JP2013242540A - Radiation-sensitive resin composition, interlayer insulator film for display device and formation method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition capable of forming an insulator film such as an interlayer insulator film for a display element or the like, excellent in transparency, heat-resistance, hardness, etching resistance and low water absorption, having high sensitivity, and with a smaller change amount in film thickness at an unexposed portion, and to provide an interlayer insulator film for a display element formed from the radiation-sensitive resin composition, and a manufacturing method thereof.SOLUTION: The radiation-sensitive resin composition includes: [A] a polymer component including, in an identical or different polymer, a structural unit (I) derived from a cyclic olefin monomer having an acid-dissociative group, and a structural unit (II) different from the structural unit (I) and having a polymerizable group; and [B] a radiation-sensitive acid generating body including a radiation sensitive acid generator. The structural unit (I) of the polymer component [A] may include a structural unit expressed by a formula (1) below.

Description

  The present invention relates to a radiation-sensitive resin composition, an interlayer insulating film for display elements, and a method for forming the same.

  The display element is generally provided with a display element interlayer insulating film for the purpose of insulating between wirings arranged in layers. As the material for forming the interlayer insulating film for display elements, the number of steps for forming a pattern is small, and since the obtained interlayer insulating film for display elements requires high flatness, the radiation-sensitive resin composition is Widely used. As described above, the radiation-sensitive resin composition is required to have good sensitivity, and the interlayer insulating film for display elements is required to have excellent heat resistance and transparency in addition to the above flatness.

  As such a radiation sensitive resin composition, a composition containing a cross-linking agent, an acid generator and an alkali-soluble resin is known (see JP 2004-4669 A). The alkali-soluble resin has a protecting group (a group that is insoluble or hardly soluble in an alkaline aqueous solution and can be dissociated by the action of an acid). After the protective group is dissociated by exposure, the alkali aqueous resin is a developer. A resin that becomes soluble. In addition, a radiation-sensitive resin composition containing a resin having an acetal structure or ketal structure and an epoxy group and an acid generator has been proposed (see Japanese Patent Application Laid-Open No. 2004-264623).

  When an attempt is made to form an interlayer insulating film for a display element using the conventional radiation-sensitive resin composition, the amount of decrease in the film thickness of the unexposed part in the development process or the post-bake process is large. There is an inconvenience that flatness is impaired or a deviation from the designed film thickness occurs. Moreover, in order to avoid this inconvenience, it is necessary to strictly adjust the development time, which leads to inefficiency of the production process.

  On the other hand, a radiation sensitive resin composition containing a polymer having an acetal structure or a ketal structure and a bulky alicyclic hydrocarbon group has been proposed (see Japanese Patent Application Laid-Open No. 2007-127691). This radiation-sensitive resin composition is a resist material for semiconductors and forms an organic film that is scheduled to be removed by etching after pattern formation. On the other hand, since the interlayer insulating film for display elements is a so-called permanent film that is not scheduled to be removed by etching unlike the organic film, the display element has etching resistance, low water absorption, hardness, and the like. High reliability inside is also required.

JP 2004-4669 A JP 2004-264623 A JP 2007-127691 A

  The present invention has been made based on the above circumstances, and can form an insulating film such as an interlayer insulating film for a display element which is excellent in transparency, heat resistance, hardness, etching resistance and low water absorption. To provide a radiation-sensitive resin composition having good sensitivity and a small amount of change in film thickness of an unexposed portion, an interlayer insulating film for a display element formed from this radiation-sensitive resin composition, and a method for forming the same With the goal.

The invention made to solve the above problems is
[A] A structural unit (I) derived from a cyclic olefin monomer having an acid-dissociable group in the same or different polymer, and a structural unit having a polymerizable group and different from the structural unit (I) ( II) a polymer component (hereinafter also referred to as “[A] polymer component”), and [B] a radiation-sensitive resin composition containing a radiation-sensitive acid generator.

  In the radiation-sensitive resin composition, the [A] polymer component has a structural unit (I) containing a cyclic olefin skeleton in the polymer main chain, so that it has excellent heat resistance and hardly undergoes thermal discoloration even in a high-temperature process. An insulating film such as an interlayer insulating film for a display element having sufficient transparency can be formed.

  Since the radiation sensitive resin composition forms a cross-linked structure between the molecular chains by including the structural unit (II) in the polymer component [A], the amount of change in the film thickness of the unexposed portion can be suppressed. . Furthermore, the radiation-sensitive resin composition can form an insulating film such as an interlayer insulating film for a display element that has sufficient hardness due to the cross-linked structure and is excellent in etching resistance and heat resistance.

  [A] The structural unit (I) of the polymer component may include a structural unit represented by the following formula (1).

（式（１）中、Ｒ^１は、下記式（ａ）及び（ｂ）のいずれかで表される基である。ｎは、１又は２である。但し、ｎが２の場合、２つのＲ^１は同一でも異なっていてもよい。）

（式（ａ）中、Ｒ^２は、単結合又は炭素数１〜６のアルカンジイル基である。Ｒ^３及びＲ^４は、それぞれ独立して、水素原子、アルキル基、シクロアルキル基又はアリール基である。但し、上記アルキル基、シクロアルキル基及びアリール基が有する水素原子の一部又は全部は置換されていてもよい。また、Ｒ^３及びＲ^４が共に水素原子である場合はない。Ｒ^５は、アルキル基、シクロアルキル基、アリール基、アラルキル基又は−Ｍ（Ｒ^１０）_３で表される基である。Ｍは、Ｓｉ、Ｇｅ又はＳｎである。Ｒ^１０は、アルキル基である。但し、Ｒ^５のアルキル基、シクロアルキル基、アリール基及びアラルキル基、並びにＲ^１０のアルキル基が有する水素原子の一部又は全部は置換されていてもよい。Ｒ^３とＲ^５とは互いに結合して、Ｒ^３が結合している炭素原子及びＲ^５が結合している酸素原子と共に環状エーテル構造を形成していてもよい。
式（ｂ）中、Ｒ^６は、単結合又は炭素数１〜６のアルカンジイル基である。Ｒ^７は、アルキル基又はシクロアルキル基である。

(In the formula (1), R ¹ is a group represented by any of the following formulas (a) and (b). N is 1 or 2. However, when n is 2, R ¹ may be the same or different.)

(In Formula (a), R ² is a single bond or an alkanediyl group having 1 to 6 carbon atoms. R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. However, some or all of the hydrogen atoms of the alkyl group, cycloalkyl group and aryl group may be substituted, and R ³ and R ⁴ are not both hydrogen atoms. ⁵ is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a group represented by -M (R ¹⁰ ) _3. M is Si, Ge or Sn, and R ¹⁰ is an alkyl group. . However, the alkyl group of R ^5, cycloalkyl group, aryl group and aralkyl group, and each other good .R ³ and R ⁵ be a part or all of the hydrogen atoms have been substituted with an alkyl group R ¹⁰ Combine , May form a cyclic ether structure together with the oxygen atom to the carbon atom and R ⁵ R ³ is attached is attached.
In formula (b), R ⁶ is a single bond or an alkanediyl group having 1 to 6 carbon atoms. R ⁷ is an alkyl group or a cycloalkyl group.

  When the cyclic olefin skeleton is a norbornene skeleton represented by the formula (1), an insulating film such as an interlayer insulating film for a display element having a higher level and excellent heat resistance can be formed.

  [C] It is preferable to further contain a compound having two or more oxetane groups (hereinafter also referred to as “[C] compound”). Since the [C] compound contains two or more oxetane groups, the compatibility with the [A] polymer component having a norbornane skeleton is improved. Therefore, an insulating film such as an interlayer insulating film for display elements obtained from the radiation sensitive resin composition is excellent in transparency.

（式（２）中、Ｒ^１１は、炭素数１〜２０の有機基である。ｍは、２以上の整数である。複数のＲ^１２は、それぞれ独立して、水素原子又は炭素数１〜５のアルキル基である。 [C] The compound is preferably a compound represented by the following formula (2).

(In the formula ^{(2), R 11} is a is .m organic group having 1 to 20 carbon atoms, an integer of 2 or more. Plurality of ^{R 12} are each independently a hydrogen atom or a carbon number 1 to 5 alkyl groups.

  Since the compound [C] is a compound represented by the above formula (2), the compatibility with the polymer component [A] is improved. Therefore, the interlayer insulation for display elements obtained from the radiation-sensitive resin composition An insulating film such as a film is superior in transparency.

（式（２−１）及び（２−２）中、Ｒ^１２は、上記式（２）と同義である。） [C] The compound is preferably a compound represented by the following formula (2-1) or (2-2).

(In the formulas (2-1) and (2-2), R ¹² has the same meaning as the above formula (2).)

  [C] Since the compound is a compound represented by the above formula (2-1) or (2-2), the compatibility with the [A] polymer component is further improved. An insulating film such as an interlayer insulating film for display elements obtained from a product is further excellent in transparency.

  In the said radiation sensitive resin composition, it is preferable that content of the [C] compound with respect to 100 mass parts of [A] polymer components is 1 mass part or more and 100 mass parts or less. The said radiation sensitive resin composition can form insulating films, such as an interlayer insulation film for display elements, which has the further outstanding transparency, when content of a [C] compound is made into the said range.

  The radiation sensitive resin composition preferably further contains a [D] sensitizer. The said radiation sensitive resin composition can improve a sensitivity more by further containing a [D] sensitizer.

  The radiation sensitive resin composition is preferably used for forming an interlayer insulating film for a display element. Such an interlayer insulating film for a display element is excellent in transparency, heat resistance, hardness, etching resistance and low water absorption, has good sensitivity, and has a small amount of change in film thickness in the unexposed area.

  The interlayer insulation film for display elements of this invention is formed from the said radiation sensitive resin composition. This interlayer insulating film for display elements is excellent in transparency, heat resistance, hardness, etching resistance and low water absorption, has good sensitivity, and has a small amount of change in film thickness in the unexposed area.

The method for forming an interlayer insulating film for a display element according to the present invention includes:
Using the radiation sensitive resin composition, forming a coating film on the substrate,
Irradiating at least a part of the coating film with radiation,
A step of developing the coating film irradiated with the radiation; and a step of heating the developed coating film.

