TWI493284B - Radiation-sensitive resin composition for forming cured film, method for producing radiation-sensitive resin composition for forming cured film, cured film, method for forming cured film and display element - Google Patents

Description

Method for producing a radiation-sensitive resin composition for forming a cured film, a method for producing a radiation-sensitive resin composition for forming a cured film, a method for forming a cured film, a cured film, and a display element

The present invention relates to a radiation sensitive resin composition for forming a cured film, a method for producing a radiation sensitive resin composition for forming a cured film, a cured film, a method for forming a cured film, and a display element.

An electronic component such as a thin film transistor (TFT) type liquid crystal display element is provided with an interlayer insulating film in order to insulate between wirings arranged in a layer. For example, a TFT type liquid crystal display element is manufactured by a step of forming a transparent electrode film on an interlayer insulating film and forming a liquid crystal alignment film thereon. As the interlayer insulating film, it is required to have sufficient heat resistance and resistance to these conditions due to exposure to a high temperature condition in the formation step of the transparent electrode film and a stripping liquid of the photoresist used in pattern formation of the electrode. Chemically reactive. Further, for the radiation sensitive resin composition for forming such a cured film, it is also required to shorten the radiation irradiation time (i.e., high radiation sensitivity) and to have good storage stability.

Moreover, in recent years, lightweight and compact flexible displays using TFT technology are spreading. As a substrate of a flexible display, a plastic substrate such as polycarbonate has been studied. The plastic substrate stretches and contracts due to heating, and as a result, there is a bad condition that impairs the function of the display. Therefore, research is being conducted to lower the heating step in the manufacture of a flexible display. For example, Japanese Laid-Open Patent Publication No. 2009-4394 discloses a coating liquid for a gate insulating film which is used in a flexible display including a polyimide precursor which can be cured even at a low temperature. However, the coating liquid does not have the ability to form a pattern by exposure and development, and thus it is impossible to form a fine pattern. Further, since the curing reaction is insufficient, the obtained cured film does not have a good level of light transmittance, flatness, linear thermal expansion resistance, and the like in addition to heat resistance and chemical resistance.

Therefore, a strategy of performing a crosslinking reaction by adding an amine compound which can also be used as a hardener of an epoxy-based material at a low temperature is also considered. However, when a general amine compound is added, it may cause a reaction with an epoxy group present in the composition over time, which may deteriorate storage stability.

In view of the above, it is also expected to develop a radiation-sensitive resin composition for forming a cured film which satisfies both storage stability and low-temperature firing and has sufficient radiation sensitivity; heat resistance and chemical resistance as characteristics required for the cured film. A cured film excellent in properties such as reagent properties, light transmittance, flatness, and linear thermal expansion resistance.

Prior art literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2009-4394

The present invention has been made in view of the above circumstances, and an object thereof is to provide a radiation-sensitive resin composition for forming a cured film which simultaneously satisfies storage stability and low-temperature firing and has sufficient radiation sensitivity; heat resistance and chemical resistance A cured film excellent in properties such as reagent properties, light transmittance, flatness, and linear thermal expansion resistance, and a display element excellent in voltage holding ratio.

The invention for solving the above problems is:

A radiation sensitive resin composition for forming a cured film, comprising:

[A] a copolymer having (a1) a carboxyl group-containing structural unit and (a2) an epoxy group-containing structural unit (hereinafter also referred to as "[A] copolymer"),

[B] a polymerizable compound having an ethylenically unsaturated bond (hereinafter also referred to as "[B] polymerizable compound"),

[C] sensitizing radiation polymerization initiator,

[D] a compound having a hydroxyl group or a carboxyl group (hereinafter, also referred to as "[D] compound"), and

[E] an amine compound;

And the viscosity at 25 ° C is 1.0 mPa ‧ s or more and 50 mPa ‧ s or less.

