10-80 mol%. In this range, more excellent water resistance and adhesion can be obtained.

In the case of the above (2), that is, when the alkali-soluble organic polymer (B1) has a hydroxyl group as a reactive group and an isocyanate group is used as a group capable of reacting with the hydroxyl group, the isocyanate group and the polymerizable group are polymerizable. A polymerizable group-introducing component having a group (polymerizable group-introducing compound) can be used. More specifically, a compound having an isocyanate group as well as a (meth) acrylolyl group as the polymerizable group is exemplified. That is, for example, 2- (meth) acryloyloxyethyl isocyanate, 3- (meth) acryloyloxypropyl isocyanate, 4- (meth) acryloyloxybutyl isocyanate, 6- (meth) acryloyloxyhexyl isocyanate, 8- (meth) acryloyl Examples include oxyoctyl isocyanate, 10- (meth) acryloyloxydecyl isocyanate, and the like. These compounds may use only 1 type and may use 2 or more types together.
The compounding quantity of the said polymeric group introduction | transduction component can be made into a suitable range with conditions.

  Further, when the organic negative composition (1) is used as the partition wall forming composition, other components can be contained in addition to the compound (A) and the polymer (B) as described above. Examples of other components include a polyfunctional monomer (C1) and a radiation sensitive polymerization initiator (D1).

  The polyfunctional monomer (C1) is preferably a polyfunctional compound that is liquid or solid at room temperature and has at least one ethylenically unsaturated group in the molecule. Examples of such multifunctional monomer (C1) include trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1 , 4-butanediol di (meth) acrylate, butylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl Glycol di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol Di (meth) acrylate, epoxy (meth) acrylate obtained by adding (meth) acrylic acid to bisphenol A diglycidyl ether, bisphenol A di (meth) acryloyloxyethyl ether, bisphenol A di (meth) acryloyloxyethyloxyethyl ether Bisphenol A di (meth) acryloyloxymethyl ethyl ether, tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Examples include hexa (meth) acrylate. These polyfunctional monomers (C1) may use only 1 type, and may use 2 or more types together.

  The content of the polyfunctional monomer (C1) with respect to the partition wall forming composition {organic negative composition (1)} is not particularly limited, but is usually 20 with respect to 100 parts by mass of the polymer (B1). It is -300 mass parts, Preferably it is 30-200 mass parts, More preferably, it is 40-150 mass parts. In this range, better adhesion and water resistance can be obtained.

The radiation-sensitive polymerization initiator (D1) is multifunctional due to exposure light such as semiconductor laser, metal halide lamp, high-pressure mercury lamp (g-line, h-line, i-line, etc.), excimer laser, extreme ultraviolet light, and electron beam. The monomer (C1) is a compound capable of generating an active species capable of initiating polymerization.
Examples of the radiation sensitive polymerization initiator (D1) include photosensitive polymerization initiators described in JP-A-2006-285035 and JP-A-2009-192613. Specifically, acylphosphine oxide compounds, biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, triazine compounds, O-acyloxy compounds And other compounds. These may use only 1 type and may use 2 or more types together. In particular, the radiation-sensitive polymerization initiator (D1) in the present invention is preferably an acylphosphine oxide-based compound, a biimidazole-based compound, or an O-acyloxime-based compound from the viewpoint of water-resistant adhesion.

  Examples of the acylphosphine oxide compound include bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and bis (2,6- Dichlorobenzoyl) -4-ethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2-naphthylphosphine oxide, bis (2 , 6-Dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-chlorophenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,4-dimethoxyphenylphosphine Oxide, bis (2,6- Chlorbenzoyl) -decylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-octylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4,6-trimethyl) Benzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3, 4,5-trimethoxybenzoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-ethoxy Phenylphosphine oxide, bis (2 Methyl-1-naphthoyl) -2-naphthylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-propylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide Bis (2-methoxy-1-naphthoyl) -4-ethoxyphenylphosphine oxide, bis (2-chloro-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2 4,4-trimethylpentylphosphine oxide and the like. These may use only 1 type and may use 2 or more types together.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2 '-Bis (2-bromophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4 , 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 '-Biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis ( 2-bromophenyl) -4,4 ', 5 '-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2 , 2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and the like. These may use only 1 type and may use 2 or more types together.

Examples of the benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and methyl 2-benzoylbenzoate. These may use only 1 type and may use 2 or more types together.
Examples of the acetophenone compound include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 4- (2- Hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2, 2-dimethoxy-1,2-diphenylethane-1-one and the like can be mentioned. These may use only 1 type and may use 2 or more types together.

Examples of benzophenone compounds include 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone. These may use only 1 type and may use 2 or more types together.
Examples of the α-diketone compound include diacetyl, dibenzoyl, and methylbenzoyl formate. These may use only 1 type and may use 2 or more types together.
Examples of the polynuclear quinone compound include anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1,4-naphthoquinone, and the like. These may use only 1 type and may use 2 or more types together.
Examples of xanthone compounds include xanthone, thioxanthone, and 2-chlorothioxanthone. These may use only 1 type and may use 2 or more types together.

  Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2- Yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4 , 6-Bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl)- , 3,6-Bis (trichloromethyl) -s-triazine, 2-(4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine. These may use only 1 type and may use 2 or more types together.

  Examples of O-acyloxime compounds include etanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) Methoxybenzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) and the like. These may use only 1 type and may use 2 or more types together.

  2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-bromophenyl) ) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonyl phenyl) -1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5 ' -Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2 '-Bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4, 4 ', 5,5'-tetraphenyl-1,2'-bi Dazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6) -Tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dimethylphenyl) -4,5,4', 5 '-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-methylphenyl) -4,5,4', 5'-tetraphenyl-1,2'-biimidazole, 2,2 Examples include '-diphenyl-4,5,4', 5'-tetraphenyl-1,2'-biimidazole. These may use only 1 type and may use 2 or more types together.

  The content of the radiation-sensitive polymerization initiator (D1) with respect to the partition wall forming composition {organic negative composition (1)} is not particularly limited, but is usually 1 with respect to 100 parts by mass of the polymer (B1). It is -150 mass parts, Preferably it is 3-140 mass parts, More preferably, it is 5-130 mass parts, Most preferably, it is 10-80 mass parts. In this range, better adhesion and water resistance can be obtained.

Further, the partition wall forming composition {organic negative composition (1)} can contain an adhesion assistant (E1), a surfactant (F1), an organic solvent (G1), and the like, if necessary.
Of these, the adhesion assistant (E1) is a component for further improving the adhesion between the base substrate and the partition walls, and a functional silane coupling agent is preferred as the adhesion assistant. That is, for example, a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group is preferable. Functional silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltri Examples include methoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and tris- (3-trimethoxysilylpropyl) isocyanurate.

  The content of the adhesion promoter (E1) with respect to the partition wall forming composition {organic negative composition (1)} is not particularly limited, but is usually 20 parts by mass or less with respect to 100 parts by mass of the polymer (B1). Preferably, it is 0.001-15 mass parts, More preferably, it is 0.01-10 mass parts, Most preferably, it is 0.1-7 mass parts. In this range, better adhesion can be obtained.

  The type of the surfactant (F1) is not particularly limited, and various types can be appropriately selected and used. The content of the surfactant (F1) with respect to the partition wall forming composition {organic negative composition (1)} is not particularly limited, but is usually 20 parts by mass or less with respect to 100 parts by mass of the polymer (B1). Yes, preferably 0.0001-15 parts by mass, more preferably 0.001-10 parts by mass, particularly preferably 0.01-5 parts by mass.

Examples of the organic solvent (G1) include alcohols such as ethylene glycol; cyclic ethers such as tetrahydrofuran; alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl ether; alkyl ethers of polyhydric alcohols such as propylene glycol monomethyl ether acetate. Acetates; Aromatic hydrocarbons such as toluene; Ketones such as methyl ethyl ketone; Esters such as ethyl acetate. These solvents (F1) may use only 1 type and may use 2 or more types together.
The content of the solvent (G1) with respect to the partition wall forming composition {organic negative composition (1)} is not particularly limited, and is used so as to have a solid content concentration suitable for the coating form and the like.
The solid content concentration of the organic negative composition (1) can be appropriately selected depending on the height of the partition wall. Although it does not specifically limit, 10-90 mass% is preferable, 30-80 mass% is more preferable, 40-70 mass% is still more preferable.
In addition, when using this organic negative composition (1), any substrate may be used as the substrate, but a substrate containing Si is particularly preferable from the viewpoint of adhesion. That is, an element substrate mainly composed of silicon such as silicon, silicon dioxide and glass (including borosilicate glass, surface modified glass, quartz glass, etc.) is preferable.

(2) Negative-type radiation-sensitive composition containing an inorganic polymer as a main component When the inorganic negative-type composition (2) is used as the partition wall-forming composition, the inorganic negative-type composition (2) includes, for example, The compositions described in JP-A No. 2004-212983, WO 04/111734, WO 05/036269, JP-A 2004-198906 and JP-A 2005-266474 can be used. Specifically, for example, an inorganic negative composition containing a compound (A), a polysiloxane (B2) as a polymer (B), a radiation sensitive acid generator (C2), and a solvent (D2). A thing (2) is mentioned.

The polysiloxane (B2) is preferably a polymer obtained by hydrolytic condensation of a hydrolyzable silane compound. More specifically, a hydrolyzable silane compound represented by the following formula (6) (hereinafter simply referred to as “compound (B21)”), and a hydrolyzable silane compound represented by the following formula (7) (hereinafter, It is preferably a polymer obtained by hydrolytic condensation of at least one hydrolyzable silane compound selected from “compound (B22)”.
R _a Si (OR ¹ ) _4-a (6)
[In Formula (6), R represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a cyano group, a cyanoalkyl group, or an alkylcarbonyloxy group, and R ¹ is 1 Represents a valent organic group, and a represents an integer of 1 to 3. ]
Si (OR ² ) ₄ (7)
In [Equation (7), ^{R 2} represents a monovalent organic group. ]

Examples of the monovalent organic group for R ¹ in the formula (6) include an alkyl group, an alkenyl group, an aryl group, an allyl group, and a glycidyl group.
Examples of the compound (B21) include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane. , Diethyldimethoxysilane, diethyldiethoxysilane and the like are preferable.

As the monovalent organic group in R ² of the formula (7), the monovalent organic group in R ¹ of the formula (6) can be applied as it is. However, it may be different may be the same as R ¹ R ² and of formula (7) (6).
Examples of the compound (7) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, Examples include tetraphenoxysilane. Among these, tetramethoxysilane and tetraethoxysilane are preferable.

  As the hydrolyzable silane compound constituting the polysiloxane, only the compound (6) and the compound (7) may be used, but if necessary, a hydrolyzable silane compound represented by the following formula (8) ( Hereinafter, “compound (B23)”) can be used in combination.

^{_{R 3 x (R 4 O)}} 3-x Si- (R 7) z -Si (OR 5) 3-y R 6 y ... (8)
[In Formula (8), R < ³ > -R < ⁶ > is the same or different, respectively represents a monovalent organic group, x and y are the same or different, and show the number of 0-2, R < ⁷ > is an oxygen atom and a phenylene group Or a group represented by — (CH ₂ ) _n — (where n is an integer of 1 to 6), and z represents 0 or 1. ]
As the monovalent organic group in R ^{3 to} R ⁶ of the formula (8), the monovalent organic group in R ¹ of the formula (6) can be applied as it is. However, R ^{3 to} R ⁶ in the formula (8) and R ^{1 in the} formula (6) may be the same or different from each other.