  According to the formation method, an interlayer insulating film for a display element having excellent heat resistance, hardly undergoing thermal discoloration even in a high temperature process, and having low water absorption, sufficient transparency, and hardness can be formed. In addition, since the amount of change in the film thickness of the unexposed portion in the development process and the heating process can be reduced, the production process margin can be improved as a result, and the yield can be improved. Furthermore, an interlayer insulating film for a display element having a fine and elaborate pattern can be easily formed by forming a pattern by an exposure process utilizing radiation sensitivity, a development process, and a heating process. Therefore, the formed interlayer insulation film for display elements can be used suitably for display elements, such as a liquid crystal display element and an organic EL display element.

  As described above, according to the present invention, the transparency, heat resistance, hardness, etching resistance, and low water absorption are excellent, the sensitivity is good, and the change in film thickness of the unexposed portion is small. Insulating film can be provided. In addition, since an insulating film such as a display element interlayer insulating film formed from the radiation-sensitive resin composition can reduce the change in film thickness, the production process margin can be improved as a result, and the yield can be improved. Furthermore, an interlayer insulating film for a display element having a fine and elaborate pattern can be easily formed by forming a pattern by an exposure process utilizing radiation sensitivity, a development process, and a heating process. Therefore, the formed interlayer insulation film for display elements can be used suitably for display elements, such as a liquid crystal display element and an organic EL display element.

<Radiation sensitive resin composition>
The radiation-sensitive resin composition of the present invention contains [A] a polymer component and [B] a radiation-sensitive acid generator as essential components, and the radiation-sensitive resin composition includes [C] ] And / or [D] a sensitizer. Furthermore, the said radiation sensitive resin composition may contain the other arbitrary component in the range which does not impair the effect of this invention. Hereinafter, each component will be described in detail.

<[A] Polymer component>
[A] The polymer component is a structural unit (I) derived from a cyclic olefin monomer having an acid dissociable group in the same or different polymers, and a structural unit (I) having a polymerizable group. Contains different structural units (II). Moreover, the [A] polymer component may have another structural unit in the range which does not impair the effect of this invention. In addition, the [A] polymer component may contain 2 or more types of each structural unit. Hereinafter, each of the structural units (I) and (II) will be described in detail.

[Structural unit (I)]
The structural unit (I) is derived from a cyclic olefin monomer having an acid dissociable group. The acid-dissociable group is a group that generates an acidic functional group composed of a carboxyl group or a phenolic hydroxyl group by the action of an acid generated by exposure to dissociate a protective group present in the polymer. .

  The cyclic olefin monomer is not particularly limited as long as it is a cyclic hydrocarbon compound having a carbon-carbon unsaturated bond, but the alicyclic monomer having a norbornene ring, the monocyclic olefin monomer Examples thereof include a monomer and a cyclic conjugated diene monomer.

  Among these, a structural unit derived from an alicyclic monomer having a norbornene ring represented by the above formula (1) is particularly desirable.

In the above formula (1), R ¹ is a group represented by any ^one of the above formulas (a) and (b). n is 1 or 2. When n is 2, two R ^{1 s} may be the same or different.

In the above formula (a), ^{R 2} is a single bond or alkanediyl group having 1 to 6 carbon atoms. R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. However, one part or all part of the hydrogen atom which the said alkyl group, a cycloalkyl group, and an aryl group have may be substituted. Moreover, there is no case where R ³ and R ⁴ are both hydrogen atoms. R ⁵ is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a group represented by —M (R ¹⁰ ) ₃ . M is Si, Ge, or Sn. R ¹⁰ is an alkyl group. However, some or all of the hydrogen atoms of the alkyl group, cycloalkyl group, aryl group and aralkyl group of R ^{5 and} the alkyl group of R ¹⁰ may be substituted. R ³ and R ⁵ may be bonded to each other to form a cyclic ether structure together with the carbon atom to which R ³ is bonded and the oxygen atom to which R ⁵ is bonded.

In formula (b), R ⁶ is a single bond or an alkanediyl group having 1 to 6 carbon atoms. R ⁷ is an alkyl group or a cycloalkyl group.

Examples of the alkanediyl group having 1 to 6 carbon atoms represented by R ² in the formula (a) include a methanediyl group, an ethanediyl group, a propanediyl group, and a butanediyl group.

R ² is preferably a single bond, a methanediyl group or an ethanediyl group, and more preferably a single bond.

Examples of the alkyl group represented by R ³ and R ⁴ include linear and branched alkyl groups having 1 to 30 carbon atoms. Examples of the linear and branched alkyl group having 1 to 30 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an n-octyl group. Group, linear alkyl group such as n-dodecyl group, n-octadecyl group, i-propyl group, i-butyl group, t-butyl group, neopentyl group, 2-hexyl group, 3-hexyl group, etc. Examples thereof include a branched alkyl group. Of these, a methyl group, an ethyl group, and an n-propyl group are preferable.

Examples of the cycloalkyl group represented by R ³ and R ⁴ include a cycloalkyl group having 3 to 20 carbon atoms. Moreover, this C3-C20 cycloalkyl group may be polycyclic. Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl, cyclooctyl, bornyl group, norbornyl group, adamantyl group and the like.

Examples of the aryl group represented by R ³ and R ⁴ include an aryl group having 6 to 14 carbon atoms. The aryl group having 6 to 14 carbon atoms may be a single ring, a structure in which single rings are connected, or a condensed ring. Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.

Examples of the substituent for the alkyl group, cycloalkyl group and aryl group represented by R ³ and R ⁴ include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, and a cycloalkyl group (for example, cyclopropyl). Group, cyclopentyl group, cyclohexyl group, cycloheptyl, cyclooctyl, bornyl group, norbornyl group, adamantyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propoxy group) , N-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and other C1-C20 alkoxy groups), acyl groups (for example, acetyl group, propionyl group, butyryl group, i- C2-C20 acyl group such as butyryl group), acylo Si group (for example, acetoxy group, ethylyloxy group, butyryloxy group, t-butyryloxy group, t-amylyloxy group and other C2-C10 acyloxy groups), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, C2-C20 alkoxycarbonyl group such as propoxycarbonyl group), haloalkyl group (for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group) , N-dodecyl group, n-tetradecyl group, n-octadecyl group and other linear alkyl groups, i-propyl group, i-butyl group, t-butyl group, neopentyl group, 2-hexyl group, 3-hexyl group Alkyl groups such as branched alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, A group in which part or all of hydrogen atoms of a cycloalkyl group such as a rubornyl group and an adamantyl group are substituted with a halogen atom), a hydroxyalkyl group (for example, a hydroxymethyl group) and the like.

Examples of the alkyl group, cycloalkyl group and aryl group represented by R ⁵ are the same as the groups in R ³ and R ⁴ . In addition, as said alkyl group, a C1-C6 alkyl group is preferable and a methyl group, an ethyl group, and n-propyl group are more preferable. As said cycloalkyl group, a C4-C8 cycloalkyl group is preferable and a cyclopentyl group and a cyclohexyl group are more preferable. Examples of the aralkyl group represented by R ⁵ include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group.

In the group represented by —M (R ¹⁰ ) ₃ of R ⁵ , examples of the alkyl group represented by R ¹⁰ include the same alkyl groups represented by R ³ and R ⁴ .

The cyclic ether structure that may be formed by combining R ³ and R ⁵ with each other is preferably a cyclic ether structure having 5 to 8 ring members, more preferably a tetrahydrofuran structure or a tetrahydropyran structure.

R ⁶ in the above formula (b) of R ¹ is exemplified by the same as R ² .

Examples of R ⁷ in the formula (b) for R ¹ are the same as those for R ³ and R ⁴ .

The above-mentioned R ^7, preferably an alkyl group having a hydrogen atom and 1 to 6 carbon atoms, more preferably a hydrogen atom.

  Examples of the structural unit (I) include structural units represented by the following formulas (1-1) to (1-10).

The structural units represented by the above formulas (1-1) to (1-10) are each 8- (1-ethoxyethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (1-ethoxybutoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (tetrahydropyranyloxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (tetrahydrofuranyloxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5- (1-ethoxyethoxycarbonyl) -2-norbornene, 5- (1-ethoxybutoxycarbonyl) -2-norbornene, 5- (1-ethoxycyclohexyloxycarbonyl)- It is a structural unit derived from 2-norbornene, 5- (tetrahydropyranyloxycarbonyl) -2-norbornene, and 5- (tetrahydrofuranyloxycarbonyl) -2-norbornene. Examples of the structural unit (I) further include a structural unit derived from 5- (1-methoxyethoxycarbonyl) -2-norbornene. In addition, these monomers may be used independently and may use 2 or more types together.

  [A] The content of the structural unit (I) in the polymer component is 10 mol% or more and 90 mol% or less, and 20 mol% or more and 60 mol% with respect to all the structural units in the [A] polymer component. The following is preferred. By making the content rate of structural unit (I) into the said specific range, a film thickness reduction amount can be suppressed more.

[Structural unit (II)]
[A] The polymer component further includes a structural unit (II) having a polymerizable group and different from the structural unit (I). This structural unit (II) is contained in at least one of a polymer having the structural unit (I) and a polymer not having the structural unit (I). [A] The polymer component further includes the structural unit (II) having a polymerizable group to form a crosslinked structure between the molecular chains, so that the amount of change in the film thickness of the unexposed portion can be suppressed. In addition, an insulating film such as an interlayer insulating film for a display element that has sufficient hardness and is excellent in etching resistance and heat resistance can be formed.

  Here, as a polymeric group, the group containing carbon-carbon double bonds, such as (meth) acryloyl, an epoxy group, etc. are mentioned, for example.

As [A] polymer component containing structural unit (I) and structural unit (II), for example, (i) It has both structural unit (I) and structural unit (II) in the same polymer. [A] When one type of polymer is present in the polymer component;
(Ii) Having one structural unit (I) in one polymer and another structural unit (II) in a different polymer, there are two types of polymers in the polymer component [A] If you do;
(Iii) one polymer having both the structural unit (I) and the structural unit (II), and the polymer different from the structural unit (I), and further different from these in the polymer Having structural unit (II) and [A] three kinds of polymers are present in the polymer component;
(Iv) In addition to the polymers of (i) to (iii) above, there may be mentioned the case where [A] the polymer component further contains one or more polymers.

