JP2011197142A - Radiation-sensitive composition, cured film and method for forming the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-sensitive composition which can be cured by low-temperature heating, has good alkali developability and high radiation sensitivity, and capable of forming a cured film with excellent hardness and solvent resistance.SOLUTION: The radiation-sensitive composition contains[A] an alkali-soluble resin, [B] at least one compound selected from the group consisting of vinyloxyalkyloxetane and vinyloxyaryloxetane compounds, and [C] a compound which generates an acid when energy is imparted thereto.

Description

  The present invention relates to a radiation-sensitive composition suitably used for forming a cured film as a protective film for display elements or an interlayer insulating film, and as a protective film or interlayer insulating film for display elements formed from this radiation-sensitive composition. The present invention relates to a cured film and a method for forming the same.

  A flexible display can be easily improved in convenience such as weight reduction and downsizing, and has recently been applied to liquid crystal electronic paper, plastic ICs, and the like. As a substrate for such a flexible display, a plastic substrate such as polycarbonate or polyethylene terephthalate has been studied instead of a glass substrate.

  Furthermore, attempts have been made to apply the flexible display technology to radiation devices such as liquid crystal display elements (LCD) and charge coupled devices (CCD). In such a radiation device, the display element is immersed in a solvent, an acid, an alkali solution, or the like during the manufacturing process. Further, when the wiring electrode layer is formed by sputtering, the element surface is locally exposed to a high temperature. Therefore, in order to prevent the element from being deteriorated or damaged by such treatment, a protective film is provided on the surface of the display element.

  However, whether it is applied to flexible displays or radiation devices, the plastics described above are slightly expanded and contracted under thermal load, which may impede the function of the display, and there is an urgent need to improve heat resistance. It has become. On the other hand, as another measure, in order to reduce the thermal stress on the plastic substrate, it is considered to lower the temperature of the manufacturing process of the flexible display or the like. One of the steps in the manufacturing process that requires a high temperature is a step of curing the interlayer insulating film and the protective film by heating, and the above-described measures for lowering the temperature require lowering the heating step.

  At present, a radiation-sensitive composition is widely used as a forming material for an interlayer insulating film or the like because it requires a small number of steps for pattern formation and has a high surface hardness after curing. As such a radiation-sensitive composition, for example, JP-A-2001-354822 discloses a radiation-sensitive composition containing a copolymer composed of an unsaturated carboxylic acid and / or an anhydride thereof, an epoxy group-containing unsaturated compound, and the like. The composition is disclosed, and it is described that an interlayer insulating film having a desired surface hardness is formed by a cleavage reaction of an epoxy group by a carboxyl group. Generally, in order to increase the surface hardness to a level required for practical use as an interlayer insulating film, a heating process at 200 ° C. or higher is required, but when heating is performed at a high temperature of 200 ° C. or higher. May cause deformation of the substrate. On the other hand, considering the heat resistance of the plastic substrate, the temperature of the heating step is preferably 180 ° C. or lower, but in this case, there is a possibility that a desired surface hardness cannot be obtained.

  JP-A-2008-77067 discloses a copolymer comprising an unsaturated carboxylic acid and / or an anhydride thereof, an epoxy group-containing unsaturated compound, a polymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator. In addition, a negative radiation sensitive composition for a spacer of a liquid crystal display device containing a thiol compound having two or more mercapto groups in one molecule is disclosed. However, although the radiation-sensitive composition of this document is excellent in terms of radiation sensitivity and adhesion to a substrate, it is not intended for curing by low-temperature heating to cope with a plastic substrate.

  On the other hand, Japanese Patent Application Laid-Open No. 2009-4394 discloses a flexible display for a flexible display which is excellent in terms of solvent resistance, specific resistance, semiconductor mobility and the like by curing a low temperature curable polyimide precursor at 180 ° C. or lower. It is disclosed that a gate insulating film can be obtained. However, since the coating liquid containing the polyimide precursor of the above document is a chemical curing system and does not have pattern forming ability by exposure and development, fine pattern formation is impossible. Further, in forming an insulating film using a coating solution containing such a polyimide precursor, it often takes 1 hour or more to heat and cure the coating film.

  JP 2009-40989 A discloses a liquid curable composition using a vinyl oxetane compound such as 3-ethyl-3- (vinyloxymethyl) oxetane. However, since this composition has no solubility in an alkaline developer, it was impossible to form a film pattern by development. Furthermore, as the protective film for display elements and the interlayer insulating film, pattern formation is often required, but the protective film for display elements and interlayer insulation of materials that are difficult to form a pattern such as the curable composition described above. Application to membrane is difficult.

  In view of the above circumstances, it is possible to cure at a low temperature so as to be suitable for the production of a cured film for flexible displays, the film formation is simple, and the alkali developability (characteristic for accurately forming a desired pattern shape) is good. Development of such a radiation sensitive composition is strongly demanded. Moreover, in the device manufacturing process of a flexible display, a laminated body may be formed in the upper layer of an interlayer insulation film through a coating process. Therefore, the interlayer insulating film is required to have solvent resistance against the solvent used when forming a laminate by coating. Furthermore, the occurrence of burn-in is low in displays such as liquid crystal panels, and high reliability as a display device is also required at the same time.

JP 2001-354822 A JP 2008-77067 A JP 2009-4394 A JP 2009-40989A

  The present invention has been made based on the above circumstances, and its purpose is that it can be cured by low-temperature heating, has good alkali developability, has high radiation sensitivity, and has solvent resistance and An object of the present invention is to provide a radiation-sensitive composition capable of forming a cured film as an interlayer insulating film for a flexible display or a protective film for a display element, which has excellent hardness and low seizure. Another object of the present invention is to provide a cured film formed using such a radiation sensitive composition.

（式（１）中、Ｒ^１は水素原子又はメチル基であり、Ｘはメチレン基、炭素数２〜２０のアルキレン基、フェニレン基又はナフチレン基であり、Ｒ^２は水素原子、炭素数１〜２０のアルキル基、ベンジル基、フェニル基又はトリル基である。
式（１´）中、Ｒ^１´は水素原子又はメチル基であり、Ｘ´はメチレン基、炭素数２〜２０のアルキレン基、フェニレン基又はナフチレン基であり、Ｒ^２´は水素原子、炭素数１〜２０のアルキル基、ベンジル基、フェニル基又はトリル基である。） The present invention made to solve the above problems
[A] alkali-soluble resin,
[B] A radiation-sensitive composition comprising: a compound represented by the following formula (1); and [C] a compound that generates an acid upon application of energy.

(In the formula (1), ^{R 1} is a hydrogen atom or a methyl group, X is a methylene group, an alkylene group having 2 to 20 carbon atoms, a phenylene group or naphthylene group, ^{R 2} represents a hydrogen atom, 1 to carbon atoms 20 alkyl groups, benzyl groups, phenyl groups or tolyl groups.
Wherein (1'), ^{R 1'is} a hydrogen atom or a methyl group, X'is a methylene group, an alkylene group having 2 to 20 carbon atoms, a phenylene group or a naphthylene group, ^{R 2'is} a hydrogen atom, a carbon It is an alkyl group, a benzyl group, a phenyl group, or a tolyl group of formula 1-20. )

  The radiation-sensitive composition contains a compound having an oxetanyl group represented by the above formula (1) as the [B] component in addition to the above-mentioned [A] component, and an acid by applying energy as the [C] component. In addition to having good radiation sensitivity and excellent alkali developability, it promotes the crosslinking reaction of the component [A] even at low temperature heating, and has excellent solvent resistance. A cured film for a display or the like having less image sticking and excellent reliability can be formed.

（式（２）中、Ｙは酸素原子又はＮ−Ｒ^３であり、このＲ^３は炭素数１〜２０のアルキル基、炭素数４〜１２の脂環式アルキル基、ベンジル基、フェニル基、トリル基又はナフチル基である。） It is preferable that the said radiation sensitive composition further contains the compound represented by [D] following formula (2).

(In Formula (2), Y is an oxygen atom or N—R ³ , and R ³ is an alkyl group having 1 to 20 carbon atoms, an alicyclic alkyl group having 4 to 12 carbon atoms, a benzyl group, a phenyl group, A tolyl group or a naphthyl group.)

  When the radiation-sensitive composition contains an unsaturated [D] component, the crosslinking reaction of the [A] component is promoted, and as a result, a cured film having excellent solvent resistance and hardness is formed. Can do.

（式（３）中、Ｒ^４は水素原子又はメチル基である。） In the said radiation sensitive composition, it is preferable that the said [A] alkali-soluble resin contains the structural unit represented by (a1) following formula (3).

(In formula (3), R ⁴ is a hydrogen atom or a methyl group.)

  When the [A] component contains the structural unit represented by the above formula (3), the alkali developability of the radiation-sensitive composition is improved, and the crosslinking reaction of the [A] component is further promoted. As a result, a cured film having excellent solvent resistance and hardness can be formed even by low-temperature heating.