  Among the compounds (8), as the compound (8) in which z = 0, hexamethoxydisilane, hexaethoxydisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1, 2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2- Tetraphenyldisilane and the like are preferable.

  Among the compounds (8), as the compound (8) in which z = 1, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1, 2-bis (triethoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (dimethoxymethyl) Silyl) -2- (trimethoxysilyl) ethane, 1- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, 1,2 -Bis (dimethoxymethylsilyl) ethane, 1,2-bis (diethoxymethylsilyl) ethane, 1,2-bis (trimethoxy) Silyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,4-bis (trimethoxysilyl) Benzene, 1,4-bis (triethoxysilyl) benzene and the like are preferable.

When the total of all the structural units contained in the polysiloxane is 100 mol%, the content of the structural unit derived from the compound (6) is preferably 30 to 100 mol%, and preferably 60 to 100 mol%. Is more preferable, and 70-100 mol% is still more preferable. If it is 30 to 100 mol%, the balance between the process margin during the curing treatment and the physical properties of the cured product can be improved.
Moreover, it is preferable that the content rate of the structural unit derived from a compound (7) is 0-70 mol%, 0-40 mol% is more preferable, 0-30 mol% is still more preferable. When the content is 0 to 70 mol%, the balance between the process margin during the curing process and the physical properties of the cured product can be improved.
Furthermore, the total content of the structural unit derived from the compound (6) and the structural unit derived from the compound (7) is preferably 100 mol% or less, more preferably 30 to 100 mol%, and more preferably 60 to 100 mol. % Is more preferable. In 30-100 mol%, the effect by including the structural unit derived from each compound of the compound (6) and compound (7) in polysiloxane in pattern formation can be acquired more effectively.
Moreover, it is preferable that the content rate of the structural unit derived from a compound (8) is 50 mol% or less, 0-40 mol% is more preferable, 0-30 mol% is still more preferable. If it is 50 mol% or less, it does not interfere with the effect of including the structural unit derived from each compound (6) and compound (7) in the polysiloxane in the pattern formation, and is derived from the compound (8) in the pattern formation. The effect including the structural unit can be obtained more effectively.

  The weight average molecular weight in terms of polystyrene by GPC of the polysiloxane is preferably 1000 to 100,000, more preferably 1000 to 10,000. When the weight average molecular weight is 1000 to 100,000, it is possible to achieve both excellent coating properties and high storage stability while suppressing unnecessary gelation before curing.

The polysiloxane can be obtained by hydrolytic condensation reaction using a hydrolyzable silane compound {the compounds (6) to (8)} as a starting material.
In preparing this polysiloxane, [1] a mixture of the compounds (6), (7) and (8) may be subjected to a hydrolytic condensation reaction, and [2] hydrolyzate of each compound and its condensate. A hydrolytic condensation reaction or a condensation reaction may be carried out using at least one of at least one of them, a hydrolyzate of a mixture of selected compounds, and a condensate thereof.
In order to adjust the curing characteristics, silsesquioxanes having a crosslinking group such as octa [(1,2-epoxy-4-cyclohexyl) dimethylsiloxy] silsesquioxane, octa [(3-glycidoxy Propyl) dimethylsiloxy] silsesquioxane or the like may be added.
Moreover, after performing a hydrolysis condensation reaction, it is preferable to perform the removal process of reaction by-products, such as lower alcohols, such as methanol and ethanol, for example. Thereby, since the purity of the organic solvent is increased, it is possible to obtain more excellent coating properties and excellent storage stability.
The polysiloxane in the inorganic negative composition (2) may be used after being isolated from the polymer solution, or may be used as it is. In addition, when using as a polymer solution, solvent substitution with the below-mentioned solvent (D2) may be carried out as needed.

The radiation sensitive acid generator (C2) is a component that generates an acid upon exposure. By containing a radiation sensitive acid generator (hereinafter also referred to simply as “acid generator”) (C2), the acid generated from the acid generator (C2) promotes crosslinking of the polysiloxane (B2). As a result, the film is cured and a pattern having excellent mechanical properties can be formed. This acid generator includes exposure {for example, radiation such as visible particle rays, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams such as electron beams (ArF excimer laser (wavelength 193 nm) or KrF excimer laser (wavelength 248 nm)). The same applies to the following).
Examples of the acid generator (C2) include onium salts such as sulfonium salts and iodonium salts, organic halogen compounds, and sulfone compounds such as disulfones and diazomethane sulfones.

Specifically, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept-2. - yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethane Triphenylsulfonium salt compounds such as sulfonate, triphenylsulfonium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, triphenylsulfonium camphorsulfonate;

4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 2-bicyclo [2. 2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexyl-phenyl diphenyl sulfonium 2- (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7, 10]} dodecanyl) -1,1-difluoroethanesulfonate, 4-cyclohexyl-phenyl diphenyl sulfonium N, N'-bis (nonafluoro -n- butanesulfonyl) imidate 4-cyclohexyl-phenyl diphenyl sulfonium salt compounds such as 4-cyclohexyl-phenyl camphorsulfonate;

4-t-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-t-butylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-t-butylphenyl Diphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-t-butylphenyldiphenylsulfonium 2- (3-tetracyclo [4.4. 0.1 ^2,5 .1 ^7,10] dodecanyl) -1,1-difluoroethanesulfonate, 4-t-butylphenyl diphenyl sulfonium N, N'-bis (nonafluoro -n- butanesulfonyl) imidate, 4-t- Butylphenyl 4-t-butylphenyl diphenyl sulfonium salt compounds such as triphenylsulfonium camphorsulfonate;

Tri (4-t-butylphenyl) sulfonium trifluoromethanesulfonate, tri (4-t-butylphenyl) sulfonium nonafluoro-n-butanesulfonate, tri (4-t-butylphenyl) sulfonium perfluoro-n-octanesulfonate, Tri (4-t-butylphenyl) sulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, tri (4-t-butylphenyl) sulfonium 2 - (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethanesulfonate, tri (4-t- butylphenyl) sulfonium N, N'-bis (nonafluoro -N-butanesulfonyl) imidate, tri (4-t-butylphenyl) sulfur Bromide tri (4-t- butylphenyl) such as camphorsulfonate sulfonium salt compound;

Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2, 2-tetrafluoroethane sulfonate, diphenyliodonium 2- (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethanesulfonate, diphenyliodonium N, N'-bis Diphenyliodonium salt compounds such as (nonafluoro-n-butanesulfonyl) imidate, diphenyliodonium camphorsulfonate;

Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, Bis (4-t-butylphenyl) iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium 2 - (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethanesulfonate, bis (4-t- butylphenyl) iodonium N, N'-bis (nonafluoro -N-butanesulfonyl) imidate, bis (4-t-butylphenyl) io Bis (4-t- butylphenyl) such as camphorsulfonate iodonium salt compounds;

1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, (4-n-Butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2-bicyclo [2.2. 1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2- (3-tetracyclo [4.4. 0.1 ^2,5 .1 ^7,10 ] dodecanyl) -1,1-difluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothio 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium salt compounds such as phenium camphorsulfonate;

1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, (3,5-Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2-bicyclo [2.2. 1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2- (3-tetracyclo [4.4. 0.1 ^2,5 .1 ^7,10 ] dodecanyl) -1,1-difluoro Ethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, 1- (3,5-dimethyl-4-hydroxyphenyl) ) 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium salt compounds such as tetrahydrothiophenium camphorsulfonate;

N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (perfluoro-n-octanesulfonyloxy) succinimide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethane sulfonyloxy) succinimide, N- (2- (3- tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) Succinimide compounds such as -1,1-difluoroethanesulfonyloxy) succinimide and N- (camphorsulfonyloxy) succinimide;

N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- ( 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy imide, N- (2- (3- tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethane-sulfonyloxy) bicyclo [2.2.1] hept Bicyclo [2.2.1] such as -5-ene-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide. And hept-5-ene-2,3-dicarboximide compounds.

  The amount of the acid generator used is usually 0.1 to 30 parts by mass with respect to 100 parts by mass of the polysiloxane contained in the inorganic negative composition (2) from the viewpoint of ensuring sensitivity and resolution. Yes, 0.1 to 20 parts by mass is preferable, and 0.1 to 15 parts by mass is more preferable. In the preferred range, the sensitivity and resolution are excellent, transparency to radiation can be sufficiently obtained, and a pattern can be obtained more easily.

As said solvent (D2), it is preferable to use an organic solvent, and each said component is normally melt | dissolved or disperse | distributed to the organic solvent. The organic solvent is at least one selected from the group consisting of alcohol solvents, ketone solvents, amide solvents, ether solvents, ester solvents, aliphatic hydrocarbon solvents, aromatic solvents, and halogen-containing solvents. Is mentioned.
Among these solvents, it is preferable to use an organic solvent having a boiling point of less than 150 ° C. In particular, it is preferable to use one or more of alcohol solvents, ketone solvents and ester solvents.

  The amount of the solvent (D2) used is usually 10 to 3500 parts by mass, preferably 20 to 3500 parts by mass, with respect to 100 parts by mass of the polysiloxane contained in the inorganic negative composition (2). 3500 mass parts is more preferable. In the preferred range, the in-plane uniformity of the film is particularly excellent.

  Furthermore, the inorganic negative composition (2) can contain an acid diffusion inhibitor in addition to the various components. The acid diffusion controller controls the unnecessary diffusion of the acid generated from the acid generator (C2), and has an action of suppressing an unintended chemical reaction in the non-irradiated region. The acid diffusion controller is preferably a nitrogen-containing organic compound whose basicity does not change upon irradiation or heating.

Examples of the nitrogen-containing organic compound include tertiary amine compounds, amide group-containing compounds, quaternary ammonium hydroxide compounds, and nitrogen-containing heterocyclic compounds.
Tertiary amine compounds include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, Tri (cyclo) alkylamines such as tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, dicyclohexylmethylamine, tricyclohexylamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methyl Aromatic amines such as aniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, 2,6-dimethylaniline, 2,6-diisopropylaniline, diphenylamine, triphenylamine, naphthylamine; triethanolamine, diethanol Alkanolamines such as niline; N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, 1,3-bis [1- (4 -Aminophenyl) -1-methylethyl] benzenetetramethylenediamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- ( 4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl)- 1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, bis (2-dimethylaminoethyl) ether , Bis (2-diethylaminoethyl) ether.

  Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt-butoxycarbonyl. Dicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N -Di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4'-diaminodiphenylmethane, N, N'-di-t-butoxycarbonylhexamethylenediamine, N, N , N ′, N′-Tetra-t-butoxycarbonylhexamethylenediamine N, N-di-t-butoxycarbonyl-1,7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8-diaminooctane, N, N′-di-t-butoxycarbonyl- 1,9-diaminononane, N, N′-di-t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxycarbonyl-1,12-diaminododecane, N, N′-di -T-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole, N -T-butoxycarbonyl-pyrrolidine, Nt-butoxycarbonyl-piperidine, Nt-butoxycarbonyl In addition to Nt-butoxycarbonyl group-containing amino compounds such as 4-hydroxy-piperidine, Nt-butoxycarbonyl-morpholine, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like.