  The structural unit (II) is not particularly limited as long as it has a polymerizable group and is a structural unit different from the structural unit (I), but includes an epoxy group-containing structural unit (II-1) and a (meth) acryloyl group-containing structure. Unit (II-2) is preferred. Here, the epoxy group is a concept including an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure). Below, an epoxy group containing structural unit and a (meth) acryloyl group containing structural unit are explained in full detail.

[Epoxy group-containing structural unit (II-1)]
The epoxy group-containing structural unit (II-1) is not particularly limited as long as it is a structural unit having an epoxy group in the structural unit. Examples of the epoxy group-containing monomer that gives such a structural unit (II-1) include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 3-methyl-3,4 acrylate. -Epoxybutyl, 3-ethyl-3,4-epoxybutyl methacrylate, 5,6-epoxyhexyl (meth) acrylate, 5-methyl-5,6-epoxyhexyl methacrylate, 5-ethyl-5-methacrylate 6-epoxyhexyl, 6,7-epoxyheptyl (meth) acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclo (meth) acrylate Hexylethyl, 3,4-epoxycyclohexylpropyl methacrylate, 3,4-epoxycyclomethacrylate Xylbutyl, 3,4-epoxycyclohexylhexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylethyl acrylate, 3,4-epoxycyclohexylpropyl acrylate Oxiranyl group-containing (meth) acrylic compounds such as 3,4-epoxycyclohexylbutyl acrylate, 3,4-epoxycyclohexylhexyl acrylate;
o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinyl Vinyl benzyl glycidyl ethers such as benzyl glycidyl ether;
vinyl phenyl glycidyl ethers such as o-vinyl phenyl glycidyl ether, m-vinyl phenyl glycidyl ether, p-vinyl phenyl glycidyl ether;
3-acryloyloxymethyloxetane, 3-acryloyloxymethyl-3-methyloxetane, 3-acryloyloxymethyl-3-ethyloxetane, 3-acryloyloxymethyl-3-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -3-phenyloxetane, 3-methacryloyloxy Methyl oxetane, 3-methacryloyloxymethyl-3-methyloxetane, 3-methacryloyloxymethyl-3-ethyloxetane, 3-methacryloyloxymethyl-3-phenyloxetane, 3- (2-methacryloyloxye) Oxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-phenyloxetane, 2 -Acryloyloxymethyloxetane, 2-acryloyloxymethyl-2-methyloxetane, 2-acryloyloxymethyl-2-ethyloxetane, 2-acryloyloxymethyl-2-phenyloxetane, 2- (2-acryloyloxyethyl) oxetane, 2- (2-acryloyloxyethyl) -2-ethyloxetane, 2- (2-acryloyloxyethyl) -2-ethyloxetane, 2- (2-acryloyloxyethyl) -2-phenyloxetane, 2-methacryloyloxymethyl Oh Cetane, 2-methacryloyloxymethyl-2-methyloxetane, 2-methacryloyloxymethyl-2-ethyloxetane, 2-methacryloyloxymethyl-2-phenyloxetane, 2- (2-methacryloyloxyethyl) oxetane, 2- (2 -Methacryloyloxyethyl) -2-ethyloxetane, 2- (2-methacryloyloxyethyl) -2-ethyloxetane, 2- (2-methacryloyloxyethyl) -2-phenyloxetane, and other oxetanyl group-containing (meth) acrylic compounds Compound;
Etc.

  Among the above epoxy group-containing monomers, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methacryloyloxymethyl-3-methyloxetane 3-methacryloyloxymethyl-3-ethyloxetane is preferable from the viewpoint of copolymerization reactivity with other monomers and developability of the radiation-sensitive resin composition. These monomers can be used alone or in combination of two or more.

[(Meth) acryloyl group-containing structural unit (II-2)]
The (meth) acryloyl group-containing structural unit (II-2) is not particularly limited as long as it is a structural unit having a (meth) acryloyloxy group as a polymerizable group.

  [A] As a method for introducing the structural unit (II-2) into the polymer in the polymer component, for example, a polymer of a monomer containing an unsaturated compound having at least one hydroxyl group in one molecule (hereinafter, And a method of reacting an unsaturated isocyanate compound with “[A1] polymer”.

  [A1] Monomers used for polymer synthesis include (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid dihydroxyalkyl ester, (meth) acrylic acid (6-hydroxyhexanoyloxy) alkyl ester, and the like. Is mentioned.

  Examples of the (meth) acrylic acid hydroxyalkyl ester include (meth) acrylic acid 2-hydroxyethyl ester, (meth) acrylic acid 3-hydroxypropyl ester, (meth) acrylic acid 4-hydroxybutyl ester, and the like. Examples of the (meth) acrylic acid dihydroxyalkyl ester include (meth) acrylic acid 2,3-dihydroxypropyl ester, (meth) acrylic acid 1,3-dihydroxypropyl ester, and (meth) acrylic acid 3,4-dihydroxybutyl ester. Examples include esters. Examples of the (meth) acrylic acid (6-hydroxyhexanoyloxy) alkyl ester include (meth) acrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester and (meth) acrylic acid 3- (6-hydroxyhexa). Noyloxy) propyl ester and the like.

  Among these monomers, from the viewpoint of copolymerization reactivity and reactivity with isocyanate compounds, acrylic acid 2-hydroxyethyl ester, acrylic acid 3-hydroxypropyl ester, acrylic acid 4-hydroxybutyl ester, methacrylic acid 2 -Hydroxyethyl ester, methacrylic acid 3-hydroxypropyl ester, methacrylic acid 4-hydroxybutyl ester, acrylic acid 2,3-dihydroxypropyl ester, methacrylic acid 2,3-dihydroxypropyl ester are preferred. These monomers can be used alone or in combination of two or more.

  The [A1] polymer obtained as described above may be used for the synthesis of the [A] polymer component as it is in the polymerization reaction solution, and after the [A1] polymer is once separated from the solution, [A] You may use for the synthesis | combination of a polymer component.

  Examples of the unsaturated isocyanate compound include an isocyanate group-containing derivative of (meth) acrylic acid. Examples of the unsaturated isocyanate compound include 2- (meth) acryloyloxyethyl isocyanate, 4- (meth) acryloyloxybutyl isocyanate, 2- (2-isocyanatoethoxy) ethyl (meth) acrylate, 1,1- (bis ( And (meth) acryloyloxymethyl) ethyl isocyanate. In addition, an unsaturated isocyanate compound can be used individually or in mixture of 2 or more types.

  Examples of commercially available unsaturated isocyanate compounds include Karenz AOI (manufactured by Showa Denko) as a commercial product of 2-acryloyloxyethyl isocyanate, Karenz MOI (manufactured by Showa Denko) as a commercial product of 2-methacryloyloxyethyl isocyanate, and methacrylic acid 2 As a commercially available product of-(2-isocyanatoethoxy) ethyl, Karenz MOI-EG (manufactured by Showa Denko), and as a commercial product of 1,1- (bisacryloyloxymethyl) ethyl isocyanate, Karenz BEI (manufactured by Showa Denko) and the like can be mentioned.

  Of these unsaturated isocyanate compounds, from the viewpoint of reactivity with the [A1] polymer, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 4-methacryloyloxybutyl isocyanate or methacrylic acid 2- (2- Isocyanatoethoxy) ethyl and 1,1- (bisacryloyloxymethyl) ethyl isocyanate are preferred.

  [A1] The reaction between the polymer and the unsaturated isocyanate compound is carried out in the presence of a suitable catalyst, if necessary, and preferably stirred in a solution of the polymer [A1] polymer containing a polymerization inhibitor at room temperature or under heating. However, it can be carried out by introducing an unsaturated isocyanate compound.

  Examples of the catalyst include di-n-butyltin (IV) dilaurate. Examples of the polymerization inhibitor include p-methoxyphenol.

  [A] As another method for introducing the structural unit (II-1) into the polymer in the polymer component, for example, a monomer polymer containing an unsaturated compound having at least one carboxyl group in one molecule (Hereinafter, also referred to as “[A2] polymer”) and a method of reacting a compound having a vinyl ether group and a (meth) acryloyloxy group.

  [A2] The method for synthesizing the polymer includes, for example, a method of polymerizing a carboxyl group-containing monomer from the viewpoint of easy material acquisition and synthesis.

  [A2] Examples of monomers used for polymer synthesis include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic acid monoester, itaconic acid monoester, and the like. It is done. Of these, (meth) acrylic acid is preferred.

  Examples of the compound having a vinyl ether group and a (meth) acryloyloxy group include a compound represented by the following formula (3).

In the above formula (3), R ¹³ is a hydrogen atom or a methyl group. R ¹⁴ is a divalent linking group. R ¹⁵ is a hydrogen atom or a monovalent organic group.

Examples of the divalent linking group represented by R ¹⁴ include a linear, branched or cyclic alkylene group having 2 to 18 carbon atoms, an alkoxyalkylene group having 2 to 20 carbon atoms, and 2 to 8 carbon atoms. A halogenated alkylene group, a polyethylene glycol skeleton excluding a terminal hydroxyl group, a polypropylene glycol skeleton excluding a terminal hydroxyl group, a polybutylene glycol skeleton excluding a terminal hydroxyl group, and an aryl group. Examples of the monovalent organic group represented by R ¹⁵ include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms and a substituted aromatic group having 6 to 11 carbon atoms. .