The radiation sensitive resin composition contains an [A] copolymer, an [B] polymerizable compound, and a [C] radiation-sensitive polymerization initiator as an alkali-soluble resin. The radiation-sensitive resin composition as a photosensitive material can easily form a fine and delicate pattern by utilizing radiation-sensitive exposure and development, and has sufficient radiation sensitivity. In addition, since the [D] compound and the [E] amine compound are contained, the viscosity of the radiation sensitive resin composition at 25 ° C can be controlled to be 1.0 mPa ‧ or more and 50 mPa ‧ or less, and can simultaneously satisfy storage stability and low temperature. Burning.

The [E] amine compound is preferably encapsulated in the [D] compound. By forming an amine compound which can encapsulate the [E] amine compound in the [D] compound, at least a part of the crystal cage compound is formed, and the radiation sensitive resin composition can contain a crystal cage compound, which can simultaneously satisfy storage stability and Low temperature firing. That is, in the state in which the [E] amine compound which promotes hardening at room temperature is crystallized, the curing reaction of the epoxy group is hardly performed, and the viscosity of the composition solution is not increased. Therefore, the radiation sensitive resin composition is a composition excellent in storage stability. On the other hand, when the radiation sensitive resin composition is heated to a predetermined temperature or higher, the crystal cage disintegrates to release the [E] amine compound, and the epoxy group-containing resin crosslinks to promote the hardening reaction. Further, in general, when the radiation sensitive resin composition is used in a solution state, in order to ensure solubility, a polar solvent is preferably used. On the other hand, the crystal cage compound is generally in the form of a solid powder. If it is dissolved in a polar solvent such as an alcohol solvent or an ether solvent, the crystal cage may be disintegrated. Therefore, it is considered to be dispersed in a composition solution or the like and used. However, in the radiation-sensitive resin composition, it is considered that the interaction between the carboxyl group and the crystal cage compound in the coexisting [A] copolymer suppresses the disintegration of the cage, and a polar solvent can be used. Further, it is conceivable that due to the above interaction, protons of the carboxyl group are added to the imidazole, and the carboxyl group is anionized to form a carbanion. It is considered that since the carbanion also has high nucleophilicity, it is also possible to achieve a synergistic effect of the cage compound promoting the hardening reaction of the epoxy group in the [A] copolymer.

The compound [D] is at least one compound selected from the group consisting of compounds represented by the following formulas (1) and (2), and the [E] amine compound is preferably an imidazole compound or a benzimidazole compound.

(In the formula (1), X is a single bond, a methylene group or an alkylene group having 2 to 6 carbon atoms. R ¹ to R ⁸ are each independently a hydrogen atom and an alkyl group having 1 to 12 carbon atoms. And a halogen atom, an alkoxy group having 1 to 12 carbon atoms or a phenyl group which may have a substituent.

In the formula (2), R ⁹ is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a nitro group or a hydroxyl group. )

By setting the [D] compound and the [E] amine compound to the above specific compounds, respectively, the cage compound can be efficiently formed.

The compound represented by the above formula (1) is preferably a compound represented by the following formula (1-1).

(In the formula (1-1), X and R ¹ to R ⁸ have the same meanings as in the above formula (1).)

By setting the compound represented by the above formula (1) to the compound represented by the above formula (1-1), the storage stability can be further improved, and the curing at a low temperature can be promoted.

For the radiation sensitive resin composition, at least a part of the [E] amine compound is preferably contained in the [D] compound. By forming a crystal cage compound by incorporating at least a part of the [E] amine compound in the radiation-sensitive resin composition into the [D] compound, storage stability and low-temperature baking can be simultaneously satisfied.

The [C] radiation-sensitive polymerization initiator is preferably at least one selected from the group consisting of an acetophenone compound and an O-mercaptopurine compound. By using the above specific compound as the [C] radiation-sensitive polymerization initiator, it is possible to further improve the heat resistance and the like as a desired property of the cured film even in the case of a low exposure amount.