Examples of the quaternary ammonium hydroxide compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, and tetra-n-butylammonium hydroxide.
Examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, 4-methylimidazole, 1-benzyl-2-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, and 2-phenylbenzimidazole; pyridine, 2- Methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4- Pyridines such as hydroxyquinoline, 8-oxyquinoline and acridine; piperazines such as piperazine and 1- (2-hydroxyethyl) piperazine, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine and 3-piperidino 1,2-propanediol, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane.

  The amount of the acid diffusion controller used is usually 15 parts by mass or less (0.001 parts by mass or more) with respect to 100 parts by mass of the polysiloxane (B2) contained in the inorganic negative composition (2). 10 mass parts or less are preferable and 5 mass parts or less are more preferable.

Further, the inorganic negative composition (2) can contain a surfactant in addition to the above-mentioned various components. A surfactant is a component that exhibits an effect of improving coating properties, striation and the like. As this surfactant, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, fluorine surfactants, Examples include poly (meth) acrylate surfactants.
The usage-amount of the said surfactant is 0.00001-1 mass part normally with respect to 100 mass parts of polysiloxane (B2) contained in an inorganic negative composition (2), and is 0.00001-0. 1 part by mass is preferable, and 0.00001 to 0.01 part by mass is more preferable.
Moreover, the solid content density | concentration of this inorganic negative composition (2) is although it does not specifically limit, 10-90 mass% is preferable, 30-80 mass% is more preferable, 50-70 mass% is still more preferable.

(3) Positive-type radiation-sensitive composition containing organic polymer as a main component Positive-type radiation-sensitive composition containing organic polymer as a main component (hereinafter also simply referred to as “organic positive-type composition (3)”) ) Include JP-A-2009-133924, JP-A-2001-281862, JP-A-11-106606, JP-A-2008-192774, JP-A-2004-309776, and JP-A-2004-125815. The composition described in the publication can be used. Specifically, for example, an organic positive composition (3) containing an alkali-soluble resin (B3) and a quinonediazide compound (C3) can be mentioned.

  The alkali-soluble resin (B3) contained in the organic positive composition (3) is not particularly limited, but is a resin having a phenolic hydroxyl group (B3-1), a monomer having a phenolic hydroxyl group, and (meth) acrylic acid. Examples thereof include a copolymer (B3-2) obtained using a monomer containing an ester, a resin having a carboxyl group (B3-3), and the like.

  Examples of the resin (B3-1) include novolak resins obtained by condensing phenols and aldehydes in the presence of a catalyst, as well as polyhydroxystyrene, hydroxystyrene and other monomers {( Copolymers with meth) acrylic acid and (meth) acrylic acid esters}, polyisopropenylphenol, isopropenylphenol and other monomers {excluding (meth) acrylic acid and (meth) acrylic acid esters} Copolymer, phenol / xylylene glycol condensation resin, cresol / xylylene glycol condensation resin, phenol / dicyclopentadiene condensation resin, and the like. These may use only 1 type and may use 2 or more types together.

  Resin (B3-2) uses the monomer which contains the monomer which has a phenolic hydroxyl group, and (meth) acrylic acid ester, and does not contain the compound which has carboxyl groups, such as (meth) acrylic acid. It is a copolymer obtained. Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene and isopropenylphenol. Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl esters having a branched or alicyclic alkyl group. The hydrogen atom of the alkyl group in the (meth) acrylic acid alkyl ester may be substituted with a hydroxyl group.

  In forming the resin (B3-2), in addition to the monomer and ester, a compound having a polymerizable unsaturated bond may be used as another monomer. Other monomers include aromatic vinyl compounds such as styrene; unsaturated acid anhydrides such as maleic anhydride; esters of the unsaturated carboxylic acids; unsaturated nitriles such as (meth) acrylonitrile; (meth) acrylamides and the like Unsaturated imides such as maleimide; unsaturated alcohols such as (meth) allyl alcohol; N-vinylaniline, vinylpyridine, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, N-vinylimidazole, N -Vinylcarbazole etc. are mentioned. These may use only 1 type and may use 2 or more types together.

  The resin (B3-3) may be a homopolymer or a copolymer, and is usually obtained using a monomer containing a compound having a carboxyl group (hereinafter referred to as “monomer (B3-3m)”). Polymer. Examples of the monomer (B3-3m) include unsaturated carboxylic acids or unsaturated dicarboxylic acids such as (meth) acrylic acid and maleic acid; monoesters of unsaturated dicarboxylic acids, and the like. These may use only 1 type and may use 2 or more types together.

  Examples of the resin (B3-3) include the following (1) to (7). That is, (1) a copolymer obtained by using a monomer (B3-3m) and a monomer having a phenolic hydroxyl group, (2) a monomer (B3-3m), and a phenolic hydroxyl group A copolymer obtained by using a monomer having a monomer and (meth) acrylic acid ester, (3) a monomer (B3-3m), a monomer having a phenolic hydroxyl group, and an aromatic vinyl Copolymer obtained by using compound and (meth) acrylic acid ester, (4) obtained by using monomer (B3-3m), aromatic vinyl compound and (meth) acrylic acid ester Copolymer obtained using (5) monomer (B3-3m), aromatic vinyl compound and conjugated diolefin, (6) monomer (B3-3m) And a copolymer obtained using (meth) acrylic acid ester and conjugated diolefin, (7 The monomer (B3-3m), (meth) acrylic acid ester, copolymer obtained by using a fatty acid vinyl compound.

  In addition, about the monomer which has a phenolic hydroxyl group in resin (B3-3), (meth) acrylic acid ester, and an aromatic vinyl compound, the illustration in the said resin (B3-2) is applicable as it is. Examples of the conjugated diolefin include 1,3-butadiene, isoprene, 1,4-dimethylbutadiene and the like. Examples of the fatty acid vinyl compound include vinyl acetate and vinyl crotonic acid.

The alkali-soluble resin (B3) may be a single polymer or a combination of two or more polymers.
The weight average molecular weight of the alkali-soluble resin (B3) is preferably 2000 or more, more preferably 2000 to 50000 in terms of polystyrene-converted weight average molecular weight by GPC.
The content of the alkali-soluble resin (B3) constituting the organic positive composition (3) is preferably 20 to 90% by weight, when the solid content in the organic positive composition is 100% by weight, and preferably 20 to 90% by weight. 80 mass% is more preferable, and 30-70 mass% is still more preferable.

  The quinonediazide compound (C3) contained in the organic positive composition (3) is a 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester or 1,2-naphthoquinone-2-diazide-4-one of a phenol compound. It is a sulfonic acid ester.

〔式（９）中、Ｘ^１〜Ｘ^１０は、それぞれ相互に同一又は異なっていてもよく、水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基又はヒドロキシル基である。尚、Ｘ^１〜Ｘ^５のうちの少なくとも１つはヒドロキシル基である。また、Ａは単結合、Ｏ、Ｓ、ＣＨ_２、Ｃ（ＣＨ_３）_２、Ｃ（ＣＦ_３）_２、Ｃ＝Ｏ、又はＳＯ_２である。〕 Although the said phenol compound will not be specifically limited if it is a compound which has at least 1 phenolic hydroxyl group, The compound represented by following formula (9)-(13) is preferable.

[In Formula (9), X ^{1 to} X ¹⁰ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. . Note that at least one of X ^{1 to} X ⁵ is a hydroxyl group. A is a single bond, O, S, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , C═O, or SO ₂ . ]

〔式（１０）中、Ｘ^１１〜Ｘ^２４は、それぞれ相互に同一又は異なってもよく、水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基又はヒドロキシル基である。尚、Ｘ^１１〜Ｘ^１５のうちの少なくとも１つはヒドロキシル基である。また、Ｒ^１〜Ｒ^４は、それぞれ相互に同一又は異なってもよく、水素原子又は炭素数１〜４のアルキル基である。〕

[In Formula (10), X < ¹¹ > -X < ²⁴ > may mutually be same or different, and is a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a hydroxyl group. Note that at least one of X ^{11 to} X ¹⁵ is a hydroxyl group. R ^{1 to} R ⁴ may be the same or different from each other, and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

〔式（１１）中、Ｘ^２５〜Ｘ^３９は、それぞれ相互に同一又は異なってもよく、水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基又はヒドロキシル基である。尚、Ｘ^２５〜Ｘ^２９のうちの少なくとも１つ及びＸ^３０〜Ｘ^３４のうちの少なくとも１つはヒドロキシル基である。また、Ｒ^５は、水素原子又は炭素数１〜４のアルキル基である。〕

[In Formula (11), X ^{25 to} X ³⁹ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. ^{Incidentally,} at least one of the at least one and ^X 30 ^{to X 34} of the X 25 ^{to X 29} is a hydroxyl group. R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

〔式（１２）中、Ｘ^４０〜Ｘ^５８は、それぞれ相互に同一又は異なってもよく、水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基又はヒドロキシル基である。尚、Ｘ^４０〜Ｘ^４４のうちの少なくとも１つ、Ｘ^４５〜Ｘ^４９のうちの少なくとも１つ及びＸ^５０〜Ｘ^５４のうちの少なくとも１つはヒドロキシル基である。また、Ｒ^６〜Ｒ^８は、それぞれ相互に同一又は異なってもよく、水素原子又は炭素数１〜４のアルキル基である。〕

[In Formula (12), X ^{40 to} X ⁵⁸ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. At least one of X ^{40 to} X ⁴⁴ , at least one of X ^{45 to} X ⁴⁹ , and at least one of X ^{50 to} X ⁵⁴ is a hydroxyl group. R ^{6 to} R ⁸ may be the same or different from each other, and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

〔式（１３）中、Ｘ^５９〜Ｘ^７２は、それぞれ相互に同一又は異なってもよく、水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基又はヒドロキシル基である。尚、Ｘ^５９〜Ｘ^６２のうちの少なくとも１つ及びＸ^６３〜Ｘ^６７のうちの少なくとも１つはヒドロキシル基である。〕

Wherein ^{(13), X} 59 ~X ⁷² may be the same or different from each other, respectively, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group or a hydroxyl group having 1 to 4 carbon atoms. ^{Incidentally,} at least one of the at least one and ^X 63 ^{to X 67} of the X 59 ^{to X 62} is a hydroxyl group. ]

Examples of the phenol compound include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3,4 , 2 ′, 4′-pentahydroxybenzophenone, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,3- Bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6-bis [1- (4 -Hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxy) Eniru) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane, and the like. These can be used alone or in combination of two or more.
Therefore, as the quinonediazide compound (C3), at least one selected from these phenol compounds is reacted with 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid. The esterified product and the like obtained by allowing them to be used can be used singly or in combination of two or more.

  The proportion of the quinonediazide compound (C3) contained in the organic positive composition (3) is preferably 10 to 100 parts by mass and more preferably 10 to 50 parts by mass when the alkali-soluble resin (B3) is 100 parts by mass. Preferably 15-50 mass parts is more preferable.

  The organic positive composition (3) may further contain a crosslinking agent; particles made of a crosslinked polymer (hereinafter referred to as “crosslinked polymer particles”); a low-molecular phenolic compound, and the like. .