  Examples of the compound having a vinyl ether group and a (meth) acryloyloxy group represented by the formula (3) include 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, and (meth) acrylic acid. 1-methyl-2-vinyloxyethyl, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 1-methyl-3-vinyloxypropyl (meth) acrylate, (meth) acrylic acid 1- Vinyloxymethylpropyl, 2-methyl-3-vinyloxypropyl (meth) acrylate, 1,1-dimethyl-2-vinyloxyethyl (meth) acrylate, 3-vinyloxybutyl (meth) acrylate, (meth) acrylic acid 1 -Methyl-2-vinyloxypropyl, 2-vinyloxybutyl (meth) acrylate, ( T) 4-vinyloxycyclohexyl acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, 3-vinyloxymethylcyclohexylmethyl (meth) acrylate, (meth) 2-vinyloxymethylcyclohexylmethyl acrylate, p-vinyloxymethylphenylmethyl (meth) acrylate, m-vinyloxymethylphenylmethyl (meth) acrylate, o-vinyloxymethylphenylmethyl (meth) acrylate, ( 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxy) propyl (meth) acrylate, 2- (meth) acrylic acid 2- ( Vinyloxyethoxy) isopropyl, (meth) acryl 2- (vinyloxyisopropoxy) propyl acid, 2- (vinyloxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyl) (meth) acrylate Loxyethoxyisopropoxy) ethyl, 2- (vinyloxyisopropoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxy) (meth) acrylate Ethoxyethoxy) propyl, (meth) acrylic acid 2- (vinyloxyethoxyisopropoxy) propyl, (meth) acrylic acid 2- (vinyloxyisopropoxyethoxy) propyl, (meth) acrylic acid 2- (vinyloxyisopropoxyiso) Propoxy) propyl, (meth) acrylic acid 2- (Vinyloxyethoxyethoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyethoxyisopropoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyisopropoxyethoxy) isopropyl, (meth) acrylic acid 2- (vinyloxy) Isopropoxyisopropoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropeno) Xyloxy) ethyl, 2- (isopropenoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxy) (meth) acrylate Ethoxye Kishietokishi) ethyl, (meth) Polyethylene glycol monovinyl ether acrylate, and (meth) acrylic acid polypropylene glycol monovinyl ether. In addition, the compound which has these vinyl ether groups and (meth) acryloyloxy group can be used individually or in mixture of 2 or more types.

  Of these compounds having a vinyl ether group and a (meth) acryloyloxy group, a compound represented by the above formula (3) is preferable, and 2- (vinyloxyethoxy) ethyl (meth) acrylate is more preferable. As commercially available products of 2- (vinyloxyethoxy) ethyl (meth) acrylate, for example, VEEA as 2- (vinyloxyethoxy) ethyl acrylate, VEEM as 2- (vinyloxyethoxy) ethyl methacrylate ( As mentioned above, the product made from Nippon Shokubai etc. is mentioned.

  [A2] The addition reaction between the polymer and the compound having a vinyl ether group and a (meth) acryloyloxy group is not particularly limited, and can be carried out by adding it to the reaction system. In the above addition reaction, since the [A2] polymer itself becomes a catalyst, the reaction can be carried out without a catalyst, but a catalyst can also be used in combination.

  [A] As another method for introducing the structural unit (II-2) into the polymer in the polymer component, for example, using the polyfunctional (meth) acrylate as a monomer, the structural unit (I) or the like The method of copolymerizing with the monomer to give is mentioned.

  Examples of polyfunctional (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol Cyclodecanediyldimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanate Nurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene Oxide-modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentylglycol di (meth) acrylate, bisphenol A diglycidyl ether both-end (meth) acrylic acid adduct, 1,4-butane Diol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone modified Pentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide Examples include modified hydrogenated bisphenol A di (meth) acrylate, propylene oxide modified hydrogenated bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol F di (meth) acrylate, and (meth) acrylate of phenol novolac polyglycidyl ether. These monomers can be used alone or in combination of two or more.

  Examples of commercially available products of polyfunctional (meth) acrylate include SA1002 (Mitsubishi Chemical), Biscoat 195, 230, 260, 215, 310, 214HP, 295, 300, 360, GPT, 400, 700, 540, 3000, 3700 (made by Osaka Organic Chemical Industry), Kayarad R-526, HDDA, NPGDA, TPGDA, MANDA, R-551, R-712, R-604, R -684, PET-30, GPO-303, TMPTA, THE-330, DPHA, DPHA-2H, DPHA-2C, DPHA-2I, D-310, D-330, DPCA-20, DPCA-30, DPCA-60 , DPCA-120, DN-0075, DN-2475, T-1420, T-2020, T-2040 TPA-320, TPA-330, RP-1040, RP-2040, R-011, R-300, R-205 (above, manufactured by Nippon Kayaku), Aronix M-210, M-220, M-233 M-240, M-215, M-305, M-309, M-310, M-315, M-315, M-325, M-400, M-6200, M-6400 (Above, manufactured by Toagosei), light acrylate BP-4EA, BP-4PA, BP-2EA, BP-2PA, DCP-A (above, manufactured by Kyoeisha Chemical), New Frontier BPE-4, BR-42M, GX-8345 (above, manufactured by Daiichi Kogyo Seiyaku), ASF-400 (manufactured by Nippon Steel Chemical), lipoxy SP-1506, SP-1507, SP-1509, SP-4010, SP-4060, V-40 -77, (manufactured by Showa Kobunshi), NK ester A-BPE-4 (Shin-Nakamura Chemical Co., Ltd.).

  Of these polyfunctional (meth) acrylates, compounds having two or more (meth) acryloyloxy groups in the molecule and compounds having three or more (meth) acryloyloxy groups in the molecule are preferred. As a compound having two or more (meth) acryloyloxy groups in the molecule, diethylene glycol di (meth) acrylate is more preferable. Examples of the compound having 3 or more (meth) acryloyloxy groups in the molecule include tri (meth) acrylate compounds, tetra (meth) acrylate compounds, penta (meth) acrylate compounds, hexa (meth) acrylate compounds, and the like. . Among these compounds having three or more (meth) acryloyloxy groups, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (Meth) acrylate and ditrimethylolpropane tetra (meth) acrylate are preferred.

  The structural unit (II) preferably has two or more (meth) acryloyloxy groups. The structural unit (II) has two or more (meth) acryloyloxy groups, and in addition to better sensitivity and storage stability, the amount of change in the film thickness of the unexposed area with respect to the development time can be further suppressed. The shape stability of the hole can be further improved. In addition, it is possible to form an insulating film such as an interlayer insulating film for a display element having excellent light resistance and heat resistance.

  [A] The content of the structural unit (II) in the polymer component is such that when the structural unit (I) and the structural unit (II) are contained in the same polymer, [A] the entire structure in the polymer component 1 mol% or more and 60 mol% or less are preferable with respect to the unit, 5 mol% or more and 55 mol% or less are more preferable, and 10 mol% or more and 55 mol% or less are more preferable.

  On the other hand, when the structural unit (I) is included in one polymer and the structural unit (II) is included in another polymer, the structural unit (II) included in the polymer including the structural unit (II) The content is preferably 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 70% by mass or less, based on the monomer charge ratio with respect to all the structural units in the polymer including the structural unit (II). Preferably, 35 mass% or more and 65 mass% or less are more preferable. The content of the structural unit (II) is the total content of all the structural units including a polymerizable group. For example, the polymer includes both the structural unit (II-1) and the structural unit (II-2). When it has, it becomes the total content rate of both.

[Other structural units]
[A] The polymer component may contain other structural units other than the structural unit (I) and the structural unit (II) as long as the effects of the present invention are not impaired.

  Examples of other structural units include those derived from a cyclic olefin monomer having no acid dissociable group. Examples of such a structural unit include structural units represented by the following formulas (X-1) to (X-12).

  Examples of other structural unit-providing monomers include (meth) acrylic acid, (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid aryl ester, and (meth) acrylic acid aralkyl. Examples include esters, unsaturated dicarboxylic acid dialkyl esters, vinyl aromatic compounds, conjugated diene compounds, and other unsaturated compounds.

Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic sec. -Butyl, (meth) acrylic acid t-butyl etc. are mentioned. Examples of the (meth) acrylic acid cycloalkyl ester include cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [5.2.1.0 ^2,6 ] decane- (meth) acrylate. Examples include 8-yl, 2- (tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxy) ethyl (meth) acrylate, and isobornyl (meth) acrylate. Examples of the (meth) acrylic acid aryl ester include phenyl acrylate. Examples of (meth) acrylic acid aralkyl esters include benzyl (meth) acrylate. Examples of the unsaturated dicarboxylic acid dialkyl ester include diethyl maleate and diethyl fumarate. Examples of the vinyl aromatic compound include styrene and α-methylstyrene. Examples of the conjugated diene compound include 1,3-butadiene and isoprene. Examples of other unsaturated compounds include N-cyclohexylmaleimide, N-phenylmaleimide, acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide. These monomers can be used alone or in combination of two or more.

Among these monomers, from the viewpoint of copolymerization reactivity, (meth) acrylic acid, methyl (meth) acrylate, n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, tricyclomethacrylate [ 5.2.1.0 ^2,6 ] decan-8-yl, styrene, p-methoxystyrene, 1,3-butadiene, 1-n-butoxyethyl (meth) acrylate, and N-cyclohexylmaleimide are preferred.

  The radiation sensitive resin composition has a pattern forming ability because the structural unit (I) of the polymer component [A] has an acid dissociable group, but in addition to the structural unit (I), the structure Other structural units such as the unit (II) may have an acid dissociable group. Here, the acid-dissociable group means a group that is dissociated by the action of an acid generated from the radiation-sensitive acid generator [B] upon exposure in the radiation-sensitive resin composition to generate a polar group such as a carboxy group. I mean.

  Examples of the monomer that gives other structural unit having an acid dissociable group include 1-n-alkoxyalkyl (meth) acrylate, t-butyl (meth) acrylate, 1-alkyl-cycloalkyl ester, and the like. A monomer containing an acid-dissociable group having a monocyclic alicyclic group and a monomer containing an acid-dissociable group having a polycyclic alicyclic group such as 2-alkyl-2-dicycloalkyl ester Etc.

[A] The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer component is preferably 2.0 × 10 ³ or more and 1.0 × 10 ⁵ or less, more preferably 5.0. × 10 ³ or more and 5.0 × 10 ⁴ or less. [A] By making Mw of a polymer component into the said specific range, the sensitivity and alkali developability of the said radiation sensitive resin composition can be improved.

[A] The number average molecular weight (Mn) in terms of polystyrene by GPC of the polymer component is preferably 2.0 × 10 ³ or more and 1.0 × 10 ⁵ or less, more preferably 5.0 × 10 ³ or more and 5.0. × 10 ⁴ or less. [A] By setting Mn of the polymer component in the specific range, the curing reactivity at the time of curing of the coating film of the radiation sensitive resin composition can be improved.

  [A] The molecular weight distribution (Mw / Mn) of the polymer component is preferably 3.0 or less, more preferably 2.6 or less. [A] By setting Mw / Mn of the polymer component to 3.0 or less, the developability of an insulating film such as an interlayer insulating film for a display element obtained can be improved.

In addition, Mw and Mn of this specification were measured by GPC under the following conditions.
Apparatus: GPC-101 (made by Showa Denko)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined 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

<[A] Polymer component synthesis method>
[A] The polymer component can be prepared by radical copolymerization of monomers giving the above structural units. For example, when synthesizing the polymer component [A] containing both the structural unit (I) and the structural unit (II) in the same polymer molecule, the monomer and the structural unit (II) that give the structural unit (I) And a monomer containing a monomer to give a copolymer). On the other hand, when the [A] polymer component having the structural unit (I) in one polymer and the structural unit (II) in a different polymer is prepared, the single unit that gives the structural unit (I) is prepared. A polymer solution containing a monomer is radically polymerized to obtain a polymer having the structural unit (I), and a polymerizable solution containing a monomer that gives the structural unit (II) is separately radically polymerized to form a structural unit ( The polymer having (II) is obtained, and finally both are mixed to form the [A] polymer component.

  [A] Examples of the solvent used in the polymerization reaction of the polymer component include the solvents exemplified in the section of preparation of the radiation-sensitive resin composition described later.

  As the polymerization initiator used in the polymerization reaction, those generally known as radical polymerization initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- ( 2,4-Dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), azo compounds such as 2,2′-azobis (methyl 2-methylpropionate); benzoyl Organic peroxides such as peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane; hydrogen peroxide and the like.

  [A] In the polymerization reaction of the polymer in the polymer component, a molecular weight modifier may be used to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and thioglycolic acid; Xanthogens such as xanthogen sulfide and diisopropylxanthogen disulfide; terpinolene, α-methylstyrene dimer and the like.

<[B] Radiation sensitive acid generator>
[B] The radiation-sensitive acid generator is a compound that generates an acid upon irradiation with radiation. As the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used. When the radiation-sensitive resin composition contains the [B] radiation-sensitive acid generator, the radiation-sensitive resin composition can exhibit radiation-sensitive characteristics and have good sensitivity. [B] The content of the radiation-sensitive acid generator in the radiation-sensitive resin composition is a form of an acid generator (hereinafter also referred to as “[B] acid generator” as appropriate) as a compound as described later. However, it may be in the form of [A] acid generating groups incorporated as part of the polymer component or other polymer, or both forms.

  [B] Examples of the acid generator include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds. In addition, each of these [B] acid generators can be used individually or in combination of 2 or more types.

[Oxime sulfonate compound]
Examples of the oxime sulfonate compound include a compound containing an oxime sulfonate group represented by the following formula (4).

In said formula (4), R <^16> is a linear or branched alkyl group, a cycloalkyl group, or an aryl group. However, in these groups, some or all of the hydrogen atoms may be substituted.

The linear or branched alkyl group represented by R ¹⁶ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The linear or branched alkyl group having 1 to 10 carbon atoms may be substituted. Examples of the substituent include an alkoxy group having 1 to 10 carbon atoms and 7,7-dimethyl-2-oxonorbornyl. And an alicyclic group containing a bridged alicyclic group such as a group. A preferred alicyclic group is a bicycloalkyl group. The aryl group represented by R ^B1 is preferably an aryl group having 6 to 11 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group may be substituted, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

  Examples of the compound containing an oxime sulfonate group represented by the above formula (4) include an oxime sulfonate compound represented by the following formula (5).

In said formula (5), R < ¹⁶ > is synonymous with said formula (4). X is an alkyl group, an alkoxy group, or a halogen atom. r is an integer of 0-3. However, when there are a plurality of Xs, the plurality of Xs may be the same or different.

  The alkyl group that can be represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom represented by X is preferably a chlorine atom or a fluorine atom. r is preferably 0 or 1. In the above formula (5), a compound in which r is 1, X is a methyl group, and the substitution position of X is ortho is preferable.

  Examples of the oxime sulfonate compound represented by the above (5) include compounds represented by the following formulas (5-1) to (5-5).

  The compounds (5-1) to (5-5) are respectively represented by (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino-5H). -Thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-p-toluenesulfonyloxyimino-5H -Thiophen-2-ylidene)-(2-methylphenyl) acetonitrile and (5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile, which are commercially available.

[Onium salt]
Examples of the onium salt include diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, and tetrahydrothiophenium salt.

  Examples of the diphenyliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium. Butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarsenate Bis (4-t-butylphenyl) iodonium trifluorome Sulphonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate, bis (4-t-butylphenyl) iodonium camphorsulfonic acid, etc. .

  Examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, triphenylsulfonium. And butyl tris (2,6-difluorophenyl) borate.

  Examples of the sulfonium salt include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts and the like.

  Examples of the alkylsulfonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (Benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate and the like can be mentioned.

  Examples of the benzylsulfonium salt include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenyl. Methylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenyl Examples include methylsulfonium hexafluorophosphate.

  Examples of the dibenzylsulfonium salt include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzylsulfonium hexafluoroantimonate, and dibenzyl-4-methoxyphenylsulfonium. Hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl- Examples include 4-hydroxyphenylsulfonium hexafluorophosphate.

  Examples of substituted benzylsulfonium salts include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and p-chlorobenzyl-4-hydroxyphenylmethyl. Sulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3- Examples include chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate.

  Examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, and 3- (p-methoxybenzyl). ) Benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, and the like.

  Examples of tetrahydrothiophenium salts include 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethane. Sulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1,1 , 2,2-Tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (5-t-butoxycarbonyloxybicyclo) [2.2.1] Heptan-2-yl) -1,1, , 2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl ) -1,1,2,2-tetrafluoroethanesulfonate and the like.

[N-sulfonyloxyimide compound]
Examples of the N-sulfonyloxyimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethyl). Phenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) Phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) Phenylmaleimide, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) ) Diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1]. ] Hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (nonafluoro) Butanesulfonyloxy) bicyclo [ 2.1] hept-5-ene-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (Camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2. 1] Hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-Methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenol) Nylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4 -Fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane -5,6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy 2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (2-trifluoromethyl) Phenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5 6-oxy-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide, N- (camphorsulfonyloxy) naphthyl dicarboxylimide, N- (4-methylphenylsulfonyloxy) naphthyl di Carboxylimide, N- (phenylsulfonyloxy) naphthyl dicarboxyl N- (2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide, N- (pentafluoroethylsulfonyloxy) naphthyl dicarboxylimide, N- (Heptafluoropropylsulfonyloxy) naphthyl dicarboxylimide, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxylimide, N- (ethylsulfonyloxy) naphthyl dicarboxylimide, N- (propylsulfonyloxy) naphthyl dicarboxylimide, N- (butylsulfonyloxy) naphthyl dicarboxylimide, N- (pentylsulfonyloxy) naphthyl dicarboxylimide, N- (hexylsulfonyloxy) naphth Tildicarboxylimide, N- (heptylsulfonyloxy) naphthyl dicarboxylimide, N- (octylsulfonyloxy) naphthyl dicarboxylimide, N- (nonylsulfonyloxy) naphthyl dicarboxylimide, etc.

[Halogen-containing compounds]
Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds.

[Diazomethane compounds]
Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, and bis (2,4-xylylsulfonyl) diazomethane. Bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane Etc.

[Sulfone compound]
Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, diaryldisulfone compounds, and the like.

[Sulfonic acid ester compounds]
Examples of the sulfonate compound include alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, and imino sulfonate.

[Carboxylic ester compounds]
Examples of the carboxylic acid ester compound include carboxylic acid o-nitrobenzyl ester.

  [B] The acid generator is preferably an oxime sulfonate compound, an onium salt, or a sulfonate compound from the viewpoint of sensitivity and solubility. As the oxime sulfonate compound, a compound represented by the above formula (4) is preferable, a compound represented by the above formula (5) is more preferable, and is represented by the above formula (5-1), which is available as a commercial product. Are particularly preferred. As the onium salt, tetrahydrothiophenium salt and benzylsulfonium salt are preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate are preferable. More preferred. As the sulfonic acid ester compound, a haloalkylsulfonic acid ester is preferable, and N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester is more preferable.

  The content of the [B] radiation sensitive acid generator in the radiation sensitive resin composition is as follows: [B] When the radiation sensitive acid generator is a [B] acid generator, [A] the polymer component 100 Preferably they are 0.1 mass part or more and 10 mass parts or less with respect to a mass part, More preferably, they are 1 mass part or more and 5 mass parts or less. [B] By setting the content of the radiation-sensitive acid generator within the specific range, the sensitivity of the radiation-sensitive resin composition is optimized, and the interlayer insulation film for display elements having high surface hardness while maintaining transparency Etc. can be formed.

<[C] Compound>
The radiation-sensitive resin composition preferably further contains a compound having two or more [C] oxetane groups as a suitable component. Since the [C] compound is a compound having two or more oxetane groups, the compatibility with the [A] polymer component having a norbornane skeleton is good. Therefore, an insulating film such as an interlayer insulating film for display elements obtained from the radiation sensitive resin composition is excellent in transparency. Here, the oxetane group is referred to as a group containing an oxetane ring structure.

[C] Although it will not specifically limit if it is a compound which has two or more oxetane groups as a compound, It is preferable that it is a compound represented by the said Formula (2). In the above formula ^{(2), R 11} is an organic group having 1 to 20 carbon atoms. m is an integer of 2 or more. Several R < ¹² > is a hydrogen atom or a C1-C5 alkyl group each independently.

Examples of the organic group having 1 to 20 carbon atoms represented by R ¹¹ include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and these groups. Examples include a group formed by combining at least one selected from at least one selected from the group consisting of —O—, —CO—, and —COO—. Of these, R ¹¹ is preferably a group containing —O—.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ¹² include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a t-butyl group. Of these, a methyl group and an ethyl group are preferable, and an ethyl group is more preferable.

  As the compound [C], a compound represented by the above formula (2-1) or (2-2) is more preferable.

  [C] Specific examples of the compound include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, di [1-ethyl- (3-oxetanyl) methyl] ether (also known as bis (3 -Ethyl-3-oxetanylmethyl) ether), 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 '-(1,3- (2-methylenyl) propanediylbis (oxymethylene) ) Bis- (3-ethyloxetane), 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, Ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, trie Lenglycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethyleneglycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, tri Methylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, penta Erythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol Ruhexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipenta Erythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bis Phenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, etc. Is mentioned.

  Among these specific examples, di [1-ethyl- (3-oxetanyl) methyl] ether represented by the above formula (2-1), 1,4-bis [ (3-Ethyl-3-oxetanylmethoxy) methyl] benzene is preferred. In addition, a [C] compound can be used individually by 1 type or in combination of 2 or more types.