The radiation sensitive resin composition preferably further contains at least one solvent selected from the group consisting of an alcohol solvent and an ether solvent. By containing the above polar solvent, the radiation sensitive resin composition can be easily dissolved, and it can be considered that, for the present invention, the crystal can be inhibited by interaction with the cage compound even in the case of using a polar solvent as described above. The collapse of the cage.

The radiation-sensitive resin composition having a viscosity at 25 ° C of 1.0 mPa ‧ s or more and 50 mPa ‧ s or less is preferably a mixture of a cage compound obtained by encapsulating the [E] amine compound in the [D] compound [A] The copolymer, the [B] polymerizable compound, and the [C] radiation sensitive polymerization initiator were prepared. If the above steps are utilized, the radiation sensitive resin composition containing the crystal cage compound can be efficiently produced.

The method for forming a cured film of the present invention comprises:

(1) a step of forming a coating film of the radiation sensitive resin composition on a substrate;

(2) a step of irradiating at least a part of the coating film with radiation;

(3) a step of developing a coating film irradiated with the above radiation; and

(4) A step of firing the coating film subjected to the above development.

According to the formation method of the present invention using the radiation-sensitive resin composition, it is possible to form a cured film in which heat resistance, chemical resistance, light transmittance, flatness, and linear thermal expansion resistance are satisfactorily satisfied.

The firing temperature in the above step (4) is preferably 200 ° C or lower. The radiation-sensitive resin composition has both storage stability and sufficient radiation sensitivity while achieving low-temperature firing as described above. Therefore, the radiation sensitive resin composition is suitably used as a material for forming a cured film such as an interlayer insulating film, a protective film, and a separator which are used in a flexible display or the like which is desired to be fired at a low temperature.

The present invention is also preferably a cured film comprising an interlayer insulating film, a protective film or a separator formed of the radiation sensitive resin composition. Further, in the present invention, it is preferable to include a display element including the cured film, and it is possible to achieve an excellent voltage holding ratio.

In the present specification, "firing" means heating a cured film such as an interlayer insulating film, a protective film, and a separator to a desired surface hardness. Further, the "cage compound" refers to a compound in which another guest molecule is encapsulated in a space formed by a host molecule in a molecular unit. The "radiation" in the "radiation-sensitive linear resin composition" is a concept including visible light, ultraviolet light, far ultraviolet light, X-ray, charged particle beam, and the like. Further, the viscosity was measured by using an E-type viscometer (VISCONIC ELD.R manufactured by Toki Sangyo Co., Ltd.), and the viscosity (mPa‧s) of the composition at 25 ° C was measured. Generally, an amine compound is known as a hardening accelerator which promotes a crosslinking reaction of an epoxy compound. In the composition, the [E] amine compound also acts on the epoxy group in the [A] component to promote the crosslinking reaction. In this case, the viscosity of the composition solution increases. When it is 50 mPa·s or more, it is not easy to control the film thickness at the time of coating, and it becomes unsuitable as a radiation-sensitive resin composition for forming a cured film.

In the composition of the present application, since the [D] compound and the [E] amine compound are contained, the viscosity of the radiation sensitive resin composition at 25 ° C can be controlled to 1.0 mPa ‧ s or more and 50 mPa ‧ s or less, which can simultaneously satisfy Storage stability and low temperature firing.

[Effect of the invention]

As described above, the radiation-sensitive resin composition for forming a cured film of the present invention can easily form a fine and delicate pattern while satisfying storage stability and low-temperature firing, and having sufficient radiation sensitivity. Further, the cured film formed of the radiation sensitive resin composition is excellent in heat resistance, chemical resistance, light transmittance, flatness, and linear thermal expansion resistance. Therefore, the radiation sensitive resin composition is suitably used as a material for forming a cured film such as an interlayer insulating film, a protective film, and a separator which are used in a flexible display or the like which is desired to be fired at a low temperature. Further, in the present invention, it is preferable to include a display element including the cured film, and it is possible to achieve an excellent voltage holding ratio.

<The radiation sensitive resin composition for forming a cured film>

The radiation sensitive resin composition for forming a cured film of the present invention contains [A] copolymer, [B] polymerizable compound, [C] radiation sensitive polymerization initiator, [D] compound, and [E] amine compound, 25 ° C The viscosity below is 1.0 mPa‧s or more and 50 mPa‧s or less. Further, the radiation-sensitive resin composition may contain an optional component as long as the effects of the present invention are not impaired. Each component will be described in detail below.

<[A] copolymer>

The [A] copolymer contained in the radiation sensitive resin composition has (a1) a carboxyl group-containing structural unit and (a2) an epoxy group-containing structural unit. As a method of obtaining the [A] copolymer, for example, an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride (hereinafter also referred to as a carboxyl group-containing structural unit (carboxy group including an acid anhydride group)) is provided by using a polymerization initiator. The "radical compound (i)") and the radically polymerizable compound having an epoxy group (hereinafter also referred to as "compound (ii)") which provides (a2) an epoxy group-containing structural unit are copolymerized in a solvent. owned. In addition, a radically polymerizable compound such as an alkyl (meth)acrylate (hereinafter also referred to as "compound (iii)") may be contained together with the compound (i) or the compound (ii). Copolymerization was carried out as (a3) to form a [A] copolymer.

Examples of the compound (i) include acrylic acid, methacrylic acid, crotonic acid, 2-propenyloxyethyl succinate, 2-methylpropenyloxyethyl succinate, and hexahydrophthalic acid 2- a monocarboxylic acid such as propylene methoxyethyl ester or hexahydrophthalic acid 2-methylpropenyl methoxyethyl ester; a dicarboxylic acid such as maleic acid, fumaric acid or citraconic acid; or a dicarboxylic acid such as maleic anhydride. Anhydride.

Among these compounds, acrylic acid, methacrylic acid, 2-acryloxyethyl succinate, and 2-methyl succinate are preferable in terms of copolymerization reactivity and solubility of the obtained copolymer to an alkaline developer. Acryl methoxyethyl ester, maleic anhydride.

For the [A] copolymer, the compound (i) may be used alone or in combination of two or more. The content of the compound (i) in the [A] copolymer is preferably 5% by mass to 40% by mass, more preferably 7% by mass to 30% by mass, particularly preferably 8% by mass to 25% by mass. By setting the content of the compound (i) at 5% by mass to 40% by mass, it is possible to obtain a radiation-sensitive resin composition which is optimized to a higher level such as radiation sensitivity, developability, and storage stability.

The compound (ii) is a radically polymerizable compound having an epoxy group (oxiranyl group, oxetane group) or the like. Examples of the radically polymerizable compound having an oxirane group include glycidyl acrylate, 2-methyl glycidyl acrylate, 3,4-epoxybutyl acrylate, and 6,7-epoxy acrylate. Epoxyalkyl acrylate such as ester, 3,4-epoxycyclohexyl acrylate or 3,4-epoxycyclohexyl acrylate; glycidyl methacrylate, 2-methylglycidyl methacrylate 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl methacrylate Epoxyalkyl methacrylate such as ester; glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, α-ethyl acrylate 6,7-ring An α-alkyl acrylate epoxyalkyl ester such as oxyheptyl ester; a glycidyl ether such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether or p-vinylbenzyl glycidyl ether.

Examples of the radically polymerizable compound having an oxetane group include 3-(methacryloxymethyl)oxetane and 3-(methacryloxymethyl)-3. -ethyloxetane, 3-(methacryloxymethyl)-2-methyloxetane, 3-(methacryloxyethyl)oxetane, 3-(methacryloxyethyl)-3-ethyloxetane, 2-ethyl-3-(methacryloxyethyl)oxetane, 3-(propylene醯oxymethyl)oxetane, 3-(acryloxymethyl)-3-ethyloxetane, 3-(acryloxymethyl)-2-methyloxa Cyclobutane, 3-(acryloxyethyl)oxetane, 3-(acryloxyethyl)-3-ethyloxetane, 2-ethyl-3-(propylene Oxyloxyethyl)oxetane, 2-(methacryloxymethyl)oxetane, 2-methyl-2-(methacryloxymethyloxy)oxycycle Butane, 3-methyl-2-(methacryloxymethyl)oxetane, 4-methyl-2-(methacryloxymethyl)oxetane, A 2-(2-(2-methyloxetanyl))ethyl acrylate, methacrylic acid 2-(2-(3-methyloxetanyl))ethyl ester, 2-(methacryloxyethyl)-2-methyloxetane, 2-(methacryl醯oxyethyl)-4-methyloxetane, 2-(acryloxymethyl)oxetane, 2-methyl-2-(acryloxymethyl)oxo Cyclobutane, 3-methyl-2-(acryloxymethyl)oxetane, 4-methyl-2-(acryloxymethyl)oxetane, methacrylic acid 2 -(2-(2-methyloxetanyl))ethyl ester, 2-(2-(3-methyloxetanyl)ethyl methacrylate, 2-(propylene oxide) (Meth) acrylate such as ethyl ethyl)-2-methyloxetane or 2-(acryloxyethyl)-4-methyloxetane.

Among these compounds, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 3-(acryloxymethyl)oxetane , 3-(methacryloxymethyl)oxetane, 3-(methacryloxymethyl)-3-ethyloxetane, 2-(methacryloxyl) The cured film such as the interlayer insulating film, the protective film, and the separator obtained by the methyl group oxetane has high adhesion to the substrate, has high heat resistance, and improves the reliability of the display element, which is preferable.

For the [A] copolymer, the compound (ii) may be used alone or in combination of two or more. The content of the compound (ii) in the [A] copolymer is preferably 10% by mass to 70% by mass, and more preferably 15% by mass to 65% by mass. By using the compound (ii) in a content ratio of 10% by mass to 70% by mass, the molecular weight of the copolymer can be easily controlled, and a radiation-sensitive resin composition which is optimized to a higher level such as developability and sensitivity can be obtained.

Examples of the compound (iii) include an alkyl (meth)acrylate, an alicyclic (meth)acrylate, an unsaturated five-membered heterocyclic ring containing an oxygen atom, and a six-membered heterocyclic (meth) acrylate. Hydroxy (meth) acrylate, aryl (meth) acrylate, unsaturated dicarboxylic acid diester, maleimide compound, hydroxyalkyl (meth) acrylate, styrene, α-A Styrene, 1,3-butadiene.

Examples of the (meth)acrylic acid alkyl ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, butyl methacrylate, butyl methacrylate, and acrylic acid. Ester, ethyl acrylate, n-butyl acrylate, secondary butyl acrylate, tertiary butyl acrylate, and the like.

Examples of the (meth) acrylate cyclic alkyl ester include cyclopentyl methacrylate, dicyclopentyl methacrylate, cyclohexyl methacrylate, and 2-methylcyclohexyl methacrylate. Tricyclodicyclopentyl methacrylate, 2-dicyclopentyloxyethyl methacrylate, methacrylic acid Ester, cyclopentyl acrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclodicyclopentyl acrylate, 2-dicyclopentyloxyethyl acrylate, acrylic acid Ester and the like.

Examples of the unsaturated five-membered heterocyclic ring and the six-membered heterocyclic methacrylate containing an oxygen atom include tetrahydrofurfuryl (meth) acrylate and tetramethyl decyl 2-propoxy decyloxypropionate. An unsaturated compound containing a tetrahydrofuran skeleton such as 3-(meth)acryloxytetrahydrofuran-2-one; 2-methyl-5-(3-furyl)-1-penten-3-one, (A) Ethyl acrylate, 1-furan-2-butyl-3-en-2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6-(2 -furyl)-2-methyl-1-hexen-3-one, 6-furan-2-yl-hex-1-en-3-one, 2-furan-2-yl-1-methyl acrylate An unsaturated compound containing a furan skeleton such as ