JP2019174793A - Radiation-sensitive composition and 1,2-naphthoquinone-2-diazide sulfonic acid derivative - Google Patents

Abstract

To provide a radiation-sensitive composition having excellent radiation sensitivity and resolution, and capable of achieving high voltage retention property.SOLUTION: There is provided a radiation-sensitive composition containing an alkali soluble polymer (A), and a compound (B) having at least one kind of structure (bb) selected from a structure represented by the formula (b1) and a structure represented by the formula (b2). In the formulae (b1) and (b2), X is an electron attracting group or a halogen atom, X may be the same or different in the case where there are a plurality of X, n1 is an integer of 0 to 3, n2 is an integer of 0 to 2, n1+n2 is 1 or more, n3 is an integer of 0 to 4, n4 is an integer of 0 to 1, n3+n4 is 1 or more, and * is bond.SELECTED DRAWING: None

Description

  The present invention relates to a radiation-sensitive composition and a 1,2-naphthoquinone-2-diazide sulfonic acid derivative.

  Conventionally, 1,2-naphthoquinone-2-diazidesulfonic acid derivatives have been used as radiation-sensitive compounds in radiation-sensitive compositions (see, for example, Patent Documents 1 to 3). However, the known 1,2-naphthoquinone-2-diazidesulfonic acid derivatives have problems such as insufficient radiation sensitivity.

JP 2002-088052 A JP 2007-156243 A JP 2006-209113 A

  It is an object of the present invention to provide a radiation-sensitive composition having excellent radiation sensitivity and resolution and exhibiting excellent voltage holding characteristics, and a 1,2-naphthoquinone-2-diazidosulfonic acid derivative And

  As a result of studies to solve the above problems, the present inventors have found that the above problems can be solved by introducing an electron withdrawing group or a halogen atom into a 1,2-naphthoquinone-2-diazide group. It came to complete. That is, the present invention relates to the following [1] to [9].

  [1] An alkali-soluble polymer (A) and a compound (B) having at least one structure (bb) selected from the structure represented by the formula (b1) and the structure represented by the formula (b2) A radiation-sensitive composition to be contained.

［式（ｂ１）および（ｂ２）中、Ｘは電子求引性基またはハロゲン原子であり、Ｘが複数ある場合はそれぞれ同一でも異なってもよく、ｎ１は０〜３の整数であり、ｎ２は０〜２の整数であり、ただしｎ１＋ｎ２は１以上であり、ｎ３は０〜４の整数であり、ｎ４は０〜１の整数であり、ただしｎ３＋ｎ４は１以上であり、＊は結合手である。］

[In the formulas (b1) and (b2), X is an electron-attracting group or a halogen atom, and when there are a plurality of Xs, they may be the same or different, n1 is an integer of 0 to 3, and n2 is N2 is an integer of 0 to 2, n1 + n2 is 1 or more, n3 is an integer of 0 to 4, n4 is an integer of 0 to 1, n3 + n4 is 1 or more, and * is a bond . ]

[2] The radiation-sensitive composition according to [1], wherein X in the formulas (b1) and (b2) is an electron withdrawing group.
[3] The electron withdrawing groups in the formulas (b1) and (b2) are a nitro group, a cyano group, a sulfo group, a carboxy group, a tosyl group, a mesyl group, a phenyl group, a trifluoromethylsulfonyl group, and carbon. The sensation according to [1], wherein the halogen atom is at least one selected from alkyl halide groups of 1 to 12, and the halogen atom is at least one selected from a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Radiation composition.

  [4] The above [1] to [1], wherein the compound (B) is at least one selected from a compound represented by the formula (B1-3-1) and a compound represented by the formula (B1-4-1) The radiation sensitive composition of any one of [3].

［式（Ｂ１−３−１）中のＱは、それぞれ独立に前記構造（ｂｂ）または水素原子であり、ｍ１〜ｍ３は０〜５の整数であり、ただしｍ１、ｍ２およびｍ３の少なくとも１つは１以上の整数であり、かつ、全てのＱが水素原子であることはない。式（Ｂ１−４−１）中のＱは、それぞれ独立に前記構造（ｂｂ）または水素原子であり、ｍ４〜ｍ６は０〜５の整数であり、ただしｍ４、ｍ５およびｍ６の少なくとも１つは１以上の整数であり、かつ、全てのＱが水素原子であることはない。］

[Q in Formula (B1-3-1) is each independently the structure (bb) or a hydrogen atom, and m1 to m3 are integers of 0 to 5, provided that at least one of m1, m2, and m3 Is an integer of 1 or more, and not all Q are hydrogen atoms. Q in formula (B1-4-1) is each independently the structure (bb) or a hydrogen atom, and m4 to m6 are integers of 0 to 5, provided that at least one of m4, m5 and m6 is It is an integer of 1 or more, and all Qs are not hydrogen atoms. ]

[5] The radiation sensitive composition according to any one of [1] to [4], wherein the compound (B) is contained in an amount of 5 to 100 parts by mass with respect to 100 parts by mass of the polymer (A). object.
[6] (1) A step of forming a coating film of the radiation-sensitive composition according to any one of [1] to [5] on a substrate, and (2) radiation on at least a part of the coating film. (3) The process of developing the coating film after irradiation, and (4) The manufacturing method of a cured film which has the process of heating the coating film after image development, and obtaining a cured film.
[7] A resin component and a decomposition product derived from the compound (B) having at least one structure (bb) selected from the structure represented by the formula (b1) and the structure represented by the formula (b2) A cured film containing
[8] A display device having the cured film according to [7].
[9] A compound (B) having at least one structure (bb) selected from the structure represented by the formula (b1) and the structure represented by the formula (b2).

  According to the present invention, there are provided a radiation-sensitive composition having excellent radiation sensitivity and resolution and exhibiting excellent voltage holding characteristics, and a 1,2-naphthoquinone-2-diazidosulfonic acid derivative. Can do.

  In the present specification, preferable upper limit values and lower limit values are described in terms of the content ratio of each component, etc., but numerical ranges defined from any combination of the described upper limit values and lower limit values are also described in this specification. It shall be.

  Hereinafter, the radiation-sensitive composition, the method for producing a cured film, the cured film, and the display element of the present invention will be described. The compound (B) of the present invention will be described in the [Radiosensitive composition] column.

[Radiation sensitive composition]
The radiation-sensitive composition of the present invention (simply referred to as “the composition of the present invention”) is represented by an alkali-soluble polymer (A), a structure represented by the formula (b1), and a formula (b2) described later. And a compound (B) having at least one structure (bb) selected from the structures described above.

<Alkali-soluble polymer (A)>
As the alkali-soluble polymer (A) (also simply referred to as “polymer (A)”), for example, a polymer having an acidic functional group such as a carboxy group, a phenolic hydroxyl group and a fluorinated hydroxyalkyl group is preferable. The alkali-soluble means that the polymer can be dissolved or swelled in an alkali developer such as an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass.

The fluorinated hydroxyalkyl group is a hydroxyalkyl group in which a part of hydrogen atoms bonded to a carbon atom is substituted with a fluorine atom, for example, a group represented by —C (R ^a1 ) (R ^a2 ) OH. In the above formula, R ^a1 is a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, and R ^a2 is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms or a fluorine having 1 to 4 carbon atoms. Alkyl group.

  Examples of the polymer having an acidic functional group include novolak resin, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, phenol-dicyclopentadiene condensation resin, polybenzoxazole precursor, polyhydroxystyrene, hydroxy Polymers having a phenolic hydroxyl group, such as a copolymer of styrene and styrene; polymers having a carboxy group, such as a carboxy group-containing epoxy (meth) acrylate resin having a novolak skeleton in the main chain, and polyamic acid It is done.

  Examples of the polymer having an acidic functional group include an ethylenically unsaturated monomer having one or more acidic functional groups (hereinafter also referred to as “unsaturated monomer (a1)”), the above (a1), And a copolymer with another copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as “unsaturated monomer (a2)”). In particular, a (meth) acrylic polymer having an acidic functional group is preferable.

  Examples of the unsaturated monomer (a1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth). Carboxy group-containing unsaturated monomers such as acrylate and p-vinylbenzoic acid; phenolic hydroxyl group-containing unsaturated monomers such as hydroxystyrene, α-methyl-p-hydroxystyrene, hydroxyphenyl acrylate, and hydroxyphenylacrylamide; 4 -Fluorinated hydroxyalkyl group-containing unsaturated monomers such as (1,1,1,3,3,3-hexafluoro-2-hydroxypropan-2-yl) styrene. Among these, it is preferable to use at least (meth) acrylic acid from the viewpoint of polymerizability.

An unsaturated monomer (a1) can be used individually or in combination of 2 or more types.
Examples of the unsaturated monomer (a2) include N-substituted maleimides such as N-arylmaleimide, N-alkylmaleimide and N-cycloalkylmaleimide; aromatic vinyl compounds such as styrene and its derivatives; Acrylic acid alkyl ester, (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid alicyclic ring-containing ester, (meth) acrylic acid aromatic ring-containing ester, oxirane ring, oxetane ring, cyclic ether ring such as oxolane ring ( (Meth) acrylic acid esters such as (meth) acrylic acid esters; aromatic ring-containing silane compounds such as styryl group-containing silane compounds; vinyl ethers such as alicyclic vinyl ethers; polymer chains of aromatic vinyl compounds, (meth) acrylic acid esters Polymer molecules such as polymer chains and polysiloxane molecular chains Mentioned macromonomer to end with a mono (meth) acryloyl groups. Among these, from the viewpoint of imparting a crosslinkable functional group to the alkali-soluble polymer, at least one selected from a (meth) acrylic acid ester having an oxirane ring and a (meth) acrylic acid ester having an oxetane ring is used. Is preferred.

  More specifically, [0060] to [0062] in JP-A-2015-004968, [0036] to [0045] in JP-A-2008-233346, and [0013] to [0013] in JP-A-2009-229567. And the monomers described in [0021].

An unsaturated monomer (a2) can be used individually or in combination of 2 or more types.
Specific examples of the copolymer of the unsaturated monomer (a1) and the unsaturated monomer (a2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. JP, 10-300922, JP 11-174224, JP 11-258415, JP 2000-56118, JP 2004-101728, JP 2006-151549. And copolymers disclosed in JP 2007-128062 A, JP 2008-233563 A, JP 2017-181928 A, JP 2017-173376 A, and the like.

  Also, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, JP-A-2008-181095. As disclosed in the publications and the like, a carboxy group-containing (meth) acrylic polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used.

  In the copolymer of (a1) and (a2), the upper limit of the content ratio of the structural unit derived from the unsaturated monomer (a1) is preferably 50% by mass, more preferably 40% by mass; The lower limit is preferably 5% by mass, more preferably 10% by mass.

  In one embodiment, the copolymer of (a1) and (a2) is an unsaturated monomer (a1), a (meth) acrylic acid ester having an oxirane ring and a (meth) acrylic acid having an oxetane ring. A copolymer with at least one selected from esters is preferred. In this copolymer, an unsaturated monomer (a2) other than these may be copolymerized.

  In the copolymer of (a1) and (a2), the content of structural units derived from at least one selected from (meth) acrylic acid ester having an oxirane ring and (meth) acrylic acid ester having an oxetane ring The upper limit is preferably 50% by mass, more preferably 40% by mass; the lower limit is preferably 5% by mass, more preferably 10% by mass, and even more preferably 15% by mass.

  The copolymer of (a1) and (a2) can be produced by a known method. For example, JP 2003-222717 A, JP 2006-259680 A, and International Publication No. 2007/029871. The structure, weight average molecular weight, and molecular weight distribution can also be controlled by the method disclosed in No. et al.

Examples of the polymer (A) also include alkali-soluble polysiloxane, polyimide or polybenzoxazole.
Specific examples of the polysiloxane include, for example, International Publication No. 2017/188047, International Publication No. 2017/1616963, International Publication No. 2017/159876, Japanese Unexamined Patent Publication No. 2013-114238, Japanese Unexamined Patent Publication No. 2012-53381, Examples thereof include copolymers disclosed in JP 2010-32977 A and the like.

  Specific examples of the polyimide or polybenzoxazole include, for example, International Publication No. 2017/1616963, International Publication No. 2017/159676, International Publication No. 2017/057281, International Publication No. 2017/159476, International Publication No. 2017 / No. 073481, International Publication No. 2017/038828, International Publication No. 2016/148176, Japanese Unexamined Patent Publication No. 2015-114355, Japanese Unexamined Patent Publication No. 2013-164432, Japanese Unexamined Patent Publication No. 2010-72143, etc. Coalescence is mentioned.

  The lower limit of the weight average molecular weight (Mw) of the polymer (A) is usually 1,000, preferably 5,000; the upper limit is usually 100,000, preferably 50,000. The upper limit of the ratio (molecular weight distribution: Mw / Mn) of the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer (A) is preferably 5.0, more preferably 3.0; The lower limit is preferably 1.0, more preferably 1.1. Mw and Mn are values in terms of polystyrene measured by gel permeation chromatography (hereinafter also referred to as “GPC”).

A polymer (A) can be used individually or in combination of 2 or more types.
In the composition of the present invention, in the solid content of 100% by mass of the composition, the lower limit of the content ratio of the polymer (A) is usually 10% by mass, preferably 15% by mass, more preferably 20% by mass. Yes; the upper limit is usually 95% by weight. In addition, solid content refers to all components other than the solvent (E) mentioned later.

<Compound (B)>
The compound (B) has at least one structure (bb) selected from the structure represented by the formula (b1) and the structure represented by the formula (b2).

式（ｂ１）および（ｂ２）中、Ｘは電子求引性基またはハロゲン原子であり、好ましくは電子求引性基であり、Ｘが複数ある場合はそれぞれ同一でも異なってもよく、ｎ１は０〜３の整数であり、ｎ２は０〜２の整数であり、ただしｎ１＋ｎ２は１以上、好ましくは１〜３であり、ｎ３は０〜４の整数であり、ｎ４は０〜１の整数であり、ただしｎ３＋ｎ４は１以上、好ましくは１〜３であり、＊は結合手である。

In the formulas (b1) and (b2), X is an electron withdrawing group or a halogen atom, preferably an electron withdrawing group, and when there are a plurality of X, they may be the same or different, and n1 is 0. N2 is an integer of 0 to 2, n1 + n2 is 1 or more, preferably 1 to 3, n3 is an integer of 0 to 4, and n4 is an integer of 0 to 1. However, n3 + n4 is 1 or more, preferably 1 to 3, and * is a bond.

  In formula (b1), in one embodiment, n1 is 1 and n2 is 0. In formula (b2), in one embodiment, n3 is 1 and n4 is 0. For example, when X is a cyano group, such an embodiment is preferable from the viewpoints of radiation sensitivity and resolution.

  The electron withdrawing group is selected from, for example, a nitro group, a cyano group, a sulfo group, a carboxy group, a tosyl group, a mesyl group, a phenyl group, a trifluoromethylsulfonyl group, and a halogenated alkyl group having 1 to 12 carbon atoms. At least one. Among these, from the viewpoint of suppressing coloration of the coating film, a nitro group, a cyano group, and a carboxy group are preferable, a nitro group and a cyano group are more preferable, and a cyano group is particularly preferable.

  As a halogen atom, it is at least 1 sort (s) chosen from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, for example. Among these, a fluorine atom and a chlorine atom are preferable from the viewpoint of chemical synthesis.

  The compound (B) is a compound that generates a carboxy group from a 1,2-quinonediazide group in the structure (bb) by irradiation with radiation. In the present invention, since the structure (bb) has X: an electron withdrawing group or a halogen atom, a high sensitivity and a high resolution effect are exhibited. In addition, for example, when a display element having a cured film formed from the composition of the present invention containing the compound (B) is produced, excellent voltage holding characteristics can be obtained. Details of the voltage holding characteristic will be described later.

  The radiation sensitive composition containing the compound (B) is a positive type, and the coating film obtained from the composition is a film hardly soluble in an alkali developer. A pattern can be formed by a development process utilizing the fact that the coating film changes from a hardly alkali-soluble state to an easily alkali-soluble state by radiation irradiation.

  The structure (bb) is a structure represented by the formula (b1-1) or (b1-2) because the coating film formed from the radiation-sensitive composition containing the compound (B) is difficult to be colored during baking. Is preferred.

式（ｂ１−１）および（ｂ１−２）中、Ｘ、ｎ１およびｎ２は、式（ｂ１）中の同一記号と同義であり、＊は結合手である。

In the formulas (b1-1) and (b1-2), X, n1 and n2 are synonymous with the same symbols in the formula (b1), and * is a bond.

The compound (B) is preferably an ester of a compound having one or more phenolic hydroxyl groups and a 1,2-naphthoquinone-2-diazide sulfonic acid compound.
The 1,2-naphthoquinone-2-diazidesulfonic acid compound is, for example, a compound represented by the formula (b1 ′), a compound represented by the formula (b2 ′), or an acid chloride of these sulfonic acids.

式（ｂ１'）および（ｂ２'）中、Ｘ、ｎ１、ｎ２、ｎ３およびｎ４は、式（ｂ１）および（ｂ２）中の同一記号と同義である。

In the formulas (b1 ′) and (b2 ′), X, n1, n2, n3, and n4 are synonymous with the same symbols in the formulas (b1) and (b2).

  Examples of the compound having one or more phenolic hydroxyl groups include compounds represented by formulas (p1-1) to (p1-6).

式（ｐ１−１）中、Ｒ¹〜Ｒ¹⁰はそれぞれ独立に水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基または水酸基であり、ただし、Ｒ¹〜Ｒ⁵の少なくとも１つは水酸基である。Ａは直接結合、−Ｏ−、−Ｓ−、−ＣＨ₂−、−Ｃ（ＣＨ₃）₂−、−Ｃ（ＣＦ₃）₂−、−ＣＯ−または−ＳＯ₂−である。

In formula (p1-1), R ^{1 to} R ¹⁰ are each independently 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, provided that R ^{1 to} R ⁵ At least one is a hydroxyl group. A is a direct bond, —O—, —S—, —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —CO— or —SO ₂ —.

式（ｐ１−２）中、Ｒ¹¹〜Ｒ²⁴はそれぞれ独立に水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基または水酸基であり、ただし、Ｒ¹¹〜Ｒ¹⁵の少なくとも１つは水酸基である。Ｙ¹〜Ｙ⁴はそれぞれ独立に水素原子または炭素数１〜４のアルキル基である。ｎは１または２である。式（ｐ１−２）において中央のベンゼン環の−Ｃ（Ｙ¹）（Ｙ²）−、−Ｃ（Ｙ³）（Ｙ⁴）−に対する結合位置は１，３−位であるが、１，４−位であってもよい。

In formula (p1-2), R ^{11 to} R ²⁴ are each independently 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, provided that R ^{11 to} R ¹⁵ At least one is a hydroxyl group. Y ^{1 to} Y ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is 1 or 2. In the formula (p1-2), the bonding position of the central benzene ring to —C (Y ¹ ) (Y ² ) — or —C (Y ³ ) (Y ⁴ ) — is 1,3-position. 4-position may be sufficient.

式（ｐ１−３）中、Ｒ²⁵〜Ｒ³⁹はそれぞれ独立に水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基または水酸基であり、ただし、Ｒ²⁵〜Ｒ³⁹の少なくとも１つは水酸基であり、好ましくは、Ｒ²⁵〜Ｒ²⁹の少なくとも１つは水酸基であり、Ｒ³⁰〜Ｒ³⁴の少なくとも１つは水酸基である。Ｙ⁵は水素原子または炭素数１〜４のアルキル基である。

In formula (p1-3), R ^{25 to} R ³⁹ are each independently 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, provided that R ^{25 to} R ³⁹ At least one is a hydroxyl group. Preferably, at least one of R ^{25 to} R ²⁹ is a hydroxyl group, and at least one of R ^{30 to} R ³⁴ is a hydroxyl group. Y ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

式（ｐ１−４）中、Ｒ⁴⁰〜Ｒ⁵⁸はそれぞれ独立に水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基または水酸基であり、ただし、Ｒ⁴⁰〜Ｒ⁵⁴の少なくとも１つは水酸基であり、好ましくは、Ｒ⁴⁰〜Ｒ⁴⁴の少なくとも１つは水酸基であり、Ｒ⁴⁵〜Ｒ⁴⁹の少なくとも１つは水酸基であり、Ｒ⁵⁰〜Ｒ⁵⁴の少なくとも１つは水酸基である。Ｙ⁶〜Ｙ⁸はそれぞれ独立に水素原子または炭素数１〜４のアルキル基である。

In the formula (p1-4), R ^{40 to} R ⁵⁸ are each independently 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, provided that R ^{40 to} R ⁵⁴ At least one is a hydroxyl group, preferably, at least one of R ^{40 to} R ⁴⁴ is a hydroxyl group, at least one of R ^{45 to} R ⁴⁹ is a hydroxyl group, and at least one of R ^{50 to} R ⁵⁴ is a hydroxyl group It is. Y ^{6 to} Y ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

式（ｐ１−５）中、Ｒ⁵⁹〜Ｒ⁷²はそれぞれ独立に水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基または水酸基であり、ただし、Ｒ⁵⁹〜Ｒ⁶²の少なくとも１つは水酸基であり、Ｒ⁶³〜Ｒ⁶⁷の少なくとも１つは水酸基である。

In formula (p1-5), R ^{59 to} R ⁷² are each independently 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, provided that R ^{59 to} R ⁶² At least one is a hydroxyl group, and at least one of R ^{63 to} R ⁶⁷ is a hydroxyl group.

式（ｐ１−６）中、Ｒ⁷³〜Ｒ⁸¹はそれぞれ独立に水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基または水酸基であり、ただし、Ｒ⁷³〜Ｒ⁷⁶の少なくとも１つは水酸基であり、Ｒ⁷⁷〜Ｒ⁸¹の少なくとも１つは水酸基である。Ｒａはそれぞれ独立に水素原子または炭素数１〜４のアルキル基であり、また、任意の２つのＲａが相互に結合して環を形成していてもよい。

In formula (p1-6), R ^{73 to} R ⁸¹ are each independently 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, provided that R ^{73 to} R ⁷⁶ At least one is a hydroxyl group, and at least one of R ^{77 to} R ⁸¹ is a hydroxyl group. Each Ra is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and any two Ras may be bonded to each other to form a ring.

  Specific examples of the compound having one or more phenolic hydroxyl groups 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, 1,1,1-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-dihydroxy Benzene, 4,4 '- [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, and a compound represented by the following formula are exemplified.

フェノール性水酸基を１つ以上有する化合物は単独でまたは２種類以上を組み合わせて用いることができる。

Compounds having one or more phenolic hydroxyl groups can be used alone or in combination of two or more.

As the compound (B), a compound in which at least one phenolic hydroxyl group (—OH) in a compound having one or more phenolic hydroxyl groups (—OH) is —OQ ¹ (Q ¹ is the structure (bb ) Is preferred. The compound (B) is preferably at least one selected from the compound represented by the formula (B1-3-1) and the compound represented by the formula (B1-4-1) from the viewpoint of chemical synthesis.

式（Ｂ１−３−１）中のＱは、それぞれ独立に前記構造（ｂｂ）または水素原子であり、ｍ１〜ｍ３は０〜５の整数であり、ただしｍ１、ｍ２およびｍ３の少なくとも１つは１以上の整数であり、かつ、全てのＱが水素原子であることはない。ｍ１〜ｍ３は、それぞれ、好ましくは１〜５、より好ましくは１〜３である。

Q in formula (B1-3-1) is each independently the structure (bb) or a hydrogen atom, and m1 to m3 are integers of 0 to 5, provided that at least one of m1, m2, and m3 is It is an integer of 1 or more, and all Qs are not hydrogen atoms. m1 to m3 are each preferably 1 to 5, and more preferably 1 to 3.

  Q in formula (B1-4-1) is each independently the structure (bb) or a hydrogen atom, and m4 to m6 are integers of 0 to 5, provided that at least one of m4, m5 and m6 is It is an integer of 1 or more, and all Qs are not hydrogen atoms. m4 to m6 are each preferably 1 to 5, and more preferably 1 to 3.

That is, the compound represented by the formula (B1-3-1) and the compound represented by the formula (B1-4-1) each have at least one structure (bb).
A compound (B) can be used individually or in combination of 2 or more types.

  In the composition of the present invention, the lower limit of the content of the compound (B) is usually 5 parts by mass, preferably 10 parts by mass, and more preferably 15 parts by mass with respect to 100 parts by mass of the polymer (A). Yes; The upper limit of the content of the compound (B) is usually 100 parts by mass, preferably 50 parts by mass, and more preferably 40 parts by mass. When the content of the compound (B) is 5 parts by mass or more, the difference in solubility in the developer between the irradiated portion and the unirradiated portion is large, and patterning can be performed satisfactorily. When the content of the compound (B) is 100 parts by mass or less, a large amount of unreacted compound (B) does not remain in the irradiation with radiation for a short time, and therefore, development can be performed satisfactorily.

  Compound (B) is, for example, a conventionally known 1,2-naphthoquinone-2- compound except that X: 1,2-naphthoquinone-2-diazide compound having an electron withdrawing group or a halogen atom is used as a starting material. Similar to the diazide derivative, it can be produced according to a conventionally known method such as those described in JP-A No. 2000-072740, JP-A No. 2002-088052 and the like. For example, a well-known condensation reaction is mentioned. In this condensation reaction, 1,2-naphthoquinone-2-di, corresponding to preferably 10 to 85 mol%, more preferably 20 to 70 mol%, based on the number of OH groups in the compound having one or more phenolic hydroxyl groups. An azidosulfonic acid compound can be used.

<Other ingredients>
The composition of the present invention contains the polymer (A) and the compound (B) as essential components, but if necessary, as other components, a thermosensitive acid-generating compound, at least one ethylenically unsaturated divalent compound. It can contain at least one selected from a polymerizable compound having a heavy bond, an epoxy resin other than the polymer (A), an adhesion assistant (C), and a surfactant (D).

  The composition of the present invention can contain a heat-sensitive acid generating compound in order to improve the transparency and hardness of the cured film. Examples of the thermosensitive acid generating compound include onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts, and phosphonium salts. The heat-sensitive acid generating compound can be used alone or in combination of two or more.

The composition of the present invention can contain a heat-sensitive acid generating compound in an amount of preferably 20 parts by mass or less, more preferably 5 parts by mass or less, with respect to 100 parts by mass of the polymer (A).
The composition of the present invention can contain a polymerizable compound having at least one ethylenically unsaturated double bond in order to improve the transparency and hardness of the cured film. Examples of the polymerizable compound include (meth) acrylates such as monofunctional (meth) acrylates, bifunctional (meth) acrylates, and trifunctional or higher functional (meth) acrylates. The number of (meth) acryloyl groups in the (meth) acrylate is preferably 2-6. Among these, trifunctional or higher functional (meth) acrylates are preferable, and examples thereof include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. The said polymeric compound can be used individually or in combination of 2 or more types.

  The composition of the present invention can contain the polymerizable compound in an amount of preferably 50 parts by mass or less, more preferably 40 parts by mass or less, with respect to 100 parts by mass of the polymer (A).

  The composition of the present invention can contain an epoxy resin other than the polymer (A) in order to improve the transparency and hardness of the cured film. The polymer (A) also includes an “epoxy resin”, but differs from the epoxy resin in that it has alkali solubility. The epoxy resin here is alkali-insoluble.

  The epoxy resin is not limited as long as the compatibility is not affected. For example, bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin , Glycidylamine type epoxy resin, heterocyclic epoxy resin, and resin obtained by (co) polymerization of glycidyl methacrylate. Among these, bisphenol A type epoxy resin, cresol novolac type epoxy resin, and glycidyl ester type epoxy resin are preferable. An epoxy resin can be used individually or in combination of 2 or more types.

The composition of the present invention can contain the epoxy resin in an amount of preferably 50 parts by mass or less with respect to 100 parts by mass of the polymer (A).
The composition of the present invention can contain an adhesion assistant (C) in order to improve the adhesion between the substrate and the coating film. Examples of the adhesion assistant (C) include functional silane coupling agents such as silane coupling agents having a reactive functional group such as a carboxy group, a methacryloyl group, a vinyl group, an isocyanate group, an epoxy group, and an amino group. It is done. Specifically, trimethoxysilylbenzoic acid, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane. As the adhesion assistant (C), for example, compounds described in JP-A-2006-12697 and JP-A-2009-204865 can also be used. The adhesion assistant (C) can be used alone or in combination of two or more.
The composition of the present invention can contain the adhesion assistant (C) in an amount of preferably 20 parts by mass or less, more preferably 10 parts by mass or less with respect to 100 parts by mass of the polymer (A).
The composition of the present invention can contain a surfactant (D) in order to improve the coating property. Examples of the surfactant (D) include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. Specific examples include JP-A-2006-12697 and JP-A-2009-204865. And surfactants described in Japanese Patent Publication No. Surfactant (D) can be used individually or in combination of 2 or more types.

  The composition of the present invention can contain the surfactant (D) in an amount of preferably 5 parts by mass or less, more preferably 2 parts by mass or less, with respect to 100 parts by mass of the polymer (A).

<Solvent (E)>
The composition of the present invention can be prepared, for example, as a liquid composition by blending the solvent (E). The solvent (E) is appropriately selected and used as long as the above components constituting the composition of the present invention are dispersed or dissolved and do not react with these components and have appropriate volatility. can do.

  Solvent (E) includes alcohol, ethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetate, propylene glycol from the viewpoints of solubility of each component, non-reactivity with each component, and ease of film formation. Monoalkyl ether, propylene glycol dialkyl ether, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, diethylene glycol monoalkyl ether acetate, lactic acid ester, aliphatic carboxylic acid ester, other ester, ketone solvent, amide solvent, Lactone solvents and aromatic hydrocarbon solvents are preferably used. Among these, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, Diethylene glycol monoethyl ether acetate, methyl methoxypropionate, and ethyl ethoxypropionate can be particularly preferably used. Others, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone , Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. Good.

A solvent (E) can be used individually or in combination of 2 or more types.
When the solvent (E) is used as in preparing the composition of the present invention as a liquid composition, the lower limit of the content ratio of components (solid content) other than the solvent (E) in the composition of the present invention is The upper limit is usually 50% by mass, preferably 40% by mass, and more preferably 30% by mass, usually 5% by mass, preferably 10% by mass, more preferably 15% by mass.
The liquid composition thus prepared can be used after being filtered using a filter having pores having a pore diameter of about 0.2 μm.

[Curing film and method for producing the same]
The cured film of the present invention contains a resin component and a decomposition product derived from the compound (B).
As said resin component, the component derived from the alkali-soluble polymer (A) mentioned above is mentioned, for example.

The decomposition product derived from the compound (B) has, for example, a structure in which — [C (═O) —C (═N ₂ )] — in the structure (bb) is transferred to a ketene structure, or When the resin component has a functional group capable of reacting with a ketene structure such as a hydroxy group, the ketene structure reacts with the functional group such as a hydroxy group to form an indenecarboxylic acid ester structure together with the resin component. is doing.

Therefore, the cured film of the present invention can have a crosslinked structure formed from the resin component and the decomposition product derived from the compound (B).
It describes about the method of manufacturing the cured film of this invention using the radiation sensitive composition of this invention. Examples of the cured film of the present invention include an interlayer insulating film, a planarizing film, a microlens, and a spacer. The thickness of the cured film is usually 0.5 to 6 μm. The cured film of the present invention has high hardness and excellent transparency and solvent resistance.

  The method for producing a cured film of the present invention includes a step (1) of forming a coating film of the radiation-sensitive composition of the present invention on a substrate, a step (2) of irradiating at least a part of the coating film with radiation, It has the process (3) which develops the coating film after irradiation, and the process (4) which heats the coating film after development and obtains a cured film.

<Step (1)>
In the step (1), the composition of the present invention is applied on a substrate, and when the composition contains a solvent (E), the solvent (E) is preferably removed by pre-baking to provide radiation sensitivity. A coating film of the composition is formed.

Examples of the substrate include a glass substrate, a silicon substrate, and a substrate in which various metal members are formed on the surface thereof.
Examples of the coating method of the composition include a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, and an ink jet method, and a spin coating method and a slit die coating method. Is preferred.

  The prebaking conditions vary depending on the type and content ratio of each component in the composition of the present invention. For example, it can be set at 60 to 110 ° C. for about 30 seconds to 15 minutes. In the present invention, as described in the evaluation of the pre-bake margin described later, the fluctuation of the required exposure amount according to the pre-bake temperature is small and excellent.

  The film thickness of the coating film of the radiation-sensitive composition (in the case of a liquid composition containing a solvent (E) or the like, the value after pre-baking) is usually 0.5 to 6 μm. For example, when an interlayer insulating film, a planarizing film, or a spacer is formed, the film thickness is preferably 3 to 6 μm, and when a microlens is formed, the film thickness is preferably 0.5 to 3 μm.

<Step (2)>
In the step (2), at least a part of the coating film formed in the step (1) is irradiated with radiation. For example, the coating film is irradiated with radiation through a mask having a predetermined pattern.
Examples of radiation include visible light, ultraviolet light, X-rays, and charged particle beams. Examples of visible light and ultraviolet light include g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), KrF excimer laser light (wavelength 248 nm), and ArF excimer laser light (wavelength 193 nm). . X-rays include, for example, synchrotron radiation. Examples of the charged particle beam include an electron beam. Among these, visible light and ultraviolet light are preferable, and radiation including at least one selected from g-line, h-line, i-line, and KrF excimer laser light is particularly preferable.

The exposure amount is usually 5 to 1000 mJ / cm ² . For example, when an interlayer insulating film, a planarizing film, or a spacer is formed, the exposure amount is preferably 5 to 500 mJ / cm ^{2, and} when a microlens is formed, the exposure amount is preferably 5 to 200 mJ / cm ^2. . Since the composition of the present invention is excellent in radiation sensitivity, a pattern can be satisfactorily formed even when the exposure dose is less than 150 mJ / cm ² .

<Step (3)>
In the step (3), the coating film after radiation irradiation is subjected to development using a developer, and the radiation irradiated part is removed. Thereby, the patterned coating film can be obtained.
For the development treatment, an alkaline developer is usually used, and examples thereof include an aqueous solution of an alkaline compound (basic compound). Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyl. Diethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4. 3.0] -5-nonane. The concentration of the alkaline compound in the alkaline developer is usually from 0.1 to 10% by mass. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution, or various organic solvents that dissolve the composition of the present invention can be used as a developing solution.

  Examples of the developing method include a liquid filling method, a dipping method, a rocking dipping method, and a shower method. The development time varies depending on the composition of the composition, but can be, for example, 30 to 120 seconds. In addition, the rinse process by running water washing | cleaning can be performed with respect to the patterned coating film, for example.

In addition, by irradiating the entire surface of the patterned coating film with radiation (post-exposure), the compound (B) remaining in the coating film can be decomposed. The exposure amount in the post-exposure is usually 200 to 500 mJ / cm ² .

<Process (4)>
In step (4), the coating film obtained in step (3), specifically, the patterned coating film is heated (post-baking treatment) to obtain a cured film.
For the heating in the curing treatment of the coating film, for example, a heating device such as a hot plate or an oven can be used. The heating temperature in the curing treatment is usually 120 to 250 ° C. The heating time in the curing process varies depending on the type of the heating device, but is, for example, 5 to 30 minutes when the heat treatment is performed on a hot plate, and 30 to 100 minutes when the heat treatment is performed in the oven. At this time, a step baking method in which a heating process is performed twice or more can also be used.

  As described above, a cured film can be obtained. In one embodiment, for example, a target interlayer insulating film, a planarizing film, a microlens, and a cured film that is a spacer can be formed on a substrate.

[Display element]
The display element of the present invention has the above-described cured film of the present invention. The cured film is, for example, a thin film transistor (TFT) planarization film or an interlayer insulating film in a display element. The display element of the present invention is, for example, a liquid crystal display element or an organic EL display element.

  For example, in the liquid crystal display element, the cured film of the present invention is suitable as a protective film on the liquid crystal side of the colored pattern in the color filter (protective film for color filter) and a protective film for electrodes (protective film for electrodes). For example, in a liquid crystal display element, the resistance characteristics of the liquid crystal such as voltage holding characteristics may be deteriorated, but the deterioration can be prevented well by providing the cured film, and thus high reliability performance of the liquid crystal display element is obtained. be able to.

  Hereinafter, the present invention will be described more specifically based on examples. However, the present invention is not limited to the following examples. In the following description, “parts by mass” is described as “parts” unless otherwise specified.

<Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)>
For the polymer (A), Mw and Mn were measured by gel permeation chromatography (GPC) under the following conditions. The molecular weight distribution (Mw / Mn) was calculated from the obtained Mw and Mn.
Device: “GPC-101” (Showa Denko)
GPC column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined (manufactured by Shimadzu LLC)
Mobile phase: Tetrahydrofuran Column temperature: 40 ° C
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

(Polymer synthesis)
[Synthesis Example 1]
In a flask equipped with a condenser and a stirrer, 7 parts of 2,2′-azobis (2,4-dimethylvaleronitrile), 200 parts of propylene glycol monomethyl ether acetate, 13 parts of methacrylic acid, 40 parts of glycidyl methacrylate, α-methyl- After charging 10 parts of p-hydroxystyrene, 15 parts of N-cyclohexylmaleimide, 12 parts of tetrahydrofurfuryl methacrylate, 10 parts of n-lauryl methacrylate, and 3 parts of α-methylstyrene dimer as a molecular weight regulator, and after purging with nitrogen Gently started stirring. After raising the reaction solution to 60 ° C., this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-1). The copolymer (A-1) was deposited and precipitated using 900 parts of hexane with respect to the obtained polymer solution. The copolymer (A-1) is separated from the liquid in which the copolymer (A-1) is precipitated, and propylene glycol monomethyl ether acetate is added to the copolymer (A-1) to obtain a solid content concentration of 30% by mass. The polymer solution containing the copolymer (A-1) was obtained. The weight average molecular weight (Mw) of the copolymer (A-1) was 8000, the number average molecular weight (Mn) was 4700, and Mw / Mn was 1.7.

[Synthesis of radiation-sensitive compounds]
[Synthesis Example 2]
A synthesis scheme of Synthesis Example 2 is shown below.

冷却管と攪拌機を備えたフラスコにおいて、０．１８７ｇ（０．１ｍｏｌ）の６−アミノ−２−ナフトエ酸（東京化成工業社のＡ１９３８）を１００ｇのプロピレングリコールモノメチルエーテルアセテートに溶かし、５０ｇの水を加えた後、２３３．０ｇのクロロスルホン酸および３３５．７ｇの１，１，２，２−テトラクロロエタンと混合して２０℃で１週間撹拌し、水層を除去してカラム分離することで化合物（ｂ−１）を得た。

In a flask equipped with a condenser and a stirrer, 0.187 g (0.1 mol) of 6-amino-2-naphthoic acid (A1938 of Tokyo Chemical Industry Co., Ltd.) was dissolved in 100 g of propylene glycol monomethyl ether acetate, and 50 g of water was added. After addition, the compound was mixed with 233.0 g of chlorosulfonic acid and 335.7 g of 1,1,2,2-tetrachloroethane and stirred at 20 ° C. for 1 week, and the aqueous layer was removed and the column was separated. (B-1) was obtained.

The obtained compound (b-1) was stirred in 100 g of concentrated sulfuric acid at 40 ° C. for 72 hours, the obtained reaction solution was dropped into water, and the precipitate was filtered to obtain the compound (b-1 ′). Obtained.
0.347 g (0.1 mol) of compound (b-1 ′) is dispersed and dissolved in 150 g of water, 10 g of concentrated hydrochloric acid is added, and 23.5 g of 30% aqueous sodium nitrite solution is added at about 10 ° C. for 1 hour. The mixture was added dropwise to diazotize, and the mixture was further stirred at 0 to 5 ° C. for 1 hour. The pH of the reaction solution was adjusted to 8 to 10 with an aqueous sodium hydroxide solution, and 1 g of potassium iodide was added to dissolve the solution (hereinafter, this solution is referred to as “diazotized aqueous solution”).

  Next, 22.2 g of 35% sodium hydroxide aqueous solution was added to 58.8 g of sodium hypochlorite aqueous solution having an effective chlorine concentration of 13.2% and mixed uniformly. After dropwise addition for a period of time, excess sodium hydroxide was neutralized with concentrated hydrochloric acid, excess sodium hypochlorite was decomposed with sodium thiosulfate, sodium chloride was added to a concentration of 17.7%, and filtration was performed. 2.18 g of compound (b-1 ″) was obtained.

0.933 g (3.0 mmol) of the compound (b-1 ″) thus obtained was replaced with 1.49 g (3.5 mmol) of 4,4 ′-[1- [4- [1- (4-hydroxyphenyl)]. −1-methylethyl] phenyl] ethylidene] bisphenol and 20.9 g of propylene glycol monomethyl ether acetate and stirred at 40 ° C. After adding 2.09 g of water, 1.69 g of triethylamine was added dropwise and stirred for 60 minutes. did. Thereafter, 0.350 g of concentrated hydrochloric acid was added to the reaction solution, 50.0 g of water was added, the aqueous layer was removed, and the mixture was separated by a column to obtain compound (B-1). At this time, the yield was 0.6%.
¹ H NMR (400 MHz, DMSO-d6) = 12.0 (m, 2H), 9.3-9.1 (m, 1H), 8.6 (m, 2H), 8.3 (m, 2H) 7.5 (m, 2H), 7.3-7.2 (m, 4H), 7.1-6.7 (m, 14H), 2.0 (m, 3H), 1.6 (m , 6H)
ESI-MS found [M + H] ⁺ = 733, 993, 1286 (exact mass: 732, 992, 1285).

[Synthesis Example 3]
Instead of 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 1.07 g (3.5 mmol) of 1,1,1- Compound (B-2) was obtained by the procedure according to Synthesis Example 2 except that tris (4-hydroxyphenyl) ethane was used. At this time, the yield was 0.5%.
¹ H NMR (400 MHz, DMSO-d6) = 11.8 (m, 2H), 9.3-9.0 (m, 1H), 8.5 (m, 2H), 8.3 (m, 2H) 7.3-7.2 (m, 6H), 7.0-6.7 (m, 10H), 2.0 (m, 3H)
ESI-MS found [M + H] ⁺ = 599, 859, 1152 (exact mass: 598.1, 858.1, 1151.1).

[Synthesis Example 4]
Instead of 6-amino-2-naphthoic acid, 16.91 g of 6-hydroxy-2-naphthonitrile (H0995 of Tokyo Chemical Industry Co., Ltd.) was replaced with Synthesis of 2-Amino-2′-hydroxy-1,1- of US6380392B1. The procedure according to Synthesis Example 2 was used except that the compound reacted by the method described in the term “binaphthyl (NOBIN)” and Kenneth J. Brown et al., J. Org. Chem. 1985, 50, 4345-4349 was used. Compound (B-3) was obtained. At this time, the yield was 0.7%.
¹ H NMR (400 MHz, DMSO-d6) = 9.4-9.1 (m, 1H), 8.5 (m, 2H), 8.2 (m, 2H), 7.6 (m, 2H) , 7.3 (m, 2H), 7.2 (m, 2H), 7.1-6.6 (m, 14H), 1.9 (m, 3H), 1.5 (m, 6H)
ESI-MS found [M + H] ⁺ = 682 939, 1122 (exact mass: 681.2, 938.2, 1121.2).
A structure (bb) of the compound (B-3) is shown below.

[Synthesis Example 5]
Instead of 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 1.07 g (3.5 mmol) of 1,1,1- Compound (B-4) was obtained by the procedure according to Synthesis Example 4 except that tris (4-hydroxyphenyl) ethane was used. At this time, the yield was 0.5%.
¹ H NMR (400 MHz, DMSO-d6) = 9.4-9.2 (m, 1H), 8.5 (m, 2H), 8.1 (m, 2H), 7.3 (m, 4H) , 7.2 (m, 2H), 7.1-6.6 (m, 10H), 1.9 (m, 3H)
ESI-MS found [M + Na] ⁺ = 569, 826, 1099 (exact mass: 547, 804, 1077).

[Synthesis Example 6]
Instead of 6-amino-2-naphthoic acid, 67.5 g 2,3-dicyano-6-nitronaphthalene (D2027 from Tokyo Chemical Industry Co., Ltd.), 10 g nickel nanoparticles, 1.0 g sodium boron and 100 g water And the compound (B-5) was obtained by the procedure according to Synthesis Example 2 except that the compound obtained by stirring at room temperature for 3 hours was used. At this time, the yield was 0.4%.
¹ H NMR (400 MHz, DMSO-d6) = 9.5-9.1 (m, 1H), 8.7 (m, 2H), 8.3 (m, 2H), 7.6-7.2 ( m, 8H), 7.1-6.6 (m, 10H), 2.0 (m, 3H), 1.5 (m, 6H)
ESI-MS found [M + Na] ⁺ = 779, 1061, 1327 (exact mass: 757, 1039, 1305).
A structure (bb) of the compound (B-5) is shown below.

[Synthesis Example 7]
Instead of 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 1.07 g (3.5 mmol) of 1,1,1- Compound (B-6) was obtained by the procedure according to Synthesis Example 6 except that tris (4-hydroxyphenyl) ethane was used. At this time, the yield was 0.3%.
¹ H NMR (400 MHz, DMSO-d6) = 9.5-9.3 (m, 1H), 8.7 (m, 2H), 8.1 (m, 2H), 7.5 (m, 2H) , 7.3 (m, 4H), 7.1-6.6 (m, 8H), 2.0 (m, 3H)
ESI-MS found [M + H] ⁺ = 624,906, 1172 (exact mass: 623, 905, 1171).

(Preparation of radiation-sensitive composition)
(A) to (E) used for the preparation of radiation-sensitive compositions such as Examples are shown below.

<< Polymer (A) >>
A-1: Copolymer (A-1) obtained in Synthesis Example 1
A-2: KAYARAD CCR-1291H (manufactured by Nippon Kayaku Co., Ltd .; cresol novolac type epoxy acrylate resin, weight average molecular weight = 8000)
<< Compound (B) and Comparative Compound (B ') >>
B-1 to B-6: Compounds obtained in Synthesis Examples 2 to 7 B'-7: 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl ] Ethylidene] Condensate of bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) B′-8: 1,1,1-tris (4-hydroxy Phenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) condensate B′-9: 4,4 ′-[1- [4- [ 1- (4-Hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-4-sulfonic acid chloride (2.0 mol)
<Adhesion aid (C)>
C-1: 3-glycidoxypropyltrimethoxysilane
Shin-Etsu Chemical's KBM-403
<< Surfactant (D) >>
D-1: Silicone surfactant, “SH28PA” manufactured by Toray Dow Corning
<< Solvent (E) >>
E-1: Diethylene glycol ethyl methyl ether E-2: Propylene glycol methyl acetate E-3: Methyl 3-methoxypropionate

[Example 1]
Into the polymer solution containing the copolymer (A-1) having a solid content concentration of 30% by mass, 25 parts of the compound (B-1) based on 100 parts of the copolymer (A-1), 3-glycol 5 parts of Sidoxypropyltrimethoxysilane (“KBM-403” from Shin-Etsu Chemical Co., Ltd.) (C-1) and 1 part of a silicone surfactant (“SH28PA” from Toray Dow Corning) (D-1) After mixing, diethylene glycol ethyl methyl ether (E-1) was blended so that the solid content concentration was 18% by mass, and then filtered through a membrane filter having a pore size of 0.2 μm to obtain a radiation sensitive composition (S-1). Was prepared.

[Examples 2 to 12, Comparative Examples 1 to 4]
Except having used each component of the kind shown in following Table 1, it operated similarly to Example 1, and the radiation sensitive composition (S-2)-(S-12) of Examples 2-12 and Comparative Examples 1-4. ), (CS-1) to (CS-4) were prepared.

[Evaluation of radiation-sensitive composition]
The following evaluation was implemented using the radiation sensitive composition of an Example and a comparative example. The evaluation results are shown in Table 1.

[Evaluation of radiation sensitivity]
A radiation sensitive composition shown in Table 1 was applied on a silicon substrate using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3 μm. Subsequently, using an exposure machine (Canon's “MPA-600FA” (ghi line mixing)), the line width and the space width are both 10 μm through a mask having a line and space pattern. Then, radiation was irradiated with the exposure amount as a variable. Then, it developed with the piling method for 60 seconds at 23 degreeC with the tetramethylammonium hydroxide aqueous solution of a 2.38 mass% density | concentration. Next, running water was washed with ultrapure water for 1 minute and then dried to form a pattern. At this time, the exposure amount necessary for completely dissolving the coating film corresponding to the space pattern having a width of 10 μm was examined. In this case exposure value is less than 150mJ / cm ² AA, the value of the exposure amount in the case of 150~200mJ / cm ² BB, the value of the exposure amount was CC the case of more than 200 mJ / cm ^2.

[Resolution evaluation]
A radiation sensitive composition shown in Table 1 was applied on a silicon substrate using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3 μm. Subsequently, using an exposure machine (Canon's “MPA-600FA” (ghi line mixture)), the minimum line width for the coating film through a mask having a line-and-space pattern with the following line width. Irradiation was performed with an optimal exposure amount capable of forming the pattern. Then, it developed with the piling method for 60 seconds at 23 degreeC with the tetramethylammonium hydroxide aqueous solution of a 2.38 mass% density | concentration. Next, running water was washed with ultrapure water for 1 minute and then dried to form a pattern. At this time, the minimum line width at which the coating film corresponding to the space pattern was completely dissolved was examined. When the line width is less than 2 μm, AA, when the line width is 2 μm or more and less than 3 μm, BB, and when the line width is 3 μm or more, CC.

[Evaluation of coloration of cured film]
On the glass substrate, the radiation sensitive composition shown in Table 1 was applied using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3 μm. Then, it developed with the piling method for 60 seconds at 23 degreeC with the tetramethylammonium hydroxide aqueous solution of a 2.38 mass% density | concentration. Next, running water was washed with ultrapure water for 1 minute, and the film was post-exposed at an exposure amount of 300 mJ / cm ² without using a mask by using an exposure machine. Subsequently, it heated at 230 degreeC for 90 minutes, and obtained the evaluation film | membrane. A color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) was used for this evaluation film, and the stimulus value (Y) and chromaticity coordinate value (x, y) in the CIE color system were measured with a C light source and a 2-degree visual field. .

[Evaluation of pre-bake margin]
A pattern was formed in the same manner as in [Evaluation of radiation sensitivity] except that pre-baking was performed at 80 ° C. or 100 ° C. At this time, the exposure amount necessary for completely dissolving the coating film corresponding to the space pattern having a width of 10 μm was examined. When the cases where pre-baking was performed at 80 ° C. and 100 ° C. were compared, the case where the exposure rate change rate was less than 10% was AA, and the case where it exceeded 10% was defined as CC. Here, the exposure rate change rate is 100 (%) × {[exposure amount at 80 ° C. (mJ / cm ² )] − [exposure amount at 100 ° C. (mJ / cm ² )]} / [80 ° C. Exposure amount (mJ / cm ² )].

[Evaluation of voltage holding ratio]
A SiO ₂ film that prevents elution of sodium ions is formed on the surface, and a radiation sensitive composition shown in Table 1 is spun on a soda glass substrate on which an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape. After coating, pre-baking was performed for 2 minutes on a hot plate at 90 ° C. to form a coating film having a thickness of 3 μm. Next, the coating film was exposed at an exposure amount of 200 mJ / cm ² through a photomask using an exposure machine (“MPA-600FA” manufactured by Canon Inc. (ghi line mixing)). Then, it developed with the piling method for 60 seconds at 23 degreeC with the tetramethylammonium hydroxide aqueous solution of a 2.38 mass% density | concentration. Next, running water was washed with ultrapure water for 1 minute, and the film was post-exposed with an exposure amount of 300 mJ / cm ² without using a mask by using an exposure machine. Subsequently, it heated at 230 degreeC for 90 minutes, the coating film was hardened, and the cured film was formed.

The substrate on which the cured film is formed and the substrate on which the ITO electrode is simply deposited in a predetermined shape are bonded together with a sealing agent mixed with 1.8 mm glass beads, and then Merck liquid crystal (MLC6608) is injected. A liquid crystal cell was produced. Next, the liquid crystal cell was irradiated with 1000 mJ / cm ² using an ultra-high pressure mercury lamp and placed in a constant temperature layer at 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured using a liquid crystal voltage holding ratio measurement system (VHR-1A type, Measured by Toyo Technica). The applied voltage at this time was a square wave of 5.5 V, and the measurement frequency was 60 Hz. Here, the voltage holding ratio is a value obtained from (liquid crystal cell potential difference 16.7 milliseconds after the start of application / voltage immediately after application). If the voltage holding ratio of the liquid crystal cell is less than 90%, it means that the liquid crystal cell cannot hold the applied voltage at a predetermined level for a time of 16.7 milliseconds, and the liquid crystal cannot be sufficiently aligned. There is a risk of causing "burn-in".

  Evaluation of the voltage holding ratio of the liquid crystal cell is “AA” when the voltage holding ratio of the liquid crystal cell measured by the above-described method is 94% or more, and when the voltage holding ratio is 90% or more and less than 94%. Is “BB”, and the case where the voltage holding ratio is less than 90% is “CC”. If the evaluation of the voltage holding ratio of the liquid crystal cell is “AA” or “BB”, this liquid crystal cell can hold the applied voltage at a predetermined level and can sufficiently align the liquid crystal. There is little risk of “burn-in”. Therefore, the liquid crystal cell has good voltage holding characteristics. On the other hand, when the evaluation of the voltage holding ratio of the liquid crystal cell is “CC”, the voltage holding characteristics are poor as described above.

Claims (9)

An alkali-soluble polymer (A);
A radiation-sensitive composition containing a compound (B) having at least one structure (bb) selected from the structure represented by formula (b1) and the structure represented by formula (b2).

[In the formulas (b1) and (b2), X is an electron-attracting group or a halogen atom, and when there are a plurality of Xs, they may be the same or different, n1 is an integer of 0 to 3, and n2 is N2 is an integer of 0 to 2, n1 + n2 is 1 or more, n3 is an integer of 0 to 4, n4 is an integer of 0 to 1, n3 + n4 is 1 or more, and * is a bond . ]   The radiation-sensitive composition according to claim 1, wherein X in the formulas (b1) and (b2) is an electron withdrawing group.   The electron withdrawing group in the formulas (b1) and (b2) is a nitro group, a cyano group, a sulfo group, a carboxy group, a tosyl group, a mesyl group, a phenyl group, a trifluoromethylsulfonyl group, and a carbon number of 1 to The radiation-sensitive composition according to claim 1, which is at least one selected from 12 halogenated alkyl groups, and the halogen atom is at least one selected from a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. . The compound (B) is at least one selected from a compound represented by the formula (B1-3-1) and a compound represented by the formula (B1-4-1). The radiation-sensitive composition according to item 1.

[Q in Formula (B1-3-1) is each independently the structure (bb) or a hydrogen atom, and m1 to m3 are integers of 0 to 5, provided that at least one of m1, m2, and m3 Is an integer of 1 or more, and not all Q are hydrogen atoms.
Q in formula (B1-4-1) is each independently the structure (bb) or a hydrogen atom, and m4 to m6 are integers of 0 to 5, provided that at least one of m4, m5 and m6 is It is an integer of 1 or more, and all Qs are not hydrogen atoms. ]   The radiation sensitive composition of any one of Claims 1-4 which contain 5-100 mass parts of said compounds (B) with respect to 100 mass parts of said polymers (A). (1) The process of forming the coating film of the radiation sensitive composition of any one of Claims 1-5 on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) The manufacturing method of a cured film which has the process of developing the coating film after irradiation, and the process of obtaining the cured film by heating the coating film after (4) image development. A cured film containing a resin component and a decomposition product derived from compound (B) having at least one structure (bb) selected from the structure represented by formula (b1) and the structure represented by formula (b2) .

[In the formulas (b1) and (b2), X is an electron-attracting group or a halogen atom, and when there are a plurality of Xs, they may be the same or different, n1 is an integer of 0 to 3, and n2 is N2 is an integer of 0 to 2, n1 + n2 is 1 or more, n3 is an integer of 0 to 4, n4 is an integer of 0 to 1, n3 + n4 is 1 or more, and * is a bond . ]   A display element having the cured film according to claim 7. A compound (B) having at least one structure (bb) selected from the structure represented by the formula (b1) and the structure represented by the formula (b2).

[In the formulas (b1) and (b2), X is an electron-attracting group or a halogen atom, and when there are a plurality of Xs, they may be the same or different, n1 is an integer of 0 to 3, and n2 is N2 is an integer of 0 to 2, n1 + n2 is 1 or more, n3 is an integer of 0 to 4, n4 is an integer of 0 to 1, n3 + n4 is 1 or more, and * is a bond . ]