  As content of the [C] compound in the said radiation sensitive resin composition, it is preferable that it is 1 mass part or more and 100 mass parts or less with respect to 100 mass parts of [A] polymer components, and is 1 mass part or more and 50 mass parts. More preferably, it is 1 part by mass or more and 25 parts by mass or less. When content of the said [C] compound is less than 1 mass part with respect to 100 mass parts of [A] polymer components, the heat resistance of a cured film and transparency improvement effect by a [C] compound are fully acquired. In the case of 100 parts by mass or more, sufficient sensitivity may not be obtained.

<[D] sensitizer>
It is preferable that the said radiation sensitive resin composition further contains a [D] sensitizer as a suitable component. The sensitivity of the said radiation sensitive resin composition can be improved more because the said radiation sensitive resin composition further contains a [D] sensitizer. [D] The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The [D] sensitizer in an electronically excited state comes into contact with the [B] radiation-sensitive acid generator to cause actions such as electron transfer, energy transfer, and heat generation, and thereby [B] radiation-sensitive acid. The generator undergoes a chemical change and decomposes to produce an acid.

  [D] Examples of the sensitizer include compounds belonging to the following compounds and having an absorption wavelength in the region of 350 nm to 450 nm.

[D] Examples of the sensitizer include pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene, and the like. Polynuclear aromatics of
Xanthenes such as fluorescein, eosin, erythrosine, rhodamine B, rose bengal;
Xanthones such as xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone, isopropylthioxanthone;
Cyanines such as thiacarbocyanine, oxacarbocyanine;
Merocyanines such as merocyanine and carbomerocyanine;
Rhodocyanines;
Oxonols;
Thiazines such as thionine, methylene blue and toluidine blue;
Acridines such as acridine orange, chloroflavin, acriflavine;
Acridones such as acridone, 10-butyl-2-chloroacridone;
Anthraquinones such as anthraquinone;
Squariums such as squalium;
Styryls;
Base styryls such as 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole;
7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [l] benzopyrano [6,7,8-ij] quinolidine- Coumarins, such as 11-non, etc. are mentioned.

  Among these [D] sensitizers, polycyclic aromatics, acridones, styryls, base styryls, coumarins, and xanthones are preferable, and xanthones are more preferable. Of the xanthones, diethylthioxanthone and isopropylthioxanthone are particularly preferred.

  As content of the [D] sensitizer in the said radiation sensitive resin composition, 0.1 mass part or more and 10 mass parts or less are preferable with respect to 100 mass parts of [A] polymer components, 0.5 mass part More preferred is 5 parts by mass or less. [D] By making content of a sensitizer into the said specific range, a sensitivity can be improved more.

<Other optional components>
The said radiation sensitive resin composition is required in the range which does not impair the effect of this invention other than [A] polymer component, [B] radiation sensitive acid generator, [C] compound, and [D] sensitizer. Depending on the above, other optional components such as a basic compound, a surfactant, an adhesion assistant, and a compound having a hindered phenol structure may be contained. These other optional components may be used alone or in combination of two or more. Hereinafter, each component will be described in detail.

<Basic compound>
The basic compound can be arbitrarily selected from those used in chemically amplified resists, and examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and carboxylic acid quaternary ammonium salts. Can be mentioned. By including a basic compound in the radiation-sensitive resin composition, the diffusion length of the acid generated from the [B] radiation-sensitive acid generator by exposure can be appropriately controlled, and the pattern developability can be improved. .

  Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , Dicyclohexylmethylamine and the like.

  Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.

  Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,8-diazabicyclo [5,3,0] -7 Undecene etc. are mentioned.

  Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.

  Examples of the carboxylic acid quaternary ammonium salt include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

  Of these basic compounds, heterocyclic amines are preferable, and 4-dimethylaminopyridine, 4-methylimidazole, and 1,5-diazabicyclo [4,3,0] -5-nonene are more preferable.

  As content of the basic compound in the said radiation sensitive resin composition, 0.001 mass part or more and 1 mass part or less are preferable with respect to 100 mass parts of [A] polymer component, and 0.005 mass part or more and 0.00. 2 parts by mass or less is more preferable. Pattern developability improves more by making content of a basic compound into the said specific range.

<Surfactant>
The surfactant can further improve the film-forming property of the radiation-sensitive resin composition. Examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant. When the radiation-sensitive resin composition contains a surfactant, the surface smoothness of the coating film can be improved, and the film thickness uniformity of the interlayer insulating film for display elements formed as a result can be further improved.

  As the fluorosurfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group at at least one of the terminal, main chain and side chain is preferable. For example, 1,1,2,2-tetrafluoro n- Octyl (1,1,2,2-tetrafluoro n-propyl) ether, 1,1,2,2-tetrafluoro n-octyl (n-hexyl) ether, hexaethylene glycol di (1,1,2,2 , 3,3-hexafluoro n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro n-butyl) ether, hexapropylene glycol di (1,1,2,2,3,3) -Hexafluoro n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro n-butyl) ether, Sodium fluoro n-dodecanesulfonate, 1,1,2,2,3,3-hexafluoro n-decane, 1,1,2,2,3,3,9,9,10,10-decafluoro n- Dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkylbetaine, fluoroalkylpolyoxyethylene ether, Fluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, carboxylic acid fluoroalkyl ester and the like can be mentioned.

  Examples of commercially available fluorosurfactants include BM-1000, BM-1100 (above, manufactured by BM CHEMIE), MegaFuck F142D, F172, F173, F183, F178, F191, F191, and F471. F476 (above, manufactured by Dainippon Ink and Chemicals), Florard FC-170C, FC-171, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-105, SC-106 (and above) Asahi Glass Co., Ltd.), F-top EF301, EF303, EF352 (above, manufactured by Shin-Akita Kasei), Footent FT-100, FT-110, FT-140A, FT-150, FT-250, FT-251, FT-300, FT-310, FT-400S, FTX-218, FT-251 (above, Neos), etc. Is mentioned.

  Examples of the silicone-based surfactant include Torre Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, and SF-8428. DC-57, DC-190, SH 8400 FLUID (above, made by Toray Dow Corning Silicone), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above, GE Toshiba Silicone), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

  The content of the surfactant in the radiation-sensitive resin composition is preferably 0.01 parts by mass or more and 2 parts by mass or less, more preferably 0.8 parts by mass with respect to 100 parts by mass of the polymer component [A]. It is 05 parts by mass or more and 1 part by mass or less. The film thickness uniformity of a coating film can be improved more by making content of surfactant into the said specific range.

<Adhesion aid>
The adhesion aid can be used to improve the adhesion between an insulating material and an inorganic substance serving as a substrate, for example, a silicone compound such as silicone, silicone oxide, or silicon nitride, or a metal such as gold, copper, or aluminum. As the adhesion assistant, a functional silane coupling agent is preferable. Examples of the functional silane coupling agent include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group (preferably an oxiranyl group), and a thiol group.

  Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltri Examples include methoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. Of these, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane are preferred. .

  As content of the adhesion | attachment adjuvant in the said radiation sensitive resin composition, 0.5 mass part or more and 20 mass parts or less are preferable with respect to 100 mass parts of [A] polymer components, and 1 mass part or more and 10 mass parts is preferable. The following is more preferable. By setting the content of the adhesion aid in the specific range, the adhesion between the formed display element interlayer insulating film and the substrate is further improved.

<Compound having a hindered phenol structure>
A compound having a hindered phenol structure is a component for preventing cleavage of a compound bond by a radical or a peroxide. Examples of the compound having a hindered phenol structure include radical scavengers such as a compound having a hindered amine structure in addition to a compound having a hindered phenol structure.

  Examples of the compound having a hindered phenol structure include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-). tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris- (3,5-di-tert-butyl-4-hydroxy Benzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N′-hexane-1,6 -Diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide), 3,3 , 3 ′, 5 ′, 5′-hexa-tert-butyl-a, a ′, a ′-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) ) -O-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate, hexamethylene Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylin) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3 5-to Azine-2-ylamine) phenol, and the like.

  Examples of the compound having a hindered amine structure include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6) -Pentamethyl-4-piperidyl) 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acroyl-2, , 6,6-tetramethyl-4-piperidyl) 2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) decandioate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl Oxy] -1- [2- (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2 -(2,2,6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6- Tetramethyl-4 Compounds such as piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate It is done.

  As content of the compound which has a hindered phenol structure in the said radiation sensitive resin composition, 0.1 mass part or more and 10 mass parts or less are preferable with respect to 100 mass parts of [A] polymer components, 1.5. More preferred is 3 parts by mass or more. By keeping the content of the compound having a hindered phenol structure within the above specified range, the voltage holding ratio of an insulating film such as an interlayer insulating film for display elements is further improved while maintaining the sensitivity of the radiation sensitive resin composition. Can be made.

<Method for preparing radiation-sensitive resin composition>
The radiation-sensitive resin composition comprises [A] a polymer component, [B] a radiation-sensitive acid generator, a [C] compound to be added as necessary, a suitable component such as a [D] sensitizer, It is prepared in a dissolved or dispersed state by mixing other optional components. For example, the radiation sensitive resin composition can be prepared by mixing each component at a predetermined ratio in a solvent.

  As the solvent, a solvent in which each component is uniformly dissolved or dispersed and does not react with each component is preferably used. Examples of the solvent include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, and aromatic hydrocarbons. , Ketones, other esters and the like.

  Examples of alcohols include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol and the like.

  Examples of ethers include tetrahydrofuran.

  Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.

  Examples of the ethylene glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate.

  Examples of the diethylene glycol alkyl ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.

  Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like.

  Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate and the like.

  Examples of the propylene glycol monoalkyl ether propionate include propylene monoglycol methyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate and the like. .

  Examples of aromatic hydrocarbons include toluene and xylene.

  Examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and the like.

  Examples of other esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, hydroxy Methyl acetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate Methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, Methyl ropoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propylbutoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionate Propyl acid, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxypropionic acid Ethyl, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methyl Butyl xylpropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxy Examples include propyl propionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

  Of these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and butyl methoxyacetate are preferred. Diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, propylene More preferred are glycol monomethyl ether and butyl methoxyacetate.

<Method for forming interlayer insulating film for display element>
The said radiation sensitive resin composition is suitable as a forming material of the interlayer insulation film for display elements. The present invention also includes a display element interlayer insulating film formed from the radiation-sensitive resin composition.

The method for forming an interlayer insulating film for a display element according to the present invention includes:
Using the radiation sensitive resin composition, a coating film forming step for forming a coating film on the substrate,
A radiation irradiation step of irradiating at least a part of the coating film;
A development step of developing the coating film irradiated with the radiation; and a heating step of heating the developed coating film.

  According to the formation method, an interlayer insulating film for a display element that is excellent in transparency, heat resistance, hardness, and the like can be formed. Further, since the amount of change in the film thickness of the unexposed portion can be suppressed, the production process margin can be improved as a result, and the yield can be improved. Furthermore, an interlayer insulating film for a display element having a fine and elaborate pattern can be easily formed by forming a pattern by exposure, development and heating utilizing photosensitivity. Therefore, the formed interlayer insulation film for display elements can be used suitably for display elements, such as a liquid crystal display element and an organic EL display element.

[Coating film forming process]
In this step, the radiation sensitive resin composition is applied onto a substrate to form a coating film. Preferably, the solvent is removed by prebaking the coated surface.

  Examples of the substrate include glass, quartz, silicone, and resin. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opening polymer of cyclic olefin, and a hydrogenated product thereof. As prebaking conditions, although it changes also with kinds, compounding ratios, etc. of each component, it can be set as 70 degreeC-120 degreeC, about 1 minute-10 minutes.

[Radiation irradiation process]
In this step, at least a part of the formed coating film is exposed to radiation and exposed. When exposing, it exposes normally through the photomask which has a predetermined pattern. As the radiation used for exposure, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is more preferable. Energy of exposure intensity at the wavelength 365nm radiation, by the value measured by luminometer (OAI model356, OAI Optical Ltd. ^Associates), is preferably ^{500J / m 2 ~6,000J / m 2} , 1,500J / m 2 ˜1,800 J / m ² is more preferable.

[Development process]
In this step, the coating film irradiated with the radiation is developed. By developing the coated film after exposure, unnecessary portions (radiation irradiated portions) are removed to form a predetermined pattern. As the developer used in the development step, an alkaline aqueous solution is preferable. Examples of the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. .

  An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant can be added to the alkaline aqueous solution. The concentration of alkali in the aqueous alkali solution is preferably from 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. Examples of the developing method include a liquid piling method, a dipping method, a rocking dipping method, and a shower method. The development time varies depending on the composition of the radiation sensitive resin composition, but is about 10 seconds to 180 seconds. Subsequent to such development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

Thickness change rate of the thickness T ₁ of the after development with respect to the film thickness T ₀ of the coating film before development is preferably 80% or more. As described above, according to the forming method using the radiation-sensitive resin composition, the amount of change in the film thickness of the unexposed portion can be suppressed, and the film thickness after development is 80% or more of the film thickness before development. Can be maintained.

[Heating process]
In this step, the developed coating film is heated. For heating, by heating a patterned thin film using a heating device such as a hot plate or oven, the curing reaction of the [A] polymer component can be promoted to obtain a cured product. As heating temperature, it is about 120 to 250 degreeC, for example. The heating time varies depending on the type of heating device, but for example, it is about 5 to 30 minutes for a hot plate and about 30 to 90 minutes for an oven. Moreover, the step baking method etc. which perform a heating process 2 times or more can also be used. In this way, a patterned thin film corresponding to the target display element interlayer insulating film can be formed on the surface of the substrate.

  Note that the use of the cured film is not limited to the interlayer insulating film for display elements, and can also be used as a spacer or a protective film. The film thickness of the interlayer insulating film for display elements is preferably 0.1 μm or more and 8 μm or less, more preferably 0.1 μm or more and 6 μm or less.

  EXAMPLES Hereinafter, although this invention is explained in full detail based on an Example, this invention is not interpreted limitedly based on description of this Example.

Mw and Mn of the polymer were measured by GPC under the following conditions.
Apparatus: GPC-101 (Showa Denko)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 combined with mobile phase: tetrahydrofuran Column temperature: 40 ° C.
Flow rate: 1.0 mL / min Sample concentration: 1.0 mass%
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

<[A] Synthesis of polymer component>
[Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 50 parts by mass of 5- (1-ethoxyethoxycarbonyl) -2-norbornene giving structural unit (I), 30 parts by mass of glycidyl methacrylate giving structural unit (II), and methacrylic acid 10 giving other structural units Stirring was started gently after charging 10 parts by mass and 10 parts by mass of styrene and substituting nitrogen. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-1). Mw of the copolymer (A-1) was 8,000. The solid content concentration of the polymer solution was 33.5% by mass. As a result of ¹³ C-NMR analysis, the content of each structural unit was structural unit (I): structural unit (II): other structural unit = 35: 32: 33 (mol%). In addition, the nuclear magnetic resonance apparatus (the JEOL make, JNM-ECX400) was used for the ¹³ C-NMR analysis for calculating | requiring the content rate of each structural unit of a polymer.

[Synthesis Example 2]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 60 parts by mass of 5- (1-ethoxybutoxycarbonyl) -2-norbornene giving structural unit (I), 20 parts by mass of methacrylic acid, 10 parts by mass of styrene and 10 parts by mass of methyl methacrylate giving other structural units. After replacing the charged nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer.
2- (Vinyloxyethoxy) ethyl methacrylate (made by Nippon Shokubai, VEEM) 128 as a compound having a vinyl ether group and a (meth) acryloyloxy group to give the structural unit (II) to the solution containing this copolymer A mass part was dropped at a constant speed with a dropping funnel over 1 hour. After the aging reaction for 12 hours, the reaction solution was cooled to room temperature to obtain a copolymer (A-2) solution. Mw of the copolymer (A-2) was 10,000. The solid content concentration of the polymer solution was 35.2% by mass. As a result of ¹³ C-NMR analysis, the content of each structural unit was structural unit (I): structural unit (II): other structural units = 37: 33: 30 (mol%).

[Synthesis Example 3]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 50 parts by mass of 5- (tetrahydropyranyloxycarbonyl) -2-norbornene giving structural unit (I), 10 parts by mass of methacrylic acid, 10 parts by mass of styrene and 30 parts by mass of hydroxyethyl methacrylate giving other structural units. Was added, and the mixture was purged with nitrogen. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a copolymer.
In order to give structural unit (II) to the solution containing this copolymer, 12 parts by mass of 2-methacryloyloxyethyl isocyanate (Karenz MOI, Showa Denko) as an unsaturated isocyanate compound, 4 as a polymerization inhibitor -After adding 0.1 mass part of methoxyphenol, it stirred at 40 degreeC for 1 hour, and also stirred at 60 degreeC for 2 hours, and was made to react. The progress of the reaction between the isocyanate group derived from 2-methacryloyloxyethyl isocyanate and the hydroxyl group of the copolymer was confirmed by IR (infrared absorption) spectrum. The IR spectrum of the reaction solution after 1 hour at 40 ° C. and further 2 hours at 60 ° C. was measured, and the peak near 2,270 cm ⁻¹ derived from the isocyanate group of 2-methacryloyloxyethyl isocyanate decreased. It was confirmed that the reaction was progressing. A copolymer (A-3) solution having a solid content concentration of 31.0% was obtained. Mw of this copolymer (A-3) was 10,000. The solid content concentration of the polymer solution was 35.5% by mass. As a result of ¹³ C-NMR analysis, the content of each structural unit was structural unit (I): structural unit (II): other structural unit = 33: 17: 50 (mol%).

[Synthesis Example 4]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 50 parts by mass of 5- (1-ethoxybutoxycarbonyl) -2-norbornene giving structural unit (I), 8 parts by mass of ethylene glycol dimethacrylate giving structural unit (II), and methacrylic acid giving other structural units After 10 parts by mass, 12 parts by mass of styrene and 20 parts by mass of hydroxyethyl methacrylate were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a copolymer. Mw of this copolymer (A-4) was 12,000. The solid content concentration of the polymer solution was 35.2% by mass. As a result of ¹³ C-NMR analysis, the content of each structural unit was structural unit (I): structural unit (II): other structural unit = 35: 5: 60 (mol%).

[Synthesis Example 5]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 25 parts by mass of 5- (tetrahydropyranyloxycarbonyl) -2-norbornene giving structural unit (I), 10 parts by mass of glycidyl methacrylate giving structural unit (II), and 5 parts by mass of styrene giving other structural units Then, 28 parts by mass of 1-n-butoxyethyl methacrylate, 32 parts by mass of N-cyclohexylmaleimide and 3 parts by mass of α-methylstyrene dimer as a molecular weight regulator were charged and purged with nitrogen, and then gently stirred. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer. Mw of this copolymer (A-5) was 9,000. The solid content concentration of the polymer solution was 35.5% by mass. As a result of ¹³ C-NMR analysis, the content of each structural unit was structural unit (I): structural unit (II): other structural unit = 36: 10: 54 (mol%).

[Synthesis Example 6]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 45 parts by mass of 3-ethyl-3-methacryloxymethyloxetane giving structural unit (II), 45 parts by mass of 1-n-butoxyethyl methacrylate, 5 parts by mass of styrene and 2-hydroxyethyl giving other structural units After 5 parts by weight of methacrylate and 3 parts by weight of α-methylstyrene dimer as a molecular weight regulator were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer. Mw of this copolymer (A-6) was 10,000. The solid content concentration of the polymer solution was 34.5% by mass. As a result of ¹³ C-NMR analysis, the content of each structural unit was structural unit (II): other structural units = 42: 58 (mol%).

[Synthesis Example 7]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 8- (1-ethoxyethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] 50 parts by weight of dodec-3-ene, 30 parts by weight of glycidyl methacrylate to give structural unit (II), 10 parts by weight of methacrylic acid to give other structural units, and 10 parts by weight of styrene were charged with nitrogen. After that, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-7). Mw of the copolymer (A-7) was 7,000. The solid content concentration of the polymer solution was 33.2% by mass. As a result of ¹³ C-NMR analysis, the content of each structural unit was structural unit (I): structural unit (II): other structural units = 33: 34: 33 (mol%).

<Preparation of radiation-sensitive resin composition>
Hereinafter, the components used for the preparation of the radiation sensitive resin compositions of Examples and Comparative Examples will be described in detail.

<[B] Acid generator>
(B-1): 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate (B-2): N-hydroxynaphthalimide-trifluoromethanesulfonate (B-3): ( 5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (Ciba Specialty Chemicals, IRGACURE PAG 103)

<[C] Compound>
(C-1): Di [1-ethyl- (3-oxetanyl) methyl] ether represented by the following formula (C-1) (C-2): 1, represented by the following formula (C-2) 4-Bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene

<[D] sensitizer>
(D-1): Isopropylthioxanthone (D-2): Diethylthioxanthone

[Example 1]
[A] As a polymer component, in a solution containing 100 parts by mass of copolymer (A-1) in terms of solid content, [B] 3 parts by mass of compound (B-2) as an acid generator and compound (B- 3) 1 part by weight, 15 parts by weight of the compound (C-1) as the [C] compound, 0.2 parts by weight of a silicone surfactant (Toray Dow Corning, SH 8400 FLUID) as the surfactant, and adhesion A radiation-sensitive resin composition (S-1) was prepared by mixing 3.0 parts by mass of γ-glycidoxypropyltrimethoxysilane as an auxiliary and filtering with a membrane filter having a pore size of 0.2 μm.

[Examples 2 to 6 and Comparative Examples 1 to 4]
[A] The same procedure as in Example 1 was conducted except that the types and amounts of the polymer component, [B] acid generator, [C] compound and [D] sensitizer were as shown in Table 1. Radiation sensitive resin compositions (S-2) to (S-7) and (CS-1) to (CS-3) were prepared. In Table 1, “-” indicates that the corresponding component was not used.

<Evaluation>
Using each prepared radiation sensitive resin composition, various characteristics of each radiation sensitive resin composition and a coating film (interlayer insulating film) formed using the composition were evaluated by the following methods. The results are shown in Table 1.

[Sensitivity (J / m ² )]
Hexamethyldisilazane (HMDS) was applied onto a 550 × 650 mm chromium film and heated at 60 ° C. for 1 minute (HMDS treatment). Each radiation-sensitive resin composition prepared as described above was applied onto the chromium-deposited glass after the HMDS treatment using a slit die coater “TR6321055-CL”. Next, after the ultimate pressure was set to 100 Pa and the solvent was removed under vacuum, a coating film having a thickness of 3.0 μm was formed by prebaking at 90 ° C. for 2 minutes. Subsequently, using a Canon MPA-600FA exposure machine, the coating film was irradiated with radiation through the mask having a 60 μm line-and-space (10 to 1) pattern with the exposure amount as a variable. Then, it developed by the puddle method at 25 degreeC using 0.4 mass% tetramethylammonium hydroxide aqueous solution. The development time was 80 seconds. Next, washing with running ultrapure water for 1 minute was performed, followed by drying to form a pattern on the chromium-deposited glass substrate after the HMDS treatment. At this time, the exposure amount (J / m ² ) necessary for completely dissolving the 6 μm space pattern was defined as sensitivity. It can be said that the sensitivity is good when this value is 500 J / m ² or less.

[Dry etching resistance (μm)]
Similar to the sensitivity evaluation, a coating film was formed on a glass substrate. Without exposure, this glass substrate was heated in a clean oven at 230 ° C. for 0.5 hours to obtain a cured film. The cured film obtained here was dry-etched using a mixed gas of CF ₄ / O ₂ = 50/10 at an output of 400 W for 70 seconds, and the amount of film loss (μm) was measured. Evaluated. It can be said that the dry etching resistance is good when the amount of film loss is less than 1 μm, and it is poor when it is 1 μm or more.

[transparency(%)]
Similar to the sensitivity evaluation, a coating film was formed on a glass substrate. Without exposure, this glass substrate was heated at 220 ° C. for 1 hour in a clean oven to obtain a cured film. The transmittance (%) at a wavelength of 400 nm was measured using a spectrophotometer (Hitachi, Ltd., 150-20 type double beam) and used for evaluation of transparency. At this time, it can be said that the transparency is good when the transmittance (%) is 90% or more, and the transparency is poor when it is less than 90%.

[Residual film rate (%)]
Similar to the sensitivity evaluation, a coating film was formed on a glass substrate. The film thickness of this coating film was measured and set as the film thickness after coating. Without exposing this coating film, it heated at 220 degreeC in the clean oven for 1 hour, and obtained the cured film. The film thickness of this cured film was defined as the film thickness after heating. The ratio (%) of the film thickness after heating to the film after application was defined as the remaining film ratio (%). When this value exceeds 70%, the remaining film ratio is good, and when the value is 70% or less, the remaining film ratio is poor.

[surface hardness]
About the board | substrate which has the cured film formed by the said transparency evaluation, the pencil hardness (surface hardness) of the cured film was measured by 8.4.1 pencil scratch test of JISK-5400-1990. When this value is 3H or more, the surface hardness of the cured film as the interlayer insulating film is good, and it can be said that the composition used for forming the cured film has sufficient curability.

[Heat resistance transparency (%)]
The substrate having the cured film formed by the evaluation of the transparency was further heated at 230 ° C. for 1 hour in a clean oven. Then, the transmittance | permeability (%) in wavelength 400nm was measured using the spectrophotometer (Hitachi Ltd., 150-20 type double beam), and it used for heat resistant transparency evaluation. At this time, when the transmittance (%) is 90% or more, the heat-resistant transparency is good, and when it is less than 90%, the heat-resistant transparency is poor.

[Evaluation of water absorption]
Similar to the sensitivity evaluation, each radiation-sensitive resin composition was applied on a silicon substrate, heated on a hot plate at 120 ° C. for 2 minutes, and then further post-cleaned at 250 ° C. for 45 minutes in a clean oven. Baking was performed to form a coating film having a thickness of 3.0 μm.
About this cured film, the gas component emitted from a cured film when it heated up from normal temperature to 200 degreeC using TDS (Thermal Desorption Spectroscopy) was detected with the mass spectrometer.
At this time, the water absorption of the cured film was evaluated by measuring the detected value of the water-derived gas peak (M / z = 18). When the peak intensity was 7.0 × 10 ⁻⁹ or less, it was judged that the water absorption of the cured film was low. In Table 1, the case where it was determined that the water absorption was low was “◯”, and the case where it was determined that the water absorption was high was “x”.

  As is clear from the results in Table 1, Examples 1 to 7 using the radiation-sensitive resin composition are not sensitive to the development time after development in addition to good sensitivity compared to the compositions of Comparative Examples 1 to 3. It was found that the film thickness change amount at the exposed portion and the film thickness change amount after post-baking can be suppressed. Moreover, it turned out that the interlayer insulation film for display elements formed from the said radiation sensitive resin composition is excellent also in dry etching tolerance, transparency, surface hardness, low water absorption, and heat-resistant transparency.

  According to the present invention, there is provided an insulating film such as an interlayer insulating film for a display element, which is excellent in transparency, heat resistance, hardness, etching resistance, and low water absorption, has good sensitivity, and has a small amount of change in film thickness in an unexposed portion. be able to. In addition, since an insulating film such as a display element interlayer insulating film formed from the radiation-sensitive resin composition can reduce the change in film thickness, the production process margin can be improved as a result, and the yield can be improved. Furthermore, an interlayer insulating film for a display element having a fine and elaborate pattern can be easily formed by forming a pattern by an exposure process, a development process and a heating process using photosensitivity. Therefore, the formed interlayer insulation film for display elements can be used suitably for display elements, such as a liquid crystal display element and an organic EL display element.

Claims (10)

[A] A structural unit (I) derived from a cyclic olefin monomer having an acid-dissociable group in the same or different polymer, and a structural unit having a polymerizable group and different from the structural unit (I) ( A polymer component containing II), and a radiation sensitive resin composition containing [B] a radiation sensitive acid generator. [A] The radiation-sensitive resin composition according to claim 1, wherein the structural unit (I) of the polymer component includes a structural unit represented by the following formula (1).

(In the formula (1), R ¹ is a group represented by any of the following formulas (a) and (b). N is 1 or 2. When n is 2, two R ¹ May be the same or different.)

(In Formula (a), R ² is a single bond or an alkanediyl group having 1 to 6 carbon atoms. R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. However, some or all of the hydrogen atoms of the alkyl group, cycloalkyl group and aryl group may be substituted, and R ³ and R ⁴ are not both hydrogen atoms. ⁵ is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a group represented by -M (R ¹⁰ ) _3. M is Si, Ge or Sn, and R ¹⁰ is an alkyl group. . However, the alkyl group of R ^5, cycloalkyl group, aryl group and aralkyl group, and each other good .R ³ and R ⁵ be a part or all of the hydrogen atoms have been substituted with an alkyl group R ¹⁰ Combine , May form a cyclic ether structure together with the oxygen atom to the carbon atom and R ⁵ R ³ is attached is attached.
In formula (b), R ⁶ is a single bond or an alkanediyl group having 1 to 6 carbon atoms. R ⁷ is an alkyl group or a cycloalkyl group.   [C] The radiation sensitive resin composition according to claim 1 or 2, further comprising a compound having two or more oxetane groups. The radiation sensitive resin composition according to claim 3, wherein the compound [C] is represented by the following formula (2).

(In the formula ^{(2), R 11} is a is .m organic group having 1 to 20 carbon atoms, an integer of 2 or more. Plurality of ^{R 12} are each independently a hydrogen atom or a carbon number 1 to 5 alkyl group.) The radiation sensitive resin composition according to claim 4, wherein the compound [C] is represented by the following formula (2-1) or (2-2).

(In the formulas (2-1) and (2-2), R ¹² has the same meaning as the above formula (2).)   [A] Content of [C] compound with respect to 100 mass parts of polymer components is 1 mass part or more and 100 mass parts or less, The radiation sensitive resin composition of Claim 3, 4 or 5.   [D] The radiation sensitive resin composition according to any one of claims 1 to 6, further comprising a sensitizer.   The radiation sensitive resin composition of any one of Claims 1-7 used in order to form the interlayer insulation film for display elements.   The interlayer insulation film for display elements formed from the radiation sensitive resin composition of Claim 8. Using the radiation-sensitive resin composition according to claim 8 to form a coating film on a substrate;
Irradiating at least a part of the coating film with radiation,
A method for forming an interlayer insulating film for a display element, comprising: developing a coating film irradiated with the radiation; and heating the developed coating film.