  As the crosslinking agent (D3), a compound having at least two alkyl etherified amino groups in the molecule; an epoxy group-containing compound; a phenol compound having an aldehyde group; a phenol compound having a methylol group; and a thiirane ring Compounds; oxetanyl group-containing compounds; isocyanate group-containing compounds (including blocked ones) and the like.

Examples of the compound having at least two alkyl etherified amino groups in the molecule include all or part of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylol melamine (at least 2). Can be used which are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, and the plurality of alkyl groups may be the same as or different from each other. In addition, the methylol group that is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed. Specific examples include hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like. These may use only 1 type and may use 2 or more types together.

Examples of the epoxy group-containing compound include phenol novolac type epoxy resin, bisphenol A type epoxy resin, resorcinol diglycidyl ether, pentaerythritol glycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, phenyl glycidyl ether, neopentyl glycol diester. Glycidyl ether, ethylene / polyethylene glycol diglycidyl ether, propylene / polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether and the like are preferable.
Examples of the phenol compound having an aldehyde group include o-hydroxybenzaldehyde. Examples of the phenol compound having a methylol group include 2,6-bis (hydroxymethyl) -p-cresol.
When the organic positive composition (3) contains the crosslinking agent (D3), the content is preferably 1 to 100 parts by mass, and 10 to 75 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (B3). Is more preferable, and 10-50 mass parts is still more preferable.

The cross-linked polymer particles (E3) include a monomer homopolymer or copolymer containing a cross-linkable compound having two or more polymerizable unsaturated bonds (hereinafter referred to as “cross-linkable monomer”). Can be used.
Examples of the crosslinkable monomer include divinylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and polypropylene glycol di (meth) acrylate. These can be used alone or in combination of two or more.

  When the crosslinked polymer particles are a copolymer, the other monomer to be polymerized with the crosslinking monomer includes an unsaturated compound having a hydroxyl group such as hydroxyethyl (meth) acrylate; (meth) acrylic Unsaturated compounds having a carboxyl group such as acid and succinic acid-β- (meth) acryloxyethyl; unsaturated compounds having a nitrile group such as (meth) acrylonitrile; unsaturated compounds having an amide group such as (meth) acrylamide Unsaturated compounds having an amino group such as dimethylamino (meth) acrylate; unsaturated compounds having an epoxy group such as epoxy (meth) acrylate obtained by reaction of glycidyl (meth) acrylate and (meth) acrylic acid; Obtained by reaction of alkyl (meth) acrylate with polyisocyanate Urethane (meth) acrylates such as compounds; aromatic vinyl compounds such as styrene and p-isopropenylphenol; (meth) acrylic acid esters such as (meth) acrylic acid alkyl esters and polyalkylene glycol (meth) acrylates; A diene compound etc. are mentioned. These may use only 1 type and may use 2 or more types together.

  When the cross-linked polymer particles (E3) are composed of a cross-linkable monomer, an unsaturated compound having a hydroxyl group and / or a carboxyl group, and a copolymer of other monomers (E31), a cross-linkable monomer The ratio of the unit amount consisting of a body (E31-m1), the unit amount consisting of an unsaturated compound having a hydroxyl group and / or a carboxyl group (E31-m2), and the unit amount consisting of another monomer (E31-m3) is , when the sum is 100 mol%, 0.1 to 10 mol%, preferably 5 to 50 mol% and 40 to 94.9 mol%, 0.5 to 7 mol%, 6-45 mol% and 48-93.5 mol% is more preferable, 1-5 mol%, 7-40 mol%, and 55-92 mol% are still more preferable.

The glass transition temperature (Tg) of the crosslinked polymer particles is preferably 20 ° C. or less, more preferably 10 ° C. or less, and still more preferably 0 ° C. or less (usually −70 ° C. or more).
The average particle diameter of the crosslinked polymer particles is preferably 30 to 100 nm, more preferably 40 to 90 nm, and still more preferably 50 to 80 nm {using a light scattering flow distribution measuring device “LPA-3000” (manufactured by Otsuka Electronics Co., Ltd.). According to a value measured by diluting a dispersion of crosslinked polymer particles according to a conventional method}.
When the organic positive composition (3) contains the crosslinked polymer particles (E3), the content of the crosslinked polymer particles is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (B3). 5-80 mass parts is more preferable, and 5-50 mass parts is still more preferable.

  Examples of the low molecular phenolic compound (F3) include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, and 1,1-bis (4-hydroxyphenyl) -1. -Phenylethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3 -Dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane, 1,1,2,2-tetra ( 4-hydroxyphenyl) ethane and the like. These may use only 1 type and may use 2 or more types together.

When the organic positive composition (3) contains a low molecular phenolic compound (F3), the content of the low molecular phenolic compound is 1 to 20 masses per 100 parts by mass of the alkali-soluble resin (B3). Part is preferable, 2 to 15 parts by mass is more preferable, and 3 to 10 parts by mass is still more preferable.
The solid content concentration of the organic positive composition (3) is not particularly limited, but is preferably 10 to 90% by mass, more preferably 30 to 80% by mass, and still more preferably 50 to 70% by mass.

(4) Positive-type radiation-sensitive composition mainly composed of inorganic polymer The positive-type radiation-sensitive composition mainly composed of inorganic polymer has an acid-dissociable group that is dissociated by an acid, and an acid. An inorganic positive composition (4) containing polysiloxane (B4) that becomes alkali-soluble when the dissociable group is dissociated and a radiation-sensitive acid generator (C4) can be mentioned.
In addition, positive composition (hereinafter, also simply referred to as “inorganic positive composition (4)”) having such an inorganic polymer as a main component is disclosed in, for example, JP-A-2007-279073 and 2007-182555. It is described in gazettes.

〔式（１４）において、Ａは置換されていてもよい炭素数３〜２０の環状の２価の炭化水素基を示し、Ｒ^１は１価の酸解離性基を示す。〕

〔式（１５）において、Ｘは単結合又は置換されていてもよい炭素数１〜２０の直鎖状もしくは分岐状の２価の炭化水素基を示し、Ｙは単結合、−ＣＯＯ−、−ＮＨＣＯ−、−ＯＣＯＯ−、−ＮＨＣＯＯ−又は−Ｏ−を示し、Ｚは単結合または置換されていてもよい炭素数１〜２０の直鎖状もしくは分岐状の２価の炭化水素基を示す（但し、ＹとＺが同時に単結合となることはない）〕 The (B4) polysiloxane contained in the inorganic positive composition (4) is composed of a structural unit (B4-1) represented by the following formula (14) and a structural unit (B4-2) represented by the following formula (15). The structural unit (B4-1) is more than 0 mol% and 70 mol% or less, and the structural unit (B4-2) is more than 0 mol% and 70 mol% or less with respect to all the structural units. Some polysiloxanes are mentioned.

[In the formula (14), A represents an optionally substituted cyclic divalent hydrocarbon group having 3 to 20 carbon atoms, and R ¹ represents a monovalent acid-dissociable group. ]

[In the formula (15), X represents a single bond or an optionally substituted linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms, Y represents a single bond, —COO—, — NHCO-, -OCOO-, -NHCOO- or -O- is shown, and Z is a single bond or a C1-C20 linear or branched divalent hydrocarbon group which may be substituted ( However, Y and Z do not become a single bond at the same time.)]

In the formula (14), the cyclic divalent hydrocarbon having 3 to 20 carbon atoms of A is a group derived from cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane; adamantane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] decane, tetracyclo [6.2.1.1 ^3,6 . Groups derived from bridged hydrocarbons such as 0 ^2,7 ] dodecane; groups derived from aromatic hydrocarbons such as benzene, toluene, ethylbenzene, i-propylbenzene, naphthalene, and the like.

  Examples of the substituent for A include an acid dissociable group that generates a carboxyl group, an alcoholic hydroxyl group or a phenolic hydroxyl group in the presence of an acid, a fluorine atom, a hydroxyl group, a carboxyl group, an epoxy group, an oxo group, an amino group, A cyano group, a cyanyl group, an isocyanyl group, a (meth) acryloyl group, a (meth) acryloyloxy group, a group having a lactonyl group, a group having a carboxylic anhydride group, an alkyl group having 1 to 4 carbon atoms, or 1 to carbon atoms 4 fluoroalkyl groups, C 1-4 hydroxyalkyl groups, C 2-5 cyanoalkyl groups, C 1-4 alkoxyl groups, C 2-5 alkoxymethyl groups, C 2-5 carbon atoms An alkoxycarbonyl group (except for acid dissociable ones), an alkoxycarbonylamino group having 2 to 5 carbon atoms, an alky having 1 to 4 carbon atoms Kishisuruhoniru group, and the like alkylaminosulfonyl group having 1 to 4 carbon atoms. One or more of these substituents can be present in each substituted derivative.

R ¹ (monovalent acid dissociable group) in the formula (14) is a group represented by the following formulas (16-1) to (16-3) or a cyclic monovalent group having 3 to 20 carbon atoms. A hydrocarbon group, a monovalent heterocyclic group having 3 to 20 atoms, a trialkylsilyl group (wherein each alkyl group has 1 to 6 carbon atoms), an oxoalkyl group having 4 to 20 carbon atoms, and the like. Can be mentioned.

〔式（１６−１）において、各Ｒ^２は相互に独立に炭素数１〜４の直鎖状もしくは分岐状のアルキル基または炭素数４〜２０の１価の脂環式炭化水素基もしくはその置換誘導体を示すか、あるいは何れか２つのＲ２が相互に結合して、それぞれが結合している炭素原子と共に炭素数４〜２０の２価の脂環式炭化水素基もしくはその置換誘導体を形成し、残りのＲ^２が炭素数１〜４の直鎖状もしくは分岐状のアルキル基または炭素数４〜２０の１価の脂環式炭化水素基もしくはその置換誘導体を示す。〕

[In the formula (16-1), each R ² is independently a linear or branched alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a group thereof. A substituted derivative, or any two R2's bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a substituted derivative thereof together with the carbon atoms to which they are bonded. The remaining R ² represents a linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a substituted derivative thereof. ]

[In Formula (16-2), R ³ represents a group represented by Formula (16-1), a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a monovalent complex having 3 to 20 atoms. A cyclic group, a trialkylsilyl group (provided that each alkyl group has 1 to 6 carbon atoms) or an oxoalkyl group having 4 to 20 carbon atoms, and a is an integer of 0 to 6. ]

In [Equation (16-3), each R ⁴ individually represent a hydrogen atom or a straight, or shows a branched or cyclic alkyl group, or bond two R ⁴ is mutually Whether R ⁵ represents a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent heterocyclic group having 3 to 20 atoms. , or either has one of R ⁴ and and R ⁵ are bonded to each other to form a ring, the alkyl group of R ^4, ring two R ⁴ is formed by bonding to each other, said R ^5, The monovalent hydrocarbon group, the monovalent heterocyclic group, and the ring formed by bonding any one of R ⁴ and R ⁵ to each other may be substituted. ]

In the formula (16-1), examples of the linear or branched alkyl group having 1 to 4 carbon atoms of R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. , 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like.
Monovalent alicyclic hydrocarbon group and any two of R ² is a divalent 4-20 carbon atoms formed together with the carbon atoms each bonded to each other are attached to the carbon atoms 4-20 R ² As the alicyclic hydrocarbon group, a group derived from cycloalkane or cycloalkene such as cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cyclooctane, etc .; adamantane, bicyclo [2.2.1] heptane , Bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] decane, tetracyclo [6.2.1.1 ^3,6 . [0 ^2,7 ] groups derived from bridged hydrocarbons such as dodecane.
As the substituent in the substituted derivative of the monovalent or divalent alicyclic hydrocarbon group, the substituents exemplified for A in the formula (6) are applied. One or more of these substituents may be present in each substituted derivative.

In the formula (16-2), as the cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms of R ³ , a cyclobutyl group, a cyclopentyl group, a cyclopentenyl group, a cyclohexyl group, a cyclohexenyl group, a cycloheptyl group, a cyclo Octyl group, adamantan-1-yl group, bicyclo [2.2.1] heptan-2-yl group, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] decane- 3-yl group, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group and the like.
Examples of the monovalent heterocyclic group having 3 to 20 atoms of R ³ include a 2-tetrahydrofuranyl group and a 2-tetrahydropyranyl group.
Further, the trialkylsilyl group of R ³ includes a trimethylsilyl group, an ethyldimethylsilyl group, a methyldiethylsilyl group, a triethylsilyl group, an i-propyldimethylsilyl group, a methyldii-propylsilyl group, and a tri-i-propylsilyl group. , T-butyldimethylsilyl group and the like.
Examples of the oxoalkyl group having 4 to 20 carbon atoms of R ³ include a 3-oxocyclopentyl group, a 3-oxocyclohexyl group, a 4-oxocyclohexyl group, a 4-methyl-2-oxooxan-4-yl group, a 5- And a methyl-2-oxooxolan-5-yl group.

In the formula (16-3), examples of the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms of R ⁴ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, Examples include n-nonyl group, n-decyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like.
Examples of the ring formed by bonding two R ⁴ to each other include a 3- to 8-membered ring formed together with a carbon atom to which two R ⁴ are bonded.

In the formula (16-3), examples of the linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms of R ⁵ include a methyl group, an ethyl group, an n-propyl group, i -Propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2 -Linear or branched alkyl groups such as ethylhexyl group, n-nonyl group, n-decyl group; cycloalkyl groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group; adamantane-1 -Yl group, adamantane-2-yl group, bicyclo [2.2.1] heptan-2-yl group, bicyclo [2.2.2] octan-2-yl group, tricyclo [5. 2.1.0 ^2,6 ] decan-3-yl group, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Groups derived from bridged hydrocarbons such as dodecan-4-yl group; phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 1-naphthyl group, 2-naphthyl group Aryl groups such as a group; aralkyl groups such as a benzyl group, an α-methylbenzyl group, an α, α-dimethylbenzyl group, and a phenethyl group.

Further, the monovalent heterocyclic group having 3 to 20 atoms of R ⁵ is derived from a non-bridged heterocyclic compound such as oxetane, thietane, tetrahydrofuran, tetrahydrothiofuran, tetrahydropyran, tetrahydrothiopyran and the like. Groups; groups derived from bridged heterocyclic compounds such as compounds represented by the following formulas (17-1) to (17-4), and the like.

Furthermore, in the formula (16-3), examples of the ring formed by bonding any one of R ⁴ and R ⁵ include a bond between a carbon atom to which R ⁴ is bonded and R ^5. And a 3- to 8-membered ring formed together with the oxygen atom.
The alkyl group of R ^4, the two rings of R ⁴ is formed by bonding to each other, said monovalent hydrocarbon radicals and monovalent heterocyclic group and one of R ⁴ R ^5, and R ⁵ As the substituent for the ring formed by bonding with each other, the substituents exemplified for A in the formula (14) are applied. One or more of these substituents may be present in each substituted derivative.

In the formula (14), the cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms which is a monovalent acid-dissociable group for R ¹ includes 3 to 3 carbon atoms for R ³ in the formula (16-2). The groups exemplified for the 20 cyclic monovalent hydrocarbon groups apply.
In addition, as the monovalent heterocyclic group having 3 to 20 atoms that is the monovalent acid-dissociable group of R ^1, the monovalent heterocyclic group having 3 to 20 atoms of R ³ in the above formula (16-2) may be used. The groups exemplified for the heterocyclic groups apply.
Furthermore, as the trialkylsilyl group which is a monovalent acid-dissociable group for R ^1, the groups exemplified for the R ³ trialkylsilyl group in the formula (16-2) are applied.
Examples of the oxoalkyl group having 4 to 20 carbon atoms that is a monovalent acid-dissociable group for R ¹ include the groups exemplified for the oxoalkyl group having 4 to 20 carbon atoms for R ³ in the above formula (16-2). Applies.

In the formula (14), the monovalent acid dissociable group for R ¹ is preferably a group represented by the formula (16-1), a group represented by the formula (16-2), and more preferably, t-butyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group, 2-methyladamantyl group, 2-ethyladamantyl group, (t-butoxycarbonylmethyl group), etc. It is.
In the polysiloxane (B4), the structural unit (B4-1) can be present alone or in combination of two or more.

In the formula (15), examples of the linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms of X and Z include, for example, a methylene group, a 1,1-ethylene group, and 1,2-ethylene. Group, propylene group, trimethylene group, tetramethylene group, hexamethylene group and the like.
Examples of the substituent for the divalent hydrocarbon group of X and Z include a fluorine atom, a hydroxyl group, a carboxyl group, an epoxy group, an oxo group, an amino group, a cyano group, a cyanyl group, an isocyanyl group, a (meth) acryloyl group, ( (Meth) acryloyloxy group, group having lactonyl group, group having carboxylic anhydride group, alkoxy group having 1 to 4 carbon atoms, alkoxycarbonyl group having 2 to 5 carbon atoms, alkoxycarbonylamino group having 2 to 5 carbon atoms , An alkoxysulfonyl group having 1 to 4 carbon atoms, an alkylaminosulfonyl group having 1 to 4 carbon atoms, and the like. One or more of these substituents can be present in each substituted derivative.
In the formula (15), any one of two bonds (-) may be bonded to X in -COO-, -NHCO-, -OCOO-, and -NHCOO- of Y.
In the polysiloxane (B4), the structural unit (B4-2) may be present alone or in combination of two or more.

  In the polysiloxane (B4), the content of the structural unit (B4-1) is more than 0 mol% and 70 mol% or less, preferably 10 to 60 mol%, particularly preferably 15 to 50 mol, based on all structural units. Mol%. In this range, excellent resolution and sensitivity can be obtained. The content rate of a structural unit (2a-2) exceeds 0 mol% and is 80 mol% or less with respect to all the structural units, Preferably it is 5-80 mol%, Most preferably, it is 5-70 mol%. In this range, the adhesiveness with other layers (such as the base substrate) is excellent, and an excellent resolution is obtained.

  The polysiloxane (B4) is further represented by a structural unit other than the above derived from a trifunctional silane compound with respect to the condensation reaction (hereinafter referred to as “other structural unit”), for example, the following formula (18). It can have one or more structural units (hereinafter also referred to as “structural unit (18)”), structural units derived from a bifunctional or tetrafunctional silane compound with respect to the condensation reaction, and the like.

〔式（１８）において、Ｒ^６は炭素数１〜２０の１価の炭化水素基又は原子数３〜２０の
１価の複素環式基を示し、１価の炭化水素基及び１価の複素環式基はそれぞれ置換されていてもよい。〕

[In the formula (18), R ⁶ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent heterocyclic group having 3 to 20 atoms, and represents a monovalent hydrocarbon group or a monovalent complex. Each cyclic group may be substituted. ]

In the formula (18), the monovalent hydrocarbon group having 1 to 20 carbon atoms of R ⁶ includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and 2-methylpropyl. Group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group A linear or branched alkyl group such as cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc .; adamantane-1-yl group, adamantane-2-yl group, bicyclo [ 2.2.1] heptan-2-yl group, bicyclo [2.2.2] octane-2-yl group, tricyclo [5.2.1.0 ^{2, 6]} decan-3-yl group, Torashikuro [6.2.1.1 ^3,6. 0 ^2,7 ] groups derived from bridged hydrocarbons such as dodecan-4-yl group; phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 1-naphthyl group, 2-naphthyl group An aryl group such as a group; an aralkyl group such as a benzyl group, an α-methylbenzyl group, an α, α-dimethylbenzyl group, or a phenethyl group; a 1-acenaphthenyl group;

In the above formula (18), the monovalent heterocyclic group having 3 to 20 atoms of R ⁶ is a non-bridged heterocyclic ring such as oxetane, thietane, tetrahydrofuran, tetrahydrothiofuran, tetrahydropyran, tetrahydrothiopyran, etc. Groups derived from formula compounds; groups derived from bridged heterocyclic compounds such as the compounds represented by formulas (17-1) to (17-4), and the like.
As the substituent for the monovalent hydrocarbon group and monovalent heterocyclic group of R ^6, the groups exemplified for the substituent for the cyclic divalent hydrocarbon group of A in Formula (14) can be applied. . One or more of these substituents can be present in each substituted derivative.

In the polysiloxane (B4), the content of the other structural unit is usually 80 mol% or less, preferably 70 mol% or less, based on all the structural units. In this range, excellent resolution can be obtained and development defects can be particularly reduced.
Moreover, when polysiloxane (B4) has a structural unit (18) as another structural unit, the content rate of a structural unit (18) becomes like this. Preferably it is 5-80 mol% with respect to all the structural units, More preferably It is 5-70 mol%, Most preferably, it is 5-60 mol%.
Furthermore, the polysiloxane (B4) is intramolecularly cross-linked and / or intermolecularly cross-linked by at least one acid dissociable linking group represented by the following formula (19-1) or the following formula (19-2). May be.

〔式（１９−１）及び式（１９−２）において、各Ｒ^７は相互に独立に水素原子又は炭素数１〜８の直鎖状、分岐状もしくは環状のアルキル基を示すか、あるいは同一の炭素原子に結合している２つのＲ^７が相互に結合して３〜８員の炭素環を形成しており、各Ｒ^８は相互に独立にメチレン基または炭素数２〜１０の直鎖状、分岐状もしくは環状のアルキレン基を示し、各ｂは相互に独立に０〜１０の整数であり、各ｃは相互に独立に１〜７の整数であり、各Ｒ^９は相互に独立に炭素数１〜５０の（ｃ＋１）価の直鎖状もしくは分岐状の飽和炭化水素基、炭素数３〜５０の（ｃ＋１）価の環状の飽和炭化水素基、炭素数６〜５０の（ｃ＋１）価の芳香族炭化水素基または原子数３〜５０の（ｃ＋１）価の複素環式基を示し、該直鎖状もしくは分岐状の飽和炭化水素基、環状の飽和炭化水素基、芳香族炭化水素基および複素環式基はそれぞれ、主鎖及び／又は側鎖にヘテロ原子が介在してもよく、またそれらの炭素原子に結合する水素原子の少なくとも一部がフッ素原子、水酸基、カルボキシル基あるいはアシル基で置換されていてもよく、各Ｕ１は相互に独立に−ＣＯＯ−、−ＮＨＣＯＯ−又は−ＮＨＣＯＮＨ−を示す（但し、−ＣＯＯ−及び−ＮＨＣＯＯ−は、２個の結合手（−）のいずれがＲ^８又はＲ^９に結合してもよい）。〕

[In Formula (19-1) and Formula (19-2), each R ⁷ independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or the same. two R ⁷ are to form a carbocyclic ring of 3-8 members bonded to each other, each R ⁸ is a straight chain methylene group or C2-10 independently of one another attached to a carbon atom of the Each b is independently an integer of 0 to 10, each c is independently an integer of 1 to 7, and each R ⁹ is independently of each other. (C + 1) -valent linear or branched saturated hydrocarbon group having 1 to 50 carbon atoms, (c + 1) -valent cyclic saturated hydrocarbon group having 3 to 50 carbon atoms, and (c + 1) having 6 to 50 carbon atoms A valent aromatic hydrocarbon group or a (c + 1) -valent heterocyclic group having 3 to 50 atoms, Is a branched saturated hydrocarbon group, a cyclic saturated hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group, and a hetero atom may be present in the main chain and / or side chain, respectively, and At least a part of hydrogen atoms bonded to the atom may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group, or an acyl group, and each U1 independently represents —COO—, —NHCOO—, or —NHCONH— ( However, -COO- and -NHCOO- has two bonds (-) is either may be attached to ^{R 8} or ^{R 9).} ]

  The weight average molecular weight in terms of polystyrene of the polysiloxane (B4) by GPC is usually 500 to 1,000,000, preferably 500 to 100,000, particularly preferably 500 to 40,000. Within this range, the glass transition point of the resin is appropriate and the solubility in a solvent is excellent. In this invention, polysiloxane (B4) can be used individually or in mixture of 2 or more types, respectively.

  The radiation-sensitive acid generator (C4) contained in the inorganic positive composition (4) is a component that generates an acid upon exposure to radiation, and is present in the polysiloxane (B4) by the action of the acid. dissociating an acid-dissociable group, resulting exposed portion becomes readily soluble in an alkaline developer, and has a function of forming a positive resist pattern. The acid generator is not particularly limited as long as it has the above-described action, but a preferable acid generator preferably includes one or more compounds that generate sulfonic acid or carboxylic acid upon exposure.

  When the acid generator (C4) can generate sulfonic acid or carboxylic acid, the sulfonic acid or carboxylic acid includes methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i -Butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl Group, heptafluoro-i-propyl group, nonafluoro-n-butyl group, nonafluoro-i-butyl group, nonafluoro-sec-butyl group, nonafluoro-t-butyl group, perfluoro-n-pentyl group, perfluoro-n - hexyl group, perfluoro--n- heptyl group, perfluoro -n- octyl group, norbornane, Jinoruborunan, Ada Pentane or or a group derived from camphor, sulfonic acid or carboxylic acid and the like having a substituent derivative of these groups (for these sulfonic or carboxylic acids are described in JP-A-2002-220471).

  As the acid generator (C4), an onium salt compound that generates the sulfonic acid or carboxylic acid, a sulfone compound that generates the sulfonic acid, a sulfonic acid compound that generates the sulfonic acid, an oxime compound that generates the sulfonic acid, Examples thereof include carboxylic acid compounds that generate carboxylic acid, diazo ketone compounds that generate sulfonic acid or carboxylic acid, and halogen-containing compounds that generate sulfonic acid or carboxylic acid.

  Examples of the onium salt compound include iodonium salts and sulfonium salts (including tetrahydrothiophenium salts). More specifically, diphenyliodonium salt, dinaphthyliodonium salt, triphenylsulfonium salt, trinaphthylsulfonium salt, diphenylmethylsulfonium salt, dicyclohexyl · 2-oxocyclohexylsulfonium salt, 2-oxocyclohexyldimethylsulfonium salt, phenyl · Benzyl methylsulfonium salt, 1-naphthyldimethylsulfonium salt, 1-naphthyldiethylsulfonium salt, 1- (naphthalen-1-yl) tetrahydrothiophenium salt, and these groups are hydroxyl group, alkyl group, alkoxyl group, cyano group And derivatives substituted with one or more substituents such as a nitro group or one or more.

  As examples of the sulfone compounds, beta-ketosulfones, and beta-sulfonyl sulfones, alpha-diazo compounds of these compounds. Examples of the sulfonic acid compounds include sulfonic acid esters, sulfonic acid i-sensitive acid generator amides, aryl sulfonic acid esters, and imino sulfonates. Examples of the oxime compound include aryl group-containing oxime sulfonic acids. Examples of the carboxylic acid compound include carboxylic acid esters, carboxylic acid imides, and carboxylic acid cyanates. Examples of the diazoketone compound include 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and the like. Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds.

The acid generator (C4) can be used alone or in admixture of two or more. Also, two or more types of acid generators (C4) that generate different sulfonic acids can be used in combination, two or more types of acid generators (C4) that generate different carboxylic acids can be used together, or acid generation that generates sulfonic acids One or more agents (C4) and one or more acid generators (C4) that generate carboxylic acid can be used in combination.
The amount of the radiation-sensitive acid generator (C4) used is usually 0.1 to 30 parts by mass, preferably 0 with respect to 100 parts by mass of the total polysiloxane, from the viewpoint of ensuring sensitivity and developability as a resist. .5 to 20 parts by mass. In this range, the sensitivity and developability are excellent, and sufficient transparency to radiation can be obtained, and a rectangular resist pattern can be easily obtained.

The inorganic positive composition (4) includes polysiloxanes other than polysiloxane (B4) (hereinafter referred to as “other polysiloxanes”), acid diffusion control agents, dissolution control agents, surfactants, antihalation agents, adhesives Various additives such as auxiliaries, storage stabilizers and antifoaming agents can be blended.
The acid diffusion control agent is a component having an action of controlling a diffusion phenomenon of an acid generated from an acid generator upon exposure in a resist film and suppressing an undesirable chemical reaction in a non-exposed region. The acid diffusion controller can be used alone or in admixture of two or more. The compounding amount of the acid diffusion controller is usually 0.1 mol% or more and 100 mol% or less, preferably 50 mol% or less, more preferably 30 mol% or less with respect to the acid generator.

Examples of the dissolution control agent include compounds having an effect of controlling dissolution contrast and / or dissolution rate when a resist is formed. The blending amount of the dissolution control agent is usually 50 parts by mass or less, preferably 30 parts by mass or less with respect to 100 parts by mass of the total polysiloxane.
The surfactant is a component having an action of improving coating properties, striations, developability and the like. The compounding quantity of surfactant is normally 2 mass parts or less with respect to 100 mass parts of all the polysiloxane.

  In use, the inorganic positive composition (4) can be used after being dissolved in a solvent so that the total solid content concentration is 1 to 25 mass%, preferably 2 to 15 mass%. As the solvent, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, alkyl 2-hydroxypropionates, alkyl 3-alkoxypropionates, fluorine-containing solvents and the like are preferable. These solvents can be used alone or in admixture of two or more.

  Among these radiation sensitive compositions, ie, organic negative composition (1), inorganic negative composition (2), organic positive composition (3), and inorganic positive composition (4), Negative-type radiation-sensitive compositions {that is, organic negative-type composition (1) and inorganic negative-type composition (2)} are preferred, and organic negative-type composition (1) is more preferred.

[3] Microarray substrate partition (including biochip partition)
The partition walls (including biochip partition walls) of the microarray substrate of the present invention are obtained using the partition wall forming composition. That is, the partition wall 20 is formed by forming the first film 21 on the base substrate 10 using the partition wall forming composition containing the compound (A) and then patterning the first film 21 by a lithography method ( 1 to 3).

The property of the partition wall is not particularly limited and can be set appropriately. At a thickness of 35 μm, the transmittance for light having a wavelength of 550 nm can be 0 to 10%. In this range, particularly excellent characteristics can be exhibited in terms of preventing color mixing.
Further, the shape of the partition wall is not particularly limited and may be appropriately selected. However, it is usually preferable that the partition walls have a width of at least 1 μm (a distance separating the cavities). Further, the width is preferably 1 to 1000 μm, more preferably 2 to 500 μm, and particularly preferably 5 to 50 μm.

[4] Biochip manufacturing method (1)
The first biochip manufacturing method of the present invention (see FIGS. 3 and 4) includes (a) a microarray substrate manufacturing process (that is, a partition wall forming process for forming a partition wall on a base substrate), and (b) a fixing process. A substance disposing step; and (c) an immobilizing step.

  The “microarray substrate manufacturing step (a)” (see FIG. 3) is a step of forming the partition walls 20 on the base substrate 10 by using the microarray substrate manufacturing method. For the microarray substrate manufacturing process, the method for manufacturing a microarray substrate can be applied as it is.

The “fixing substance disposing step (b)” (see FIG. 4) is a step of disposing a fixing substance 51 for fixing the target material 52 in the region 30 (that is, the cavity) partitioned by the partition wall 20. .
The fixing material 51 is a material that connects the target material and the base substrate. Examples of the immobilizing substance include polylysine, collagen, laminin, sialic acid oligosaccharide, mannose-binding lectin, integrin family ligand, peptide, antigen or antibody, and nucleic acid. These may use only 1 type and may use 2 or more types together.
The method for immobilizing the immobilizing substance is not particularly limited, and may be immobilization using chemical bonds, immobilization using physical adsorption, or other immobilization methods.

  In the fixing substance arranging step (b), the fixing substance 51 is applied to the surface (including the surface of the base substrate and the surface of the partition wall) in the cavity 30 of the base substrate 10 on which the partition wall 20 is formed in advance. A surface treatment for assisting the arrangement of the substrate, a surface treatment for suppressing adhesion of a target material, which will be described later, and the like can be performed. Examples of the surface treatment include a method of imparting a property that prevents non-specific adhesion to a lipid membrane (cell membrane) with ethylenediamine or the like.

The “fixing step (c)” (see FIG. 4) is a step of fixing the target material 52 to the fixing material 51.
The target substance 52 is a substance that can specifically bind to a target biopolymer or the like. More specifically, examples of the target substance include biological substances. Examples of the biological substance include eukaryotic cells, prokaryotic cells, viruses, and liposomes. Furthermore, DNA, RNA, PNA, BNA, artificial nucleic acid, protein (peptide), sugar chain, probes combining these, and the like, which are smaller than these, can be mentioned. These may use only 1 type and may use 2 or more types together.

  The method for fixing the target material 52 is not particularly limited, and may be fixation using chemical bonds or fixation using physical adsorption.

[5] Biochip manufacturing method (2)
The second biochip manufacturing method of the present invention (see FIGS. 3 and 5) includes (a) a microarray substrate manufacturing process (that is, a partition wall forming process for forming a partition wall on a base substrate), and (d) a support material. An arrangement step.

  The “microarray substrate manufacturing step (a)” (see FIG. 3) is a step of forming the partition walls 20 on the base substrate 10 by using the microarray substrate manufacturing method. For the microarray substrate manufacturing process, the method for manufacturing a microarray substrate can be applied as it is.

  In the “(d) loading substance arranging step” (see FIG. 5), the loading substance 53 having the target substance 52 on the surface of the solid phase body 54 is placed in the cavity 30 of the base substrate 10 on which the partition wall 20 is formed. It is a process to arrange in.

The solid phase butter 54 is a solid phase for supporting the target material 52 on the surface thereof. The solid phase carrier 54 is usually a particle. The kind of particle | grains is not specifically limited, Although an organic particle may be sufficient and an inorganic particle may be sufficient, Preferably it is an inorganic particle. Furthermore, among inorganic particles, particles made of metal and / or metal oxide are more preferable. As particles made of metal and / or metal oxide, for example, magnetic particles can be used. Magnetic particles are particles having magnetism. When magnetic particles are used, the target material 52 can be easily magnetically isolated by an external magnetic field when the target material 52 is isolated from the solid phase simple substance 54.
Examples of the material constituting the magnetic particles include iron, cobalt or nickel salts, oxides, borides or sulfides, and rare earth elements having high magnetic susceptibility (for example, hematite or ferrite). These materials may use only 1 type and may use 2 or more types together.
Specific examples of the magnetic particles include ferromagnetic alloys such as magnetite, iron-lead alloy, iron-platinum alloy, and cobalt-platinum alloy. These magnetic particles may use only 1 type and may use 2 or more types together.
When the solid phase carrier 54 is a particle, the particle size is not particularly limited, and nanoparticles, microparticles, milliparticles, and the like can be appropriately used.

In addition, in order to connect the target material 52 to the surface of the solid phase body 54, a fixing material may be arranged on the surface. For the immobilizing substance, the description of the immobilizing substance 51 described in the step (b) in the first biochip manufacturing method can be applied as it is.
Moreover, the description of the target material 52 described in the step (c) in the first biochip manufacturing method can be applied to the target material 52 as it is.

  Further, the method for disposing the support material 53 having the target material 52 on the surface of the solid phase body 54 in the cavity 30 of the base substrate 10 on which the partition wall 20 is formed is not particularly limited. This is performed by applying a dispersion liquid containing the material to the base substrate 10 on which the partition walls 20 are formed.

  Further, in the step (d), in order to prevent the support material from moving out of the cavity of the microarray substrate, a material (for example, nanoparticles) having a size smaller than the support material can be disposed in the cavity. . Further, a substance having a catalytic function or an enzyme function for efficiently functioning the biochip, that is, promoting the reaction (hybridization) between the target substance and the target sample such as DNA or RNA is disposed in the cavity. be able to.

[6] Biochip The biochip of the present method is obtained by the method for producing a biochip of the present invention. A microarray substrate (pre-biochip) 101 illustrated in FIGS. 1 and 2 includes at least a base substrate 10 and partition walls 20. And it has the area | region 30 on the board | substrate divided by this partition 20. As shown in FIG. This partitioned region 30 is surrounded by the partition wall 20 and is recognized as a recess (ie, cavity 30) in appearance. A plurality of cavities 30 are usually provided in one microarray substrate (pre-biochip) 101. The cavity 30 can be used as a so-called well. Furthermore, as illustrated in FIG. 4 (last stage), the biochip includes a fixing material 51 disposed on at least the substrate (element substrate) surface in the cavity 30 and a target material fixed to the fixing material 51. 52. Alternatively, as illustrated in FIG. 5 (the last stage), the biochip includes a support material 53 having a target material 52 on the surface of a solid phase mass 54 disposed in the cavity 30.

The opening shape of the cavity is not particularly limited, and may be a quadrangle, a circle, a triangle, another polygon, or another shape. .
Further, the cavity may have a bottom shape that is the same shape as the opening (ie, may be a cavity that has been deeply drilled in), may have a stagnation shape, and may have other shapes. There may be.
Further, the cavity may have a bottom surface that penetrates the partition wall layer and has a bottom layer (elementary substrate or other layer) on which the partition layer is laminated, or a bottom surface in the partition layer without penetrating the partition layer. You may have.

  Biochip of the present invention can be used and biochips for DNA sequencing, such as biochips for diagnosis, as bio-chip functions by detecting fluorescence.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to this embodiment. In the description of Examples, “part” and “%” are based on mass unless otherwise specified.

[1] Preparation of Compound (A) Dispersion [Preparation Example 1] Dispersion (A1)
C.I represented by the following formula (20) I. Pigment Red 254 (compound A) 10 parts by mass, Disperbyk-2001 (produced by Big Chemie Japan Co., Ltd., 3 parts by mass of dispersant (in terms of solid content), propylene glycol monomethyl ether acetate (solvent) are mixed for 12 hours using a bead mill. Dispersion was performed to obtain a dispersion (A1) having a solid content concentration of 20% by mass in which CI Pigment Red 254 was dispersed.

[Preparation Example 2] Dispersion (A2)
C. I. C.I. represented by the following formula (21) instead of Pigment Red 254 I. Pigment Red 264 (compound A) was used in the same manner as in Preparation Example 1 except that C.I. I. A dispersion (A2) having a solid content concentration of 20% by mass in which Pigment Red 264 was dispersed was obtained.

[Preparation Example 3] Dispersion (A3)
C. I. Instead of C.I. Pigment Red 254, C.I. I. Pigment Red 177 (not Compound A) was used in the same manner as in Preparation Example 1 except that C.I. I. A dispersion (A3) having a solid concentration of 20% by mass in which Pigment Red 177 was dispersed was obtained.

[Preparation Example 4] Dispersion (A4)
C. I. 10 parts of Pigment Red 123, 3 parts by weight of Disperbyk-2001 (manufactured by Big Chemie Japan Co., Ltd., dispersant), solid propylene glycol, and propylene glycol monomethyl ether acetate (solvent) are mixed and dispersed in a bead mill for 12 hours. . I. A dispersion (A4) having a solid content concentration of 20% by mass in which CI Pigment Red 123 was dispersed was obtained.

[2] Synthesis of Polymer (B) {Alkali-Soluble Organic Polymer (B1)} [Synthesis Example 1] Synthesis of Polymer (B11) In a flask equipped with a condenser and a stirrer, 2,2′-azobisiso 3 parts by mass of butyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate were charged. Subsequently, as a monomer, 10 parts by weight of methacrylic acid, 25 parts by weight of tricyclo [5.2.1.0 ^2.6 ] decanyl methacrylate, 20 parts by weight of isobornyl acrylate, 30 parts by weight of n-butyl acrylate, While charging 15 parts by mass of p-isopropenylphenol, 5 parts by mass of 1-methyl-4-isopropylidene-1-cyclohexene was charged as a molecular weight regulator, followed by nitrogen substitution. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a polymer (B11) solution. (Mw = 10,000, Mn = 6,000, solid concentration 31.2% by mass)

[Synthesis Example 2] Synthesis of polymer (B12) As shown in Table 1, each compound of tricyclo [5.2.1.0 ^2.6 ] decanyl methacrylate, isobornyl acrylate, and n-butyl acrylate A solution of the polymer (B12) was obtained in the same manner as in Synthesis Example 1 except that the ratio was changed and benzyl methacrylate was used instead of p-isopropenylphenol. (Mw = 10,000, Mn = 4,000, solid content concentration 30% by mass)

[Synthesis Example 3] Synthesis of Polymer (B13) As shown in Table 1, the blending ratios of methacrylic acid and tricyclo [5.2.1.0 ^2.6 ] decanyl methacrylate were changed, and p -A solution of the polymer (B13) was obtained in the same manner as in Synthesis Example 1 except that benzyl methacrylate was used instead of isopropenylphenol. (Mw = 10,000, Mn = 4,000, solid content concentration 30% by mass)
The polymer (B13) is a raw material polymer of the polymer (B15) and the polymer (B16), and in this example, the polymer (B13) itself is not used as it is.

[Synthesis Example 4] Synthesis of polymer (B14) As shown in Table 1, except that each blending ratio of methacrylic acid and n-butyl acrylate was changed, and further 15 parts by mass of hydroxyethyl acrylate was added. In the same manner as in Synthesis Example 3, a polymer (B14) solution was obtained. (Mw = 10,000, Mn = 4,000, solid content concentration 30% by mass)
The polymer (B14) is a raw material polymer of the polymer (B17), and in this example, the polymer (B14) itself is not used as it is.

[Synthesis Example 5] Synthesis of Polymer (B15) To 100 parts by mass of the polymer (B13) obtained in Synthesis Example 3, 15 parts by mass of glycidyl methacrylate (polymerizable group-introducing component) and 1.4 parts by mass of tetrabutylammonium bromide. And 0.05 parts by mass of 4-methylphenol were added and reacted at 80 ° C. for 10 hours {for the reaction between the carboxyl group of the polymer (B13) and the epoxy group of the polymerizable group-introducing component} To obtain a polymer solution (B15) having a polymerizable group. (Mw = 11,000, Mn = 4,500, solid content concentration 30% by mass)

[Synthesis Example 6] Synthesis of Polymer (B16) To 100 parts by mass of the polymer (B13) obtained in Synthesis Example 3, 15 parts by mass of 4-hydroxybutyl acrylate glycidyl ether (polymerizable group-introducing component), tetrabutylammonium. Bring in 1.4 parts by mass of bromide and 0.05 parts by mass of 4-methylphenol and react at 80 ° C. for 10 hours {reaction between carboxyl group of polymer (B13) and epoxy group of polymerizable group introduction component The solution of the polymer (B16) having a polymerizable group was obtained. (Mw = 11,000, Mn = 4500, solid content concentration 30% by mass)

[Synthesis Example 7] Synthesis of Polymer (B17) To 100 parts by mass of the polymer (B14) obtained in Synthesis Example 4, 2-methacryloyloxyethyl isocyanate (polymerizable group-introducing component, trade name “Karenz MOI”, Showa Denko Co., Ltd.) 18 parts by mass, 0.3 parts by mass of dibutyltin laurate and 0.1 parts by mass of 4-methoxyphenol were added and stirred at 40 ° C. for 1 hour, and further stirred at 60 ° C. for 2 hours. Then, the reaction {for the reaction between the hydroxyl group of the polymer (B14) and the isocyanate group of the polymerizable group-introducing component} was performed to obtain a solution of the polymer (B17) having a polymerizable group. (Mw = 11,000, Mn = 4,500, solid content concentration 35.0 mass%)
In Synthesis Example 7, the progress of the reaction was followed by IR (infrared) absorption spectrum, and it was confirmed that the peak near 2270 cm ⁻¹ derived from the isocyanate group of 2-methacryloyloxyethyl isocyanate decreased with time. It was.

[3] Preparation of barrier rib forming composition [Example 1]
60 parts by mass of the dispersion (A1) containing the compound (A) obtained in [1], 100 parts by mass of the polymer (B11) obtained in [2], 60 parts by mass of the following polyfunctional monomer (C1) Part, 19 parts by mass of the following radiation sensitive polymerization initiator (D1), 4 parts by mass of the following radiation sensitive polymerization initiator (D2), 3 parts by mass of the following adhesion assistant (E1), 0. 1 part by mass and the following organic solvent (G1) were mixed to obtain a partition wall forming composition (Example 1) having a solid content concentration of 50% by mass.

接着助剤（Ｅ１）：シランカップリング剤、Ｅ：トリス−（３−トリメトキシシリルプロピル）イソシアヌレート（商品名「Ｙ−１１５９７」、モメンティブ社製）
界面活性剤（Ｆ１）：フッ素系界面活性剤（商品名「ＦＴＸ−２１８Ｆ」、ネオス社製）
有機溶媒（Ｇ１）：プロピレングリコールモノメチルエーテルアセテート Multifunctional monomer (C1): Dipentaerythritol hexaacrylate (trade name “Kayarad DPHA”, manufactured by Nippon Kayaku Co., Ltd.)
Radiation sensitive polymerization initiator (D1): 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651”, manufactured by Ciba Specialty Chemicals)
Radiation-sensitive polymerization initiator (D2): a compound having a structure represented by the following formula (23) (trade name “Lucirin LR8953X”, manufactured by BASF)

Adhesion aid (E1): Silane coupling agent, E: Tris- (3-trimethoxysilylpropyl) isocyanurate (trade name “Y-11597”, manufactured by Momentive)
Surfactant (F1): Fluorosurfactant (trade name “FTX-218F”, manufactured by Neos)
Organic solvent (G1): Propylene glycol monomethyl ether acetate

[Example 2]
A partition wall forming composition (Example 2) having a solid concentration of 60% by mass was obtained in the same manner as in Example 1 except that the dispersion liquid (A2) was used instead of the dispersion liquid (A1).

[Example 3]
In place of 60 parts by mass of the polyfunctional monomer (C1), 50 parts by mass of the polyfunctional monomer (C2) (trade name “Aronix M-450”, manufactured by Toagosei Co., Ltd.) was used. Radiation polymerization initiator (D1) 19 parts by mass and (D2) 4 parts by mass, radiation sensitive polymerization initiator (D3) (trade name “Irgacure OXE01”, manufactured by Ciba Specialty Chemicals) 2 parts by mass In the same manner as in Example 1 except that the adhesion assistant (E1) was not used, a partition wall forming composition (Example 3) having a solid concentration of 50% by mass was obtained.

[Example 4]
A partition wall forming composition (Example 4) having a solid concentration of 50% by mass was obtained in the same manner as in Example 3 except that the polymer (B12) was used instead of the polymer (B11).

[Example 5]
The same procedure as in Example 4 was performed except that the radiation sensitive polymerization initiator (D4) (trade name “Irgacure OXE02”, manufactured by Ciba Specialty Chemicals) was used instead of the radiation sensitive polymerization initiator (D3). Thus, a partition wall forming composition (Example 5) having a solid content concentration of 50% by mass was obtained.

[Example 6]
60 parts by mass of the dispersion (A1) obtained in [Preparation Example 1], 100 parts by mass of the polymer (B15) obtained in [Synthesis Example 5], 50 parts by mass of the polyfunctional monomer (C2), Solid content concentration by mixing 20 parts by mass of radiation polymerization initiator (D1), 20 parts by mass of radiation sensitive polymerization initiator (D2), 0.1 part by mass of surfactant (F1), and organic solvent (G1). A 50% by mass composition for forming partition walls (Example 6) was obtained.

[Example 7]
60 parts by mass of the dispersion (A1) obtained in [Preparation Example 1], 100 parts by mass of the polymer (B16) obtained in [Synthesis Example 6], 50 parts by mass of the polyfunctional monomer (C2), Radiation polymerization initiator (D5) (trade name “Irgacure 819”, manufactured by Ciba Specialty Chemicals) 10 parts by mass, surfactant (F1) 0.1 part by mass, organic solvent (G1), A partition wall forming composition (Example 7) having a solid content concentration of 50% by mass was obtained.

[Example 8]
In the same manner as in Example 7 except that the polymer (B17) obtained in [Synthesis Example 7] was used in place of the polymer (B16), a partition wall forming composition having a solid content concentration of 50 mass% ( Example 7) was obtained.

[Comparative Example 1]
A partition wall forming composition (Comparative Example 1) having a solid content concentration of 60% by mass was obtained in the same manner as in Example 1 except that 95 parts by mass of the dispersion (A3) was used instead of the dispersion (A1). It was.
[Comparative Example 2]
A partition wall forming composition (Comparative Example 2) having a solid content concentration of 60% by mass was obtained in the same manner as in Example 1 except that 95 parts by mass of the dispersion liquid (A4) was used instead of the dispersion liquid (A1). It was.

In addition, each component in Table 2 is as follows.
(C1) polyfunctional monomer; dipentaerythritol hexaacrylate (trade name “Kayarad DPHA”, manufactured by Nippon Kayaku Co., Ltd.)
(C2) polyfunctional monomer; trade name “Aronix M-450”, manufactured by Toagosei Co., Ltd.
(D1) radiation-sensitive polymerization initiator; 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651”, manufactured by Ciba Specialty Chemicals),
(D2) Radiation sensitive polymerization initiator; trade name “Lucirin LR8953X”, manufactured by BASF Corporation,
(D3) Radiation sensitive polymerization initiator; trade name “Irgacure OXE01”, manufactured by Ciba Specialty Chemicals,
(D4) Radiation sensitive polymerization initiator; trade name “Irgacure OXE02”, manufactured by Ciba Specialty Chemicals,
(D5) Radiation sensitive polymerization initiator; trade name “Irgacure 819”, manufactured by Ciba Specialty Chemicals,
(E1) Adhesion aid; silane coupling agent, E: tris- (3-trimethoxysilylpropyl) isocyanurate (trade name “Y-11597”, manufactured by Momentive,
(F1) Surfactant; Fluorosurfactant (trade name “FTX-218F”, manufactured by Neos Corporation.

[4] Evaluation (1) Measurement of transmittance of light having a wavelength of 550 nm with respect to the barrier ribs The barrier rib forming compositions of Examples 1 to 8 and Comparative Examples 1 and 2 were applied on a silicon wafer by spin coating. Then, it heated at 110 degreeC with the hotplate for 5 minutes, and obtained the 1st film | membrane with a thickness of 35 micrometers. About the obtained 1st film | membrane, the transmittance | permeability of the wavelength 550nm light with respect to a partition is measured using a spectrophotometer (the Hitachi make, model "U-2010 form"). The obtained results are also shown in Table 1.

(2) Evaluation of Adhesion of Partition Walls to Base Substrate Each of the partition wall forming compositions of Examples 1 to 8 and Comparative Examples 1 and 2 was applied on a silicon wafer by spin coating. Then, it heated at 110 degreeC with the hotplate for 5 minutes, and obtained the 45-micrometer-thick 1st film | membrane.
Next, ultraviolet light of 300 to 1000 mJ / cm ² was irradiated through a mask using an ultrahigh pressure mercury lamp (manufactured by OSRAM, HBO, output 1,000 W). The amount of exposure was confirmed using an illuminometer (illuminometer manufactured by Oak Manufacturing Co., Ltd., model “UV-M10”) connected to a probe (receiver, model “UV-35”)}.
Thereafter, the exposed first film was developed at room temperature using a 2.38 wt% tetramethylammonium hydroxide aqueous solution as a developer, washed with running water, and further blown with nitrogen. Subsequently, heating was performed at 220 ° C. for 1 hour using an oven to obtain a pattern (partition) having 10 square-shaped recesses (cavities) having a thickness (partition wall height) of 35 μm, a pitch of 30 μm, and 25 μm × 25 μm. .

The obtained partition walls were observed with a scanning electron microscope (manufactured by Hitachi, model “S-4200”) at a magnification of 1000 times, and adhesion evaluation was performed according to the following criteria.
“A”: When the inside of each of the ten cavities is observed, peeling between the partition walls and the substrate cannot be confirmed.
“B”: When the inside of each of the ten cavities was observed, one or more separations between the partition walls and the substrate could be confirmed.

(3) Water resistance evaluation of partition The partition (partition formed on the substrate) subjected to the adhesion evaluation of (2) was immersed in water and kept at 55 ° C. for 24 hours. Thereafter, water was removed by nitrogen blowing. Next, the immersed partition walls were observed with a scanning electron microscope (manufactured by Hitachi, model “S-4200”) at a magnification of 1000 times, and adhesion evaluation was performed according to the following criteria.
“A”: When the inside of each of the ten cavities is observed, separation between the partition walls and the base substrate cannot be confirmed.
“B”: When the inside of each of the ten cavities was observed, one or more separations between the partition walls, the base substrate, and the like were confirmed.

(4) Well shape Using a scanning electron microscope (Hitachi, Model “S-4200”), the cavity shape (well shape) formed by the partition wall subjected to the adhesion evaluation in (2) above was used. And evaluated according to the following criteria.
“A”: When the inside of each of the ten cavities was observed, all the ten cavities had a square shape of 25 μm × 25 μm.
“B”: When the inside of each of the ten cavities was observed, one or more cavities were not in a square shape of 25 μm × 25 μm.

  The present invention is not limited to that shown in the specific examples above, it can be the embodiment and various modifications within the scope of the present invention depending on the purpose, application.

10: Substrate (substrate),
20; partition wall, 21; first film,
30; cavity, compartmentalized area,
40; mask pattern,
51; immobilization material, 52; target material, 53; support material, 54; solid phase carrier,
100; biochip,
101: Microarray substrate (pre-biochip).

Claims (10)

In a method of manufacturing a microarray substrate, comprising: a substrate; a partition partitioning the surface of the substrate; and a region on the substrate partitioned by the partition.
A first film forming step of forming a first film on a substrate using a radiation-sensitive composition containing a compound (A) represented by the following formula (1);
And a partition wall forming step of forming the partition walls by patterning the first film by a lithography method.

[In Formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a perfluoroalkyl group having 1 to 10 carbon atoms, or an amino acid having 0 to 5 carbon atoms. Represents a group. ] The radiation-sensitive composition further contains a polymer (B), a polyfunctional monomer (C) and a radiation-sensitive polymerization initiator (D), and
The method for producing a microarray substrate according to claim 1, wherein the polymer (B) is an alkali-soluble polymer. A partition forming composition for forming the partition in a microarray substrate having a substrate, a partition partitioning the substrate surface, and a region on the substrate partitioned by the partition,
A composition for forming a partition wall comprising a compound (A) represented by the following formula (1).

[In Formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a perfluoroalkyl group having 1 to 10 carbon atoms, or an amino acid having 0 to 5 carbon atoms. Represents a group. ] Furthermore, it contains a polymer (B), a polyfunctional monomer (C) and a radiation sensitive polymerization initiator (D), and
The partition-forming composition according to claim 3, wherein the polymer (B) is an alkali-soluble polymer.   A partition wall for a microarray substrate obtained by using the partition wall forming composition according to claim 3. (A) A microarray substrate manufacturing process for manufacturing the microarray substrate using the method for manufacturing a microarray substrate according to claim 1 or 2,
(B) a fixing substance arranging step of arranging a fixing substance for fixing the target substance in the region;
(C) An immobilization step of immobilizing a target material on the immobilization material, and a biochip manufacturing method comprising: (A) A microarray substrate manufacturing process for manufacturing the microarray substrate using the method for manufacturing a microarray substrate according to claim 1 or 2,
(D) A biochip manufacturing method comprising: a support material disposing step of disposing a support material having a target material on a surface thereof in a first region.   The method for producing a biochip according to claim 6, wherein the immobilizing substance is polylysine, collagen, laminin, sialic acid oligosaccharide, mannose-binding lectin, integrin family ligand, peptide, antigen or antibody and nucleic acid.   The biochip manufacturing method according to claim 7, wherein the target material is a biological material.   A biochip obtained by the method for producing a biochip according to claim 7.

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