（式（４）中、Ｒ^５は水素原子又はメチル基であり、Ｒ^６は水素原子又は炭素数１〜６のアルキル基であり、ｎは０〜１２の整数である。
式（５）中、Ｒ^７は水素原子又はメチル基であり、ｎは０〜１２の整数である。
式（６）中、Ｒ^８は水素原子又はメチル基であり、Ｒ^９は水素原子、炭素数１〜６のアルキル基、フェニル基又はハロゲンであり、ｎは０〜１２の整数である。
式（６´）中、Ｒ^８´は水素原子又はメチル基であり、Ｒ^９´は水素原子、炭素数１〜６のアルキル基、フェニル基又はハロゲンであり、ｎは０〜１２の整数である。） In the radiation-sensitive composition, the [A] alkali-soluble resin is a structural unit represented by (a2) the following formulas (4), (5), (6), and (6 ′) as structural units. It is preferable to include at least one structural unit selected from the group consisting of:

(In the formula (4), ^{R 5} is a hydrogen atom or a methyl group, ^{R 6} is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n is an integer from 0 to 12.
In Formula (5), R ⁷ is a hydrogen atom or a methyl group, and n is an integer of 0 to 12.
In Formula (6), R ⁸ is a hydrogen atom or a methyl group, R ⁹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen, and n is an integer of 0 to 12.
In formula (6 ′), R ^{8 ′} is a hydrogen atom or a methyl group, R ^{9 ′} is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen, and n is an integer of 0 to 12. is there. )

  When the radiation-sensitive composition has a structural unit containing an oxiranyl group or an oxetanyl group in the molecule, the hardness and solvent resistance of a cured film obtained by low-temperature curing can be further increased.

  It is preferable that the said radiation sensitive composition further contains [E] radical photopolymerization initiator. As a result, in addition to the crosslinking reaction of the [A] component, radical polymerization of the [B] component (in the case of including the [D] component, polymerization of the [B] component with the [D] component, or between the [D] components Polymerization) can be promoted. As a result, the solvent resistance and hardness of the cured film obtained through low-temperature heating can be improved, and the anti-seizure property can also be improved.

  The said radiation sensitive composition can be used suitably for forming the cured film as a protective film for display elements, or an interlayer insulation film.

The method for forming the cured film of the present invention is as follows.
(1) The process of forming the coating film of the said radiation sensitive composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) a step of developing the coating film irradiated with light in step (2), and (4) a step of heating the coating film developed in step (3).

  By the above-described steps using the radiation-sensitive composition, the cured film has high hardness, excellent solvent resistance, good anti-seizure properties, and is highly reliable as a protective film for display elements and interlayer insulating films in display devices. Can be formed efficiently.

  Since the cured film of the present invention is formed using the radiation-sensitive composition, it has a high hardness and excellent solvent resistance even with low-temperature heating, and exhibits high reliability due to good anti-seizure properties. it can.

  In the present specification, the “structural unit” means one unit included in the polymer structure and may be present repeatedly.

  As described above, the radiation-sensitive composition of the present invention exhibits high radiation sensitivity, has a high surface hardness even when heated at a low temperature, and can form a cured film excellent in alkali developability. In addition, it is possible to form a cured film having excellent reliability and less seizure as a protective film or interlayer insulating film of a display device or the like and excellent in reliability. Therefore, the radiation-sensitive composition can be suitably used as a material for forming a cured film as a protective film for display elements of a flexible display or an interlayer insulating film.

It is typical sectional drawing for description of evaluation of the pattern shape after image development.

  The radiation-sensitive composition of the present invention comprises [A] an alkali-soluble resin, [B] a compound represented by the above formula (1) (hereinafter also simply referred to as “compound [B]”) and [C] energy. Contains a compound that generates an acid upon application (hereinafter, also simply referred to as “acid generator”). The component (A) includes (a1) the structural unit represented by the above formula (3) (hereinafter also simply referred to as “structural unit (a1)”), (a2) the above formulas (4) to (6) and ( 6 ′) (hereinafter also simply referred to as “structural unit (a2)”). In addition to the above-mentioned components [A] to [C], the radiation-sensitive composition includes [D] a compound represented by the above formula (2) as a suitable component (hereinafter also simply referred to as “compound [D]”). Or [E] may contain a photoradical polymerization initiator. The radiation-sensitive composition may contain other optional components. Hereinafter, each component will be described.

<[A] alkali-soluble resin>
The component [A] is an alkali-soluble resin and is not particularly limited as long as it is soluble in an alkali developer used in the development processing step of the radiation-sensitive composition containing the component. [A] The alkali-soluble resin is preferably a copolymer having a reactive functional group. Preferable examples of the reactive functional group include a carboxyl group, an epoxy group, and a (meth) acryloyl group. [A] By using a resin having these reactive functional groups as the alkali-soluble resin, the cross-linking reaction between the components [A] when exposing and curing the radiation-sensitive composition is enhanced. In particular, a cured film having desired characteristics can be easily formed.

  The alkali-soluble resin having a reactive functional group such as a carboxyl group or an epoxy group can be synthesized by copolymerizing a radical polymerizable monomer having such a reactive functional group with another radical polymerizable monomer. A copolymer having a (meth) acryloyl group is synthesized by reacting an isocyanate compound having a (meth) acryloyl group after copolymerizing a radical polymerizable monomer having a hydroxyl group with another radical polymerizable monomer. Can do.

  [A] The alkali-soluble resin is a structural unit derived from a radical polymerizable monomer having a reactive functional group such as a carboxyl group, an epoxy group, or a (meth) acryloyl group, and these radical polymerizable monomers and other radical polymerization monomers. The content is preferably 10 to 90% by mass, particularly preferably 20 to 80% by mass, based on the total of structural units derived from the functional monomer. In the component [A], by setting the structural unit derived from the radical polymerizable monomer having a reactive functional group to 10 to 90% by mass, the curing reactivity when exposing the radiation-sensitive composition can be improved. it can.

<Structural unit (a1)>
[A] The alkali-soluble resin preferably contains a building unit (a1) as a structural unit derived from a radical polymerizable monomer having a carboxyl group. The structural unit (a1) is a structural unit derived from acrylic acid or methacrylic acid. When the radiation sensitive composition contains the structural unit (a1), the alkali developability of the radiation sensitive composition is improved, and the crosslinking reaction of the component [A] is further promoted. Even at low temperature heating, a cured film having excellent solvent resistance and hardness can be formed.

  The content of the structural unit (a1) when the radiation-sensitive composition includes the structural unit (a1) may be determined in consideration of the required alkali development degree and the hardness of the cured film. For example, the component [A] The amount is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 10 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass.

Examples of the radical polymerizable monomer that gives a structural unit having a carboxyl group other than the structural unit (a1) include:
Monocarboxylic acids such as crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid;
Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
The acid anhydride of the said dicarboxylic acid etc. can be mentioned.

<Structural unit (a2)>
[A] It is also preferred that the alkali-soluble resin contains the structural unit (a2). The structural unit (a2) is a structural unit derived from an epoxy group-containing unsaturated compound having radical polymerizability. Examples of the epoxy group include an oxanyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure). When the component [A] has a structural unit containing an oxiranyl group or an oxetanyl group in the molecule, the hardness and solvent resistance of a cured film obtained by low-temperature curing can be further increased.

  Specific examples of the epoxy group-containing unsaturated compound that yields the structural unit (a2) represented by the above formula (4) include, for example, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl acrylate, methacrylic acid- 3,4-epoxybutyl, methacrylate-3-methyl-3,4-epoxybutyl, methacrylate-3-ethyl-3,4-epoxybutyl, acrylic acid-5,6-epoxyhexyl, methacrylate-5 6-epoxyhexyl, methacrylic acid-5-methyl-5,6-epoxyhexyl, methacrylic acid-5-ethyl-5,6-epoxyhexyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7- An epoxy heptyl etc. are mentioned.

  Specific examples of the epoxy group-containing unsaturated compound that yields the structural unit (a2) represented by the above formula (5) include, for example, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylethyl methacrylate, 3,4-epoxycyclohexylpropyl methacrylate, 3,4-epoxycyclohexylbutyl methacrylate, 3,4-epoxycyclohexylhexyl methacrylate, 3,4-epoxycyclo Hexyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylethyl acrylate, 3,4-epoxycyclohexylpropyl acrylate, 3,4-epoxycyclohexylbutyl acrylate, 3, 4-epoki Carboxymethyl hexyl acrylate cyclohexane and the like.

  Specific examples of the epoxy group-containing unsaturated compound that yields the structural unit (a2) represented by the above formula (6) include, for example, 3- (acryloyloxymethyl) oxetane and 3- (acryloyloxymethyl) -3-methyloxetane. , 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -3-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -3- Acrylic acid esters such as ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -3-phenyloxetane;

  3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -3-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -3 -Methacrylic acid esters such as phenyloxetane. The structural unit (a2) can be used alone or in combination of two or more.

  Specific examples of the epoxy group-containing unsaturated compound that yields the structural unit (a2) represented by the above formula (6 ′) include, for example, 2- (acryloyloxymethyl) oxetane, 2- (acryloyloxymethyl) -2- Methyl oxetane, 2- (acryloyloxymethyl) -2-ethyloxetane, 2- (acryloyloxymethyl) -2-phenyloxetane, 2- (2-acryloyloxyethyl) oxetane, 2- (2-acryloyloxyethyl)- Acrylic acid esters such as 2-ethyloxetane, 2- (2-acryloyloxyethyl) -2-ethyloxetane, 2- (2-acryloyloxyethyl) -2-phenyloxetane;

  2- (methacryloyloxymethyl) oxetane, 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 -Methacrylic acid esters such as phenyloxetane. The structural unit (a2) can be used alone or in combination of two or more.

  What is necessary is just to change content of the said structural unit (a2) according to the hardness of the required interlayer insulation film, for example, 1 mass part or more and 30 mass parts or less are preferable with respect to 100 mass parts of said [A] component. 5 parts by mass or more and 20 parts by mass or less are more preferable. By setting the content of the structural unit (a2) in the above range, an interlayer insulating film having a desired hardness can be formed. In addition, when employ | adopting combining the said structural unit (a2) 2 or more types, those total amounts should just be in the said range.

  Among the epoxy group-containing unsaturated compounds, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3- (methacryloyloxymethyl) -3-Methyloxetane and 3- (methacryloyloxymethyl) -3-ethyloxetane are preferable from the viewpoints of copolymerization reactivity with other radical polymerizable monomers and developability of the radiation-sensitive composition.

Examples of the radical polymerizable monomer having a hydroxyl group that gives other structural units include:
Acrylic acid hydroxyalkyl esters such as acrylic acid-2-hydroxyethyl ester, acrylic acid-3-hydroxypropyl ester, acrylic acid-4-hydroxybutyl ester, acrylic acid-4-hydroxymethylcyclohexylmethyl ester;
Methacrylic acid-2-hydroxyethyl ester, methacrylic acid-3-hydroxypropyl ester, methacrylic acid-4-hydroxybutyl ester, methacrylic acid-5-hydroxypentyl ester, methacrylic acid-6-hydroxyhexyl ester, methacrylic acid-4- Mention may be made of methacrylic acid hydroxyalkyl esters such as hydroxymethyl-cyclohexylmethyl ester.

  Among these radical polymerizable monomers having a hydroxyl group, acrylic acid-2-hydroxyethyl ester is used from the viewpoint of copolymerization reactivity with other radical polymerizable monomers and reactivity with an isocyanate compound having a (meth) acryloyl group. Acrylic acid-3-hydroxypropyl ester, acrylic acid-4-hydroxybutyl ester, methacrylic acid-2-hydroxyethyl ester, methacrylic acid-4-hydroxybutyl ester, acrylic acid-4-hydroxymethyl-cyclohexylmethyl ester, methacrylic acid Acid-4-hydroxymethyl-cyclohexylmethyl ester is preferred.

  Examples of isocyanate compounds having a (meth) acryloyl group that are reacted with a radical polymerizable monomer having a hydroxyl group and a copolymer of another radical polymerizable monomer include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and the like. Mention may be made of acrylic acid derivatives or methacrylic acid derivatives. Examples of commercially available products of 2-acryloyloxyethyl isocyanate include Karenz AOI (manufactured by Showa Denko KK), and examples of commercially available products of 2-methacryloyloxyethyl isocyanate include Karenz MOI (manufactured by Showa Denko KK). Can be mentioned.

Examples of other radical polymerizable monomers to be copolymerized with a radical polymerizable monomer having a reactive functional group such as a carboxyl group, an epoxy group, a hydroxyl group,
Alkyl acrylates such as methyl acrylate and i-propyl acrylate;
Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate;
Cyclohexyl acrylate, acrylate-2-methylcyclohexyl, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, acrylate-2- (tricyclo [5.2.1.0 ^{2, 6} ] Acrylic alicyclic alkyl ester such as decan-8-yloxy) ethyl, isobornyl acrylate;
Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, methacrylic acid-2- (tricyclo [5.2.1.0 ^{2, 6} ] decano-8-yloxy) ethyl, methacrylic acid alicyclic alkyl esters such as isobornyl methacrylate;
Aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate and aralkyl esters of acrylic acid;
Aryl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate and aralkyl esters of methacrylic acid;
Dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Unsaturated 5-membered ring methacrylates and unsaturated 6-membered ring methacrylates containing 1 atom of oxygen such as tetrahydrofurfuryl methacrylate, tetrahydrofuryl methacrylate, tetrahydropyran-2-methyl methacrylate;
4-methacryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-cyclohexyl- 2 oxygen atoms such as 1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane Unsaturated heterocyclic 5-membered methacrylates containing:

4-acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxymethyl-2, 2-diethyl- 1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-acryloyloxymethyl-2-cyclopentyl-1,3-dioxolane, 4-acryloyloxymethyl-2- Cyclohexyl-1,3-dioxolane, 4-acryloyloxyethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxypropyl-2-methyl-2-ethyl-1,3-dioxolane, 4- Acryloyloxybutyl-2-methyl-2-ethyl-1,3-dioxola Unsaturated five-membered heterocyclic acrylic acid esters containing oxygen 2 atoms and the like;
Vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, 4-isopropenylphenol;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -N-substituted maleimides such as maleimide propionate, N- (9-acridinyl) maleimide;
Conjugated diene compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene;
Other unsaturated compounds such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride and vinyl acetate can be mentioned.

Among these other radical polymerizable monomers, styrene, 4-isopropenylphenol, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, tetrahydrofurfuryl methacrylate, 1,3- Butadiene, 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, N-cyclohexylmaleimide, N-phenylmaleimide, benzyl methacrylate and the like are radical polymerizable monomers having the above reactive functional groups and From the viewpoints of the copolymerization reactivity and developability of the radiation-sensitive composition.

[A] The polystyrene-reduced mass average molecular weight (hereinafter referred to as “Mw”) by GPC (gel permeation chromatography) of the alkali-soluble resin is preferably 2.0 × 10 ^{3 to} 1.0 × 10 ⁵ , more preferably. Is 5.0 × 10 ^{3 to} 5.0 × 10 ⁴ . [A] By making Mw of alkali-soluble resin into the said range, the radiation sensitivity and alkali developability of a radiation sensitive composition can be improved.

Moreover, [A] polystyrene conversion number average molecular weight (hereinafter referred to as “Mn”) by GPC (gel permeation chromatography) of the alkali-soluble resin is preferably 2.0 × 10 ^{3 to} 1.0 × 10 ⁵ , More preferably, it is 5.0 * 10 < ³ > -5.0 * 10 < ⁴ >. By setting Mn of the copolymer to 2.0 × 10 ^{3 to} 1.0 × 10 ⁵ , curing reactivity when exposing the radiation-sensitive composition can be improved.

  Furthermore, [A] molecular weight distribution “Mw / Mn” of alkali-soluble resin (where “Mn” is the polystyrene-equivalent number average molecular weight of [A] alkali-soluble resin measured by gel permeation chromatography). Preferably it is 3.0 or less, More preferably, it is 2.6 or less. [A] By setting Mw / Mn of the alkali-soluble resin to 3.0 or less, the developability of the obtained interlayer insulating film can be improved. [A] A radiation-sensitive composition containing an alkali-soluble resin can easily form a desired pattern shape without causing development residue during development.

  [A] Examples of the solvent used in the polymerization reaction for producing the alkali-soluble resin include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, and propylene glycol monoalkyls. Examples include ether acetate, propylene glycol monoalkyl ether propionate, aromatic hydrocarbons, ketones, and other esters.

These solvents include
Examples of alcohols include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol and the like;
Ethers such as tetrahydrofuran;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Examples of 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, diethylene glycol ethyl methyl ether and the like;
Examples of propylene glycol monoalkyl ethers 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;
As propylene glycol monoalkyl ether propionate, for example, 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, Methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxypropionic acid Butyl, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate Methyl propoxyacetate, 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- Butyl toxipropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxy Examples include esters such as propyl propionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

  Among these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and butyl methoxyacetate are preferable, particularly diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate and butyl methoxyacetate are preferred.

As the polymerization initiator used in the polymerization reaction for producing the component [A], those generally known as radical polymerization initiators can be used. Examples of radical polymerization initiators include:
2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), etc. An azo compound of
And organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane; and hydrogen peroxide.

  When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.

In the polymerization reaction for producing the copolymer of the component [A], a molecular weight modifier can be used to adjust the molecular weight. Specific examples of molecular weight regulators include
Halogenated hydrocarbons such as chloroform and carbon tetrabromide;
mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid;
Xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide;
Examples include terpinolene and α-methylstyrene dimer.

<Compound [B]>
The compound [B] is a vinyloxyalkyloxetane compound or a vinyloxyaryloxetane compound, and has a function of mainly promoting the crosslinking reaction of the component [A] at the time of exposure, and the radiation-sensitive composition is described later. [E] In the case of including the radical photopolymerization initiator, the compound [B] itself undergoes a polymerization reaction, thereby improving alkali developability and further improving the hardness of the cured film.

  Specific examples of the vinyloxyalkyloxetane compound represented by the above formula (1) include, for example, 3-methyl-3- (vinyloxymethyl) oxetane, 3-ethyl-3- (vinyloxymethyl) oxetane, 3-propyl-3- (vinyloxymethyl) oxetane, 3-benzyl-3- (vinyloxymethyl) oxetane, 3-phenyl-3- (vinyloxymethyl) oxetane, 3-ethyl-3- (2-vinyloxyethyl) Oxetane, 3-ethyl-3- (3-vinyloxypropyl) oxetane, 3-ethyl-3- (4-vinyloxybutyl) oxetane, 3-ethyl-3- (5-vinyloxypentyl) oxetane, 3-ethyl-3 -(6-vinyloxyhexyl) oxetane, 3-ethyl-3- (12-vinyloxydodecyl) oxetane, 3-ethyl- - [(alpha-methylvinyloxy) methyl] oxetane, 3-butyl -3 - [(alpha-methylvinyloxy) methyl] oxetane, 3-phenyl-3- (6-vinyloxy-hexyl) oxetane;

  Specific examples of the vinyloxyaryl oxetane compound represented by the above formula (1) include, for example, 3-methyl-3- (vinyloxyphenyl) oxetane, 3-ethyl-3- (vinyloxyphenyl) oxetane, 3-propyl-3- (vinyloxyphenyl) oxetane, 3-benzyl-3- (vinyloxyphenyl) oxetane, 3-phenyl-3- (vinyloxyphenyl) oxetane, 3-methyl-3- (vinyloxynaphthyl) Oxetane, 3-ethyl-3- (vinyloxynaphthyl) oxetane, 3-propyl-3- (vinyloxynaphthyl) oxetane, 3-benzyl-3- (vinyloxynaphthyl) oxetane, 3-phenyl-3- (vinyloxy Naphthyl) oxetane, 3-ethyl-3-[(α-methylvinyloxy) phenyl] oxetane, 3- Tyl-3-[(α-methylvinyloxy) phenyl] oxetane, 3-ethyl-3-[(α-methylvinyloxy) naphthyl] oxetane, 3-butyl-3-[(α-methylvinyloxy) naphthyl] And oxetane. The structural unit (a1) can be used alone or in combination of two or more.

  Specific examples of the vinyloxyalkyloxetane compound represented by the above formula (1 ′) include, for example, 2-methyl-2- (vinyloxymethyl) oxetane, 2-ethyl-2- (vinyloxymethyl) oxetane, 2 -Propyl-2- (vinyloxymethyl) oxetane, 3-benzyl-3- (vinyloxymethyl) oxetane, 2-phenyl-2- (vinyloxymethyl) oxetane, 2-ethyl-2- (2-vinyloxyethyl) oxetane 2-ethyl-2- (3-vinyloxypropyl) oxetane, 2-ethyl-2- (4-vinyloxybutyl) oxetane, 2-ethyl-2- (5-vinyloxypentyl) oxetane, 2-ethyl-2- (6-vinyloxyhexyl) oxetane, 2-ethyl-2- (12-vinyloxydodecyl) oxetane, 2-ethyl-2 [(Alpha-methylvinyloxy) methyl] oxetane, 2-butyl -2 - [(alpha-methylvinyloxy) methyl] oxetane, 2-phenyl-2- (6-vinyloxy-hexyl) oxetane and the like.

  Specific examples of the vinyloxyaryl oxetane compound represented by the above formula (1 ′) include, for example, 2-methyl-2- (vinyloxyphenyl) oxetane and 2-ethyl-2- (vinyloxyphenyl) oxetane. 2-propyl-2- (vinyloxyphenyl) oxetane, 2-benzyl-2- (vinyloxyphenyl) oxetane, 2-phenyl-2- (vinyloxyphenyl) oxetane, 2-methyl-2- (vinyloxynaphthyl) ) Oxetane, 2-ethyl-2- (vinyloxynaphthyl) oxetane, 2-propyl-2- (vinyloxynaphthyl) oxetane, 2-benzyl-2- (vinyloxynaphthyl) oxetane, 2-phenyl-2- (vinyl) Loxynaphthyl) oxetane, 2-ethyl-2-[(α-methylvinyloxy) phenyl] oxetane, 2 2-butyl-2-[(α-methylvinyloxy) phenyl] oxetane, 2-ethyl-2-[(α-methylvinyloxy) naphthyl] oxetane, 2-butyl-2-[(α-methylvinyloxy) naphthyl ] Oxetane etc. are mentioned. The above compound [B] may be used alone or in combination of two or more.

  Preferable examples of compound [B] include 3-ethyl-3- (6-vinyloxymethyl) oxetane, 3-ethyl-3- (vinyloxyhexyl) oxetane, 3-phenyl-3- (vinyloxymethyl) oxetane. , 3-phenyl-3- (6-vinyloxyhexyl) oxetane, 2-ethyl-2- (vinyloxymethyl) oxetane, and the like.

  What is necessary is just to change as content of the [B] component in the said radiation sensitive composition according to the hardness and solvent resistance of the target cured film. As content of [B] component, 10 mass parts or more and 50 mass parts or less are preferable with respect to 100 mass parts of [A] component, and 20 mass parts or more and 40 mass parts or less are more preferable.

<[C] acid generator>
The radiation sensitive composition of the present invention contains a [C] acid generator together with the above [A] component and [B] component. This acid generator is a compound capable of releasing an acidic active substance that acts as a catalyst when accelerating the crosslinking and curing of the [A] alkali-soluble resin by applying energy. The energy that causes the generation of acid from the acid generator may be light or heat, and may be sensitive to either energy. By using such an acid generator, the hardness and solvent resistance of the resulting cured film can be further improved. Examples of the light applied to the acid generator include visible light, ultraviolet light, and far ultraviolet light. The heat includes infrared rays.

  In the formation of a cured film using the radiation-sensitive composition, if the emphasis is on the curing reaction at the time of exposure, an acid generator that is more sensitive to light than heat may be used. If an emphasis is placed on the curing reaction in the heating step after development (hereinafter also simply referred to as “post-bake”), an acid generator that is more sensitive to heat than light may be used. In addition, as an acid generator when emphasizing a curing reaction by heat, an acid active substance is not released at the time of pre-baking at a relatively low temperature (for example, 70 to 120 ° C.) in the coating film forming process of the radiation-sensitive composition, What has the property to discharge | release an acidic active substance at the time of the post-baking of comparatively high temperature (for example, 120-180 degreeC) in the heating process after image development is preferable. When using an acid generator that is sensitive to both light and heat, adjust the exposure amount and exposure time during exposure, and the heating temperature and heating time during post-baking to advance the curing reaction at the desired stage. Can do.

  Examples of the acid generator include diphenyliodonium salts, triphenylsulfonium salts, sulfonium salts, benzothiazonium salts, ammonium salts, phosphonium salts, onium salts such as tetrahydrothiophenium salts, and sulfonimide compounds.

  Examples of diphenyliodonium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyl Iodonium butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarce Bis (4-tert-butylphenyl) iodonium trifluorometa Examples include sulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium camphorsulfonic acid, and the like. .

  Examples of triphenylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, triphenyl Examples include sulfonium butyl tris (2,6-difluorophenyl) borate.

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

As these sulfonium salts,
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, etc .;

  Examples of benzylsulfonium salts include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, and benzyl-4-methoxyphenylmethyl. Sulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethyl Sulfonium hexafluorophosphate, etc .;

  Examples of dibenzylsulfonium salts include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexa Fluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4 -Hydroxyphenylsulfonium hexafluorophosphate and the like;

  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 benzothiazonium salts include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-methoxy Benzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, and the like.

  Examples of tetrahydrothiophenium salts include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 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, 2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydro Ofenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4,7-dibutoxy-1 -Naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate and the like.

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide (trade name “SI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) succinimide (trade name “SI-”). 106 "(manufactured by Midori Chemical Co., Ltd.)), N- (4-methylphenylsulfonyloxy) succinimide (trade name" SI-101 "(manufactured by Midori Chemical Co., Ltd.)), N- (2-trifluoromethylphenyl) Sulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide N- (2-fluoropheny Sulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide (trade name “PI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) diphenylmaleimide, 4-methylphenylsulfonyloxy ) Diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (phenylsulfonyl) Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide (trade name “NDI-100” (manufactured by Midori Chemical Co., Ltd.)), N- (4-methylphenylsulfonyloxy) ) Bishik [2.2.1] Hept-5-ene-2,3-dicarboxylimide (trade name “NDI-101” (manufactured by Midori Chemical Co., Ltd.)), N- (trifluoromethanesulfonyloxy) bicyclo [2. 2.1] Hept-5-ene-2,3-dicarboxylimide (trade name “NDI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (nonafluorobutanesulfonyloxy) bicyclo [2.2. 1] Hept-5-ene-2,3-dicarboxylimide (trade name “NDI-109” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) bicyclo [2.2.1] hept- 5-ene-2,3-dicarboxylimide (trade name “NDI-106” (manufactured by Midori Chemical Co., Ltd.)),

  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-trifluoromethylphenylsulfonyloxy) bicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabi Chlo [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 Trifluoromethylphenylsulfonyloxy) 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 (trade name “NAI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (camphor Sulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-106” (manufactured by Midori Chemical Co., Ltd.)), N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-101” (Midori Chemical) )), N- (phenylsulfonyloxy) naphthyl dicarboxylimide (product) Name “NAI-100” (manufactured by Midori Chemical Co., Ltd.)), N- (2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide, N— (Pentafluoroethylsulfonyloxy) naphthyl dicarboxylimide, N- (heptafluoropropylsulfonyloxy) naphthyl dicarboxylimide, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-109” (Midori Chemical) N- (Ethylsulfonyloxy) naphthyl dicarboxylimide, N- (propylsulfonyloxy) naphthyl dicarboxylimide, N- (butylsulfonyloxy) naphthyl dicarboxylimide (trade name “ AI-1004 "(manufactured by Midori Chemical Co., Ltd.)), N- (pentylsulfonyloxy) naphthyl dicarboxylimide, N- (hexylsulfonyloxy) naphthyl dicarboxylimide, N- (heptylsulfonyloxy) naphthyl dicarboxylimide, N- (octylsulfonyloxy) naphthyl dicarboxylimide, N- (nonylsulfonyloxy) naphthyl dicarboxylimide, etc. are mentioned.

  Among these acid generators, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, and tetrahydrothiophenium salt are preferably used from the viewpoint of improving the hardness and solvent resistance of the obtained cured film. Among these, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium Hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexa Fluorophosphate, 1- (4,7-dibutoxy-1 Naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylic imide is preferably used.

  [C] An acid generator may be used individually by 1 type, and may be used in combination of 2 or more type. The amount when the component [C] is used is preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the component [A]. By making the usage-amount of a [B] component into the said range, the hardness and solvent resistance of the cured film formed using the radiation sensitive composition can be improved, and also the deposit of a deposit in the formation process of a coating film Generation | occurrence | production can be prevented and coating film formation can be made easy.

<Compound [D]>
Compound [D] is an unsaturated dicarboxylic acid anhydride derivative. When the radiation-sensitive composition contains [E] photoradical polymerization initiator described later, it becomes a copolymerization component with compound [B]. .

  Specific examples of the unsaturated dicarboxylic acid anhydride derivative include maleic anhydride, maleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-pentylmaleimide, N-hexylmaleimide, and N-heptylmaleimide. N-octylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N-norbornylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N-naphthylmaleimide and the like. Compound [D] can be used individually or in combination of 2 or more types.

  Preferable examples of the structural unit represented by the above formula (2) include maleic anhydride, N-cyclohexylmaleimide, and N-phenylmaleimide.

  In the radiation-sensitive composition, the content of the [D] component may be determined in consideration of the hardness of the target dura and the like and solvent resistance. The content of the component [D] is preferably 10 parts by mass or more and 50 parts by mass or less, and more preferably 20 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the total amount of the [A] polymer. When the content of the component [D] is in the above range, the radiation-sensitive composition exhibits moderate alkali solubility upon irradiation with light, and improves the hardness and solvent resistance of the resulting cured film and the like. it can.

<[E] Photoradical polymerization initiator>
[E] component used for the radiation sensitive composition of this invention is radical photopolymerization initiator. The radical photopolymerization initiator is not particularly limited as long as it is a component that generates an active species capable of initiating polymerization of the ethylenically unsaturated double bond of the compound [B] in response to light. Examples of such radical photopolymerization initiators include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and the like. As the light with which the component [E] is irradiated, the light used for the acid generator is suitable.

  Examples of O-acyloxime compounds used as photoradical polymerization initiators include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O— Acetyloxime), 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like.

  Preferred examples of these O-acyloxime compounds include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone -1- [9-Ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime). These O-acyloxime compounds can be used alone or in admixture of two or more.

  Examples of the acetophenone compound used as the photo radical polymerization initiator include an α-aminoketone compound and an α-hydroxyketone compound.

  Examples of α-aminoketone compounds include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and the like can be mentioned.

  Examples of α-hydroxyketone compounds include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, and the like.

  Of these acetophenone compounds, α-aminoketone compounds are preferred, such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl). ) -1- (4-morpholin-4-yl-phenyl) -butan-1-one is particularly preferred. These acetophenone compounds can be used alone or in admixture of two or more.

  Examples of the biimidazole compound used as the photo radical polymerization initiator include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2. '-Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) ) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'- Examples include tetraphenyl-1,2'-biimidazole.

  Among the above-mentioned biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2, 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 5'-tetraphenyl-1,2'-biimidazole is preferred, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole Is particularly preferred. These biimidazole compounds can be used alone or in admixture of two or more.

  In the radiation-sensitive composition of the present invention, when a biimidazole compound is used as the [C] radical photopolymerization initiator, an aliphatic or aromatic compound having a dialkylamino group (hereinafter, “ Amino sensitizer ") can be added.

  Examples of such amino sensitizers include 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone. Of these amino sensitizers, 4,4'-bis (diethylamino) benzophenone is particularly preferred. The amino sensitizers can be used alone or in admixture of two or more.

  Furthermore, when a biimidazole compound and an amino sensitizer are used in combination, a thiol compound can be added as a hydrogen radical donor. A biimidazole compound is sensitized by an amino sensitizer and cleaved to generate an imidazole radical, but may not exhibit high polymerization initiation ability as it is. However, by adding a thiol compound to a system in which a biimidazole compound and an amino sensitizer coexist, a hydrogen radical is donated from the thiol compound to the imidazole radical. As a result, the imidazole radical is converted to neutral imidazole, and a component having a sulfur radical having a high polymerization initiating ability is generated, thereby increasing the curing reactivity during exposure of the radiation-sensitive composition, As a result, a cured film having desired characteristics can be easily formed.

Examples of such thiol compounds include
Aromatic thiol compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole;
Aliphatic monothiol compounds such as 3-mercaptopropionic acid and methyl 3-mercaptopropionate;
Bifunctional or higher functional aliphatic thiol compounds such as pentaerythritol tetra (mercaptoacetate) and pentaerythritol tetra (3-mercaptopropionate) are listed. Of these thiol compounds, 2-mercaptobenzothiazole is particularly preferable.

  When a biimidazole compound and an amino sensitizer are used in combination in the radiation-sensitive composition, the addition amount of the amino sensitizer is preferably 0.1 to 50 mass with respect to 100 parts by mass of the biimidazole compound. Part, more preferably 1 to 20 parts by mass. By setting the addition amount of the amino sensitizer to 0.1 to 50 parts by mass, the curing reactivity upon exposure of the radiation-sensitive composition is further enhanced.

  Moreover, when using together a biimidazole compound, an amino-type sensitizer, and a thiol compound, as addition amount of a thiol compound, Preferably it is 0.1-50 mass parts with respect to 100 mass parts of biimidazole compounds, More preferably, it is 1-20 mass parts. By setting the addition amount of the thiol compound to 0.1 to 50 parts by mass, the curing reactivity during exposure is further improved, and it becomes easier to obtain a cured film having a desired shape.

  The photo radical polymerization initiator preferably contains at least one selected from the group consisting of an O-acyloxime compound and an acetophenone compound, and is at least one selected from the group consisting of an O-acyloxime compound and an acetophenone compound. More preferably, it contains seeds as well as a biimidazole compound.

  The amount of the radical photopolymerization initiator used is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of [A] alkali-soluble resin. By making the usage-amount of an [E] component into the said range, the curing reactivity at the time of exposure of a radiation sensitive composition can be improved.

  Further, the ratio of the O-acyloxime compound and the acetophenone compound in the photoradical polymerization initiator is preferably 40% by mass or more, more preferably based on the total amount of the photoradical polymerization initiator of the [E] component. It is 45 mass% or more, Most preferably, it is 50 mass% or more. By using the O-acyloxime compound and the acetophenone compound at such a ratio, high curing reactivity can be obtained even in the case of a low exposure amount, and as a result, a cured film having more excellent hardness and solvent resistance is formed. It becomes possible.

<Other optional components>
The radiation-sensitive composition of the present invention preferably comprises the above-mentioned [A], [B] and [C] components as essential components, and further contains a [D] component and / or [E] component. Correspondingly, [F] a crosslinking aid which is an imidazole ring-containing compound, [G] a polymerizable compound having at least one ethylenically unsaturated double bond (excluding the [B] component and the [D] component), [ H] surfactant and [I] adhesion assistant can be contained.

<[F] Crosslinking aid>
[F] The crosslinking aid of the component is an imidazole ring-containing compound represented by the following formula (7).

（式（７）中、Ｚ^１、Ｚ^２、Ｚ^３及びＲ^１０は、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜２０の直鎖状、分岐状又は環状の炭化水素基を示し、Ｚ^２とＺ^３は互いに連結して環を形成してもよい。）

(In Formula (7), Z < ¹ >, Z < ² >, Z < ³ > and R < ¹⁰ > are respectively independently a C1-C20 linear, branched or cyclic which may have a hydrogen atom or a substituent. And Z ² and Z ³ may be linked to each other to form a ring.)

As a specific example of the hydrocarbon group in the formula (7),
Methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group N-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group An alkyl group having 1 to 20 carbon atoms such as n-octadecyl group, n-nonadecyl group, n-eicosyl group;
A cycloalkyl group having 3 to 20 carbon atoms such as a cyclopentyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group;
Aryl groups having 6 to 20 carbon atoms such as phenyl group, toluyl group, benzyl group, methylbenzyl group, xylyl group, mesityl group, naphthyl group, anthryl group;
Examples thereof include a bridged alicyclic hydrocarbon group having 6 to 20 carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclododecyl group, an adamantyl group, a methyladamantyl group, an ethyladamantyl group, and a butyladamantyl group.

The hydrocarbon group may be substituted. Specific examples of the substituent include
A hydroxyl group;
Carboxyl group;
Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl A hydroxyalkyl group having 1 to 4 carbon atoms such as a 4-hydroxybutyl group;
An alkoxy group having 1 to 4 carbon atoms such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group;
A cyano group;
A cyanoalkyl group having 2 to 5 carbon atoms such as a cyanomethyl group, a 2-cyanoethyl group, a 3-cyanopropyl group, a 4-cyanobutyl group;
An alkoxycarbonyl group having 2 to 5 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, or a t-butoxycarbonyl group;
An alkoxycarbonylalkoxy group having 3 to 6 carbon atoms such as a methoxycarbonylmethoxy group, an ethoxycarbonylmethoxy group, or a t-butoxycarbonylmethoxy group;
Halogen atoms such as fluorine and chlorine;
Examples thereof include fluoroalkyl groups such as a fluoromethyl group, a trifluoromethyl group, and a pentafluoroethyl group.

In the above formula (7), Z ² and Z ³ may be connected to each other to form a cyclic structure, preferably an aromatic ring, or a saturated or unsaturated ring structure having 2 to 20 carbon atoms. As the nitrogen-containing heterocycle represented by the formulas (7) and (8), for example, a benzimidazole ring may be formed as in the case where the following formula (8) is employed.

（式（８）中、Ｗは、互いに独立して、置換基を有していてもよい炭素数１〜２０の直鎖状、分岐状又は環状の炭化水素基を示す。式中の点線は、上記式（７）におけるイミダゾリル環中の、Ｚ^２とＺ^３が結合している炭素原子間の二重結合を示すものである。）

(In Formula (8), W represents a C1-C20 linear, branched or cyclic hydrocarbon group which may have a substituent independently of each other. The dotted line in the formula is And represents a double bond between carbon atoms to which Z ² and Z ³ are bonded in the imidazolyl ring in the above formula (7).)

In addition, as a hydrocarbon group of W of Formula (8), the thing similar to the hydrocarbon group in the said Formula (7) can be mentioned. By using a compound in which Z ² and Z ³ are linked to each other to form a benzimidazole ring, a radiation-sensitive composition having high curability can be obtained.

  Particularly preferred compounds of the [F] component include 2-phenylbenzimidazole, 2-methylimidazole, and 2-methylbenzimidazole. The [F] component imidazole ring-containing compound can be used alone or in admixture of two or more. A typical use amount of the imidazole ring-containing compound of the [F] component which is an optional component is 0.01 to 10 parts by mass with respect to 100 parts by mass of the alkali-soluble resin of the [A] component. By making the usage-amount of the [F] component in a radiation sensitive composition into 0.01-10 mass parts, the interlayer insulation film which has still higher surface hardness can be obtained.

<[G] Polymerizable compound having at least one ethylenically unsaturated double bond>
As the polymerizable compound having at least one ethylenically unsaturated double bond as the component [G], for example, monofunctional (meth) acrylate, bifunctional (meth) acrylate, trifunctional or higher (meth) acrylate is preferably used. Can be used.

  Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl- Examples include 2-hydroxypropyl phthalate. Examples of commercial products of these monofunctional (meth) acrylates include Aronix M-101, M-111, M-114 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, TC-120S. (Nippon Kayaku Co., Ltd.), Biscote 158, 2311 (Osaka Organic Chemical Co., Ltd.) and the like.

  Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate. As a commercial item of these bifunctional (meth) acrylates, for example, Aronix M-210, M-240, M-6200 (manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, R -604 (manufactured by Nippon Kayaku Co., Ltd.), Viscoat 260, 312, and 335HP (manufactured by Osaka Organic Chemical Industries, Ltd.).

  Examples of the tri- or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, Examples thereof include dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Commercially available products of these tri- or higher functional (meth) acrylates include, for example, Aronix M-309, M-400, M-405, M-450, M-7100, M-8030, and M- 8060 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-60, DPCA-120 (above, Nippon Kayaku Co., Ltd.), Biscoat 295, 300, 360, GPT, 3PA, 400 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.).

  Of these (meth) acrylates, trifunctional or higher functional (meth) acrylates are preferable from the viewpoint of improving the curability of the radiation-sensitive composition. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are particularly preferable. These monofunctional, bifunctional, or trifunctional or higher (meth) acrylates are used alone or in combination.

  The use ratio of the [G] component in the radiation-sensitive composition is preferably 50 parts by mass or less, more preferably 30 parts by mass or less with respect to 100 parts by mass of the [A] alkali-soluble resin. By including the [G] component at such a ratio, it is possible to improve the curability of the radiation-sensitive composition and to suppress the occurrence of film roughness in the coating film forming process on the substrate. It becomes.

<[H] surfactant>
In the radiation-sensitive composition, a surfactant can be used as the [H] component in order to further improve the coating property at the time of coating film formation. Examples of the surfactant that can be suitably used include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant.

  Examples of fluorosurfactants include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,1) 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether and other fluoroethers; sodium perfluorododecylsulfonate; 1,1,2 , 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexaph Fluoroalkanes such as orodecane; sodium fluoroalkylbenzenesulfonates; fluoroalkyloxyethylene ethers; fluoroalkylammonium iodides; fluoroalkylpolyoxyethylene ethers; perfluoroalkylpolyoxyethanols; perfluoroalkylalkoxylates And fluorine-based alkyl esters.

  Commercially available products of these fluorosurfactants include BM-1000, BM-1100 (manufactured by BM Chemie), MegaFack F142D, F172, F173, F183, F178, F191, F191, and F471. (Above, Dainippon Ink & Chemicals, Inc.), Florard FC-170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M Limited), Surflon S-112, S-113 S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (Manufactured by Asahi Glass Co., Ltd.), F-top EF301, 303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.) and the like.

  Specific examples of the silicone-based surfactant are commercially available product names such as DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SH 8400 FLUID, SZ-6032 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above, GE Toshiba) Silicone Co., Ltd.).

  Nonionic surfactants include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like. Polyoxyethylene aryl ethers; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; (meth) acrylic acid copolymers and the like. As a typical commercially available nonionic surfactant, Polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.). These surfactants can be used alone or in combination of two or more.

  In the radiation-sensitive composition, the surfactant of the [H] component is used in an amount of preferably 5 parts by mass or less, more preferably 2 parts by mass or less, with respect to 100 parts by mass of the [A] alkali-soluble resin. [H] By using the surfactant in an amount of 5 parts by mass or less, it is possible to suppress film roughness when a coating film is formed on the substrate.

<[I] Adhesion aid>
In the radiation-sensitive composition of the present invention, an adhesion assistant as component [I] can be used to improve the adhesion to the substrate. As such an adhesion assistant, a functional silane coupling agent is preferably used. Examples of functional silane coupling agents include silane coupling agents having reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, and epoxy groups (preferably oxiranyl groups). Specific examples of functional silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxy Examples thereof include propyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. In the radiation-sensitive composition, such an adhesion assistant is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 3 parts by mass or more and 15 parts by mass or less with respect to [A] 100 parts by mass of the alkali-soluble resin. Used in the amount of. By adjusting the amount of the adhesion aid to 1 part by mass or more and 20 parts by mass or less, the adhesion between the formed interlayer insulating film and the substrate is improved.

<Radiation sensitive composition>
The radiation-sensitive composition of the present invention comprises the above-mentioned [A], [B] and [C] components, and [D] and [E] components as suitable components, and optional components ([F] to [I]) It is prepared by mixing the components) uniformly. Usually, the radiation-sensitive composition is preferably used after being dissolved in an appropriate solvent and stored in a solution state. For example, a solution-type radiation-sensitive composition can be prepared by mixing the [A], [B], and [C] components, and the above-described preferred components and optional components in a predetermined ratio in a solvent. it can.

  The solvent for preparing the radiation-sensitive composition is not particularly limited as long as it dissolves the above components uniformly and does not react with the components. Examples of such a solvent include the same solvents as those exemplified as the solvent that can be used for producing the [A] alkali-soluble resin.

  Among such solvents, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters, and diethylene glycol alkyl ethers from the standpoints of solubility of each component, non-reactivity with each component, ease of film formation, etc. Is preferably used. Among these solvents, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether , Propylene glycol monomethyl ether acetate, methyl 2- or 3-methoxypropionate, or ethyl 2- or 3-ethoxypropionate can be particularly preferably used.

  Furthermore, in order to improve the in-plane uniformity of the film thickness of the coating film to be formed, a high boiling point solvent can be used in combination with the above solvent. Examples of the high-boiling solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl. Ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, Examples include phenyl cellosolve acetate. Of the high boiling point solvents, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.

  When a high boiling point solvent is used in combination as a solvent for the radiation-sensitive composition, the amount used is 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, based on the total amount of the solvent. it can. By setting the use ratio of the high boiling point solvent to 50% by mass or less, it is possible to improve the film thickness uniformity of the coating film and at the same time suppress the decrease in radiation sensitivity.

  When preparing the radiation-sensitive composition in a solution state, components other than the solvent in the solution (that is, [A] alkali-soluble resin and [B] compound having a specific structure and [C] acid generator, and other optional components The ratio of the total amount of the components can be arbitrarily set according to the purpose of use and the desired film thickness, but is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 It is -35 mass%. The solution of the radiation-sensitive composition thus prepared can be used after being filtered using a Millipore filter having a pore size of about 0.2 μm.

<Method for forming cured film>
Next, a method for forming a cured film of the present invention using the above radiation sensitive composition will be described. The method includes the following steps in the order described below.
(1) The process of forming the coating film of the radiation sensitive composition of this invention on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) a step of developing the coating film irradiated with light in step (2), and (4) a step of heating the coating film developed in step (3).

(1) The process of forming the coating film of a radiation sensitive composition on a board | substrate In the process of said (1), apply | coating the solution of the radiation sensitive composition of this invention to a substrate surface, Preferably prebaking is performed. To remove the solvent and form a coating film of the radiation-sensitive composition. Examples of the types of substrates that can be used include glass substrates, silicon wafers, plastic substrates, and substrates on which various metals are formed. When applied to a flexible display or the like, a plastic substrate having appropriate flexibility and strength can be suitably used. Examples of such a plastic substrate material include polyethylene terephthalate (PET), polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide.

  The method for applying the solution of the composition is not particularly limited. For example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an ink jet method may be used. Can be adopted. Among these coating methods, spin coating, slit die coating, and bar coating are preferable. The pre-baking conditions vary depending on the type of each component, the use ratio, and the like, but can be, for example, 60 to 90 ° C. for 30 seconds to 10 minutes. The film thickness of the coating film to be formed is preferably 0.1 to 8 μm, more preferably 0.1 to 6 μm, and further preferably 0.1 to 4 μm as a value after pre-baking.

(2) Step of irradiating light to at least a part of the coating film In the step (2), the formed coating film is irradiated with light through a mask having a predetermined pattern. The light used at this time is preferably light used for the acid generator. Examples of the ultraviolet light among the above light include g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet light include a KrF excimer laser. Among these lights, ultraviolet rays are preferable, and among the ultraviolet rays, light containing g-line and / or i-line is particularly preferable. The exposure amount is preferably 30 to 1,500 J / m ² .

(3) Development step (3) In the development step, the coating film irradiated with light in the step (2) is developed to remove the irradiated portion and form a desired pattern. it can. Examples of the developer used for the development processing include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propyl. Amine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5 An aqueous solution of an alkali (basic compound) such as diazabicyclo [4,3,0] -5-nonane can be used. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the above alkaline aqueous solution, or an alkaline aqueous solution containing a small amount of various organic solvents for dissolving the radiation-sensitive composition is used as a developer. Can be used.

  As a developing method, for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method or the like can be used. The development time varies depending on the composition of the radiation-sensitive composition, but can be, for example, 30 to 120 seconds. After the development step, the patterned thin film is rinsed with running water.

(4) Heating Step Next, in (4) the heating step, the thin film is cured by heating and curing (post-baking) the thin film using a heating device such as a hot plate or an oven. The temperature in this heating step is preferably 120 to 180 ° C, particularly preferably 120 to 150 ° C. The heating time varies depending on the type of heating equipment, but for example, it can be 5 to 40 minutes when heat treatment is performed on a hot plate, and 30 to 80 minutes when heat treatment is performed in an oven, Particularly preferably, it is within 30 minutes when heat treatment is performed on a hot plate, and within 60 minutes when heat treatment is performed in an oven. In this way, a patterned thin film corresponding to the target cured film can be formed on the surface of the substrate.

<Curing film as protective film for display element or interlayer insulating film>
As described above, the cured film of the present invention formed by heating at a low temperature has sufficient surface hardness and excellent solvent resistance and voltage holding ratio, as will be apparent from the examples described later. ing. Therefore, this cured film is suitably used as a protective film for display elements of display devices and an interlayer insulating film.

  EXAMPLES Hereinafter, although a synthesis example and an Example demonstrate this invention further in detail, this invention is not limited to these Examples.

Hereinafter, the mass average molecular weight (Mw) and the number average molecular weight (Mn) of the copolymer were measured by gel permeation chromatography (GPC) under the following conditions.
Apparatus: GPC-101 (made by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Column temperature: 40 ° C
Elution solvent: Tetrahydrofuran (Wako Pure Chemical Industries, Ltd.)
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection amount: 100 μm
Detector: Differential refractometer Standard material: Monodispersed polystyrene The solution viscosity of the radiation-sensitive composition was measured at 30 ° C. using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.).

<[A] Synthesis of alkali-soluble resin>
[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) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 16 parts by weight of methacrylic acid, 16 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 58 parts by weight of methyl methacrylate, and 10 parts by weight of styrene were charged, and after nitrogen substitution, Stirring started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a resin solution containing an alkali-soluble resin [A-1]. The obtained alkali-soluble resin [A-1] had a polystyrene-reduced mass average molecular weight (Mw) of 8,000 and a molecular weight distribution (Mw / Mn) of 2.3. Further, the solid content concentration of the resin solution here (referring to the ratio of the mass of the copolymer contained in the polymer solution to the total mass of the polymer solution; the same shall apply hereinafter) was 34.4% by mass. .

[Synthesis Example 2]
A flask equipped with a condenser and a stirrer was charged with 8 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 20 parts by mass of methacrylic acid, 45 parts by mass of n-lauryl methacrylate, and 35 parts by mass of styrene 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 resin solution containing an alkali-soluble resin [A-2]. The obtained alkali-soluble resin [A-2] had a polystyrene equivalent weight average molecular weight (Mw) of 8,000 and a molecular weight distribution (Mw / Mn) of 2.3. Moreover, the solid content concentration of the resin solution here was 31.9 mass%.

[Comparative Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 18 parts by mass of 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane under a nitrogen stream and dissolved in 75 parts by mass of N-methyl-2-pyrrolidone. Then, 9.5 parts by mass of 1,2,3,4-cyclobutanetetracarboxylic anhydride was added, and this was stirred at room temperature for 8 hours to carry out a polymerization reaction. The obtained polyamic acid solution was diluted to 10% by mass with N-methyl-2-pyrrolidone. To this solution, 26 parts by mass of acetic anhydride and 16 parts by mass of pyridine were added as an imidization catalyst, reacted at room temperature for 30 minutes, and then reacted at 40 ° C. for 90 minutes to obtain a polyimide solution. This solution was poured into a mixed solution of a large amount of methanol and water, and the resulting white precipitate was filtered and dried to obtain a white polyimide [P-1] powder. This polyimide powder was dissolved in propylene glycol monomethyl ether to obtain a solution containing polyimide [P-1].

<Preparation of radiation-sensitive composition>
[Examples 1 to 11 and Comparative Examples 1 to 4]
[A] alkali-soluble resin obtained in the above synthesis example and [B] to [E] components were mixed in the amounts shown in Table 1 below, and propylene glycol monomethyl ether so that the solid content concentration was 30% by mass. After dissolving in acetate, the solution was filtered through a Millipore filter having a pore size of 0.5 μm to prepare a composition solution.

In Table 1, the symbol of a component shows the following compound.
B-1: 3-ethyl-3- (vinyloxymethyl) oxetane B-2: 3-ethyl-3- (6-vinyloxyhexyl) oxetane B-3: 3-phenyl-3- (6-vinyloxyhexyl) ) Oxetane b-1: n-butyl vinyl ether (comparative example)
C-1: benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate C-2: 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate C-3: 2-nitrobenzylcyclohexyl carbamate D-1: N-cyclohexylmaleimide D-2: Maleic anhydride d-1: Succinic anhydride E-1: 1- [9-Ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate (trade name IRGACURE OXE 02, manufactured by Ciba Specialty Chemicals)
E-2: 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one (trade name Irgacure 379, manufactured by Ciba Specialty Chemicals)
P-2: Adduct of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate and ε-caprolactone (trade name Celoxide 2081, manufactured by Daicel Chemical Industries, Ltd.)

Compound B-1 is represented by the following formula (in formula (1), X is a methylene group, R ¹ is a hydrogen atom, and R ² is an ethyl group).
3-ethyl-3- (vinyloxymethyl) oxetane

Compound B-2 is represented by the following formula (in formula (1), X is a hexamethylene group, R ¹ is a hydrogen atom, and R ² is an ethyl group).
3-ethyl-3- (6-vinyloxyhexyl) oxetane

Compound B-3 is represented by the following formula (in formula (1), X is a methylene group, R ¹ is a hydrogen atom, and R ² is a phenyl group).
3-Phenyl-3- (6-vinyloxyhexyl) oxetane

<Characteristic evaluation as cured film>
Using the radiation-sensitive composition prepared as described above, various properties as a cured film were evaluated as follows.

[Evaluation of radiation sensitivity]
Except Example 9, after apply | coating the said composition using a spinner on the silicon substrate, it prebaked on a hotplate at 90 degreeC for 2 minute (s), and formed the coating film with a film thickness of 3.0 micrometers. The obtained coating film was irradiated with a predetermined amount of ultraviolet rays by a mercury lamp through a pattern mask having a line and space pattern having a width of 10 μm. Subsequently, after developing for a predetermined time at 25 ° C. with a 0.05 wt% aqueous solution of potassium hydroxide, it was washed with pure water for 1 minute. At this time, the minimum ultraviolet irradiation amount capable of forming a line and space pattern having a width of 10 μm was measured. When this value is less than 800 J / m ² , it can be said that the sensitivity is good. This value is shown in Table 2 as radiation sensitivity.

  In Example 9, a PET film (Teijin Tetron film O3, thickness 188 μm) was used instead of the silicon substrate, and a coating film was formed by a bar coater. Pre-baking was performed in a clean oven at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Subsequent evaluation was performed in the same manner as in the other examples except for evaluation of voltage holding ratio.

[Evaluation of pattern shape]
In the same manner as in the above [Evaluation of Radiation Sensitivity], the above composition was applied onto a silicon substrate using a spinner, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm Formed. The obtained coating film was irradiated with a predetermined amount of ultraviolet rays with a mercury lamp through a pattern mask having a square pattern with a side of 50 μm, and then predetermined with a 0.05 wt% potassium hydroxide aqueous solution at 25 ° C. After time development, the substrate was washed with pure water for 1 minute to form a square pattern. The edge shape of the obtained square pattern was observed with a scanning electron microscope, and the pattern shape was evaluated based on the angle α between the substrate surface and the pattern edge shown in FIG. At this time, when the angle α is 30 degrees or more, it can be said that the pattern shape is good. On the other hand, when the angle α is less than 30 degrees, the pattern shape is bad. The reason why the angle α is less than 30 degrees and the skirt at the end of the pattern becomes long is that the solubility in the developer is low.

[Evaluation of solvent resistance]
The above composition was applied onto a silicon substrate using a spinner and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays by a mercury lamp so that the cumulative irradiation amount was 1,000 J / m ² . Next, this silicon substrate is heated on a hot plate at 150 ° C. for 30 minutes with respect to the samples of the examples and comparative examples, so that the coating film is heat-treated, and the thickness (T1) of the obtained cured film is determined. It was measured. And after immersing the silicon substrate in which this cured film was formed in dimethyl sulfoxide temperature-controlled at 70 degreeC for 20 minutes, the film thickness (t1) of the said cured film was measured, and the film thickness change rate by immersion {(T1-T1) / T1} × 100 [%] was calculated. It can be said that the solvent resistance is excellent when the absolute value of this value is less than 5%. The results are shown in Table 2.

[Evaluation of pencil hardness (surface hardness)]
About the board | substrate which has the cured film formed in said [solvent resistance evaluation], the pencil hardness (surface hardness) of the cured film was measured by the 8.4.1 pencil scratch test of JIS K-5400-1990. When this value is 3H or more, the surface hardness as a cured film is good, and it can be said that the radiation-sensitive composition used for forming the cured film has sufficient curability. The results are shown in Table 2.

[Evaluation of voltage holding ratio]
Examples 1 to 11 and Comparative Examples using a spinner on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed on the surface and ITO (indium-tin oxide alloy) electrodes were deposited in a predetermined shape After the compositions 1 to 3 were applied, prebaking was performed on a 90 ° C. hot plate for 2 minutes to form a coating film having a thickness of 2.0 μm. Development was performed by a dip method at 25 ° C. for 80 seconds in a 2.38 mass% tetramethylammonium hydroxide aqueous solution. Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an integrated dose of 3,000 J / m ² without using a photomask. Subsequently, this substrate was heat-treated in a clean oven at 150 ° C. for 30 minutes under a post-bake temperature condition to form a cured film.

  Next, after spraying a 5.5 μm diameter bead spacer on the substrate having this cured film, the liquid crystal injection port is placed in a state where this is opposed to a soda glass substrate on which the ITO electrode is deposited in a predetermined shape. The four sides are bonded together using a sealing agent mixed with 0.8 mm glass beads, and a liquid crystal cell is sealed by injecting liquid crystal MLC6608 (trade name) manufactured by Merck and sealing the liquid crystal injection port. Produced.

This liquid crystal cell is placed in a constant temperature layer of 60 ° C., and a liquid crystal voltage holding ratio measurement system VHR-1A (trade name) manufactured by Toyo Technica is used to form a square wave with an applied voltage of 5.5 V and a measurement frequency of 60 Hz. The voltage holding ratio of the cell was measured. The results are shown in Table 2. Here, the voltage holding ratio is a value obtained by the following formula. The lower the value of the voltage holding ratio of the liquid crystal cell, the higher the possibility of causing a problem called “burn-in” when forming the liquid crystal panel. On the other hand, it can be said that the higher the value of the voltage holding ratio, the lower the possibility of occurrence of “burn-in” and the higher the reliability of the liquid crystal panel.
Voltage holding ratio (%) = (liquid crystal cell potential difference after 16.7 milliseconds from the reference time) / (voltage applied at 0 milliseconds [reference time]) × 100

  From the results shown in Table 2, the radiation-sensitive compositions prepared in Examples 1 to 11 have high radiation sensitivity, and can obtain a cured film having high surface hardness by low-temperature heating. It was found that the cured film had excellent solvent resistance and voltage holding ratio. On the other hand, in Comparative Example 1 in which no acid generator was added, pattern formation by exposure and development was not performed, the pattern shape was poor, and the evaluation was poor in all evaluations such as hardness and solvent resistance. In Comparative Example 2 using b-1 which does not have a cyclic ether moiety instead of the [B] component, sufficient curability is not exhibited by heating at a low temperature, and the solvent resistance of the cured film and The voltage holding ratio was also inferior. In Comparative Example 3 using a polyimide solution, pattern formation by exposure and development could not be performed, sufficient curability was not exhibited by heating at a low temperature, and the solvent resistance of the cured film was inferior. Furthermore, in Comparative Example 4 using a diepoxy compound as a polymer, pattern formation by exposure and development was not performed, and the pattern shape was poor. Evaluation of solvent resistance and hardness was not satisfactory. In addition, in Example 11 using succinic anhydride which is a saturated dicarboxylic anhydride instead of the [D] component, the evaluation results were the same as those in Examples 1 and 2 in which the [D] component was not added. Thereby, it turns out that it is preferable to use the specific compound which has an unsaturated double bond as [D] component. That is, it was found that by using the radiation-sensitive composition of the present invention, it is possible to form a cured film that satisfies various properties such as required surface hardness at a lower temperature than before.

  The radiation-sensitive composition of the present invention has good radiation sensitivity, can form a cured film by heating at a low temperature, and can form a cured film having excellent solvent resistance and anti-seizure properties. Therefore, it can be suitably used as a material for forming a cured film such as a protective film for display elements and an interlayer insulating film in display devices including flexible displays.

Claims (8)

[A] alkali-soluble resin,
[B] Radiation-sensitive containing at least one compound selected from the group consisting of compounds represented by the following formulas (1) and (1 ′), and [C] a compound that generates an acid upon application of energy. Sex composition.

(In the formula (1), ^{R 1} is a hydrogen atom or a methyl group, X is a methylene group, an alkylene group having 2 to 20 carbon atoms, a phenylene group or naphthylene group, ^{R 2} represents a hydrogen atom, 1 to carbon atoms 20 alkyl groups, benzyl groups, phenyl groups or tolyl groups.
Wherein (1'), ^{R 1'is} a hydrogen atom or a methyl group, X'is a methylene group, an alkylene group having 2 to 20 carbon atoms, a phenylene group or a naphthylene group, ^{R 2'is} a hydrogen atom, a carbon It is an alkyl group, a benzyl group, a phenyl group, or a tolyl group of formula 1-20. ) [D] The radiation-sensitive composition according to claim 1, further comprising a compound represented by the following formula (2).

(In Formula (2), Y is an oxygen atom or N—R ³ , and R ³ is an alkyl group having 1 to 20 carbon atoms, an alicyclic alkyl group having 4 to 12 carbon atoms, a benzyl group, a phenyl group, A tolyl group or a naphthyl group.) The radiation-sensitive composition according to claim 1 or 2, wherein the [A] alkali-soluble resin contains (a1) a structural unit represented by the following formula (3).

(In formula (3), R ⁴ is a hydrogen atom or a methyl group.) Said [A] alkali-soluble resin is further (a2) at least 1 type of structure selected from the group which consists of a structural unit respectively represented by following formula (4), (5), (6) and (6 '). The radiation sensitive composition of Claim 1, Claim 2, or Claim 3 containing a unit.

(In the formula (4), ^{R 5} is a hydrogen atom or a methyl group, ^{R 6} is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n is an integer from 0 to 12.
In Formula (5), R ⁷ is a hydrogen atom or a methyl group, and n is an integer of 0 to 12.
In Formula (6), R ⁸ is a hydrogen atom or a methyl group, R ⁹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen, and n is an integer of 0 to 12.
In formula (6 ′), R ^{8 ′} is a hydrogen atom or a methyl group, R ^{9 ′} is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen, and n is an integer of 0 to 12. is there. )   [E] The radiation-sensitive composition according to any one of claims 1 to 4, further comprising a photoradical polymerization initiator.   The radiation sensitive composition of any one of Claims 1-5 used in order to form the cured film as a protective film for display elements, or an interlayer insulation film. (1) The process of forming the coating film of the radiation sensitive composition of Claim 6 on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A step of developing the coating film irradiated with light in step (2), and (4) a step of heating the coating film developed in step (3). A cured film formed using the radiation-sensitive composition according to claim 6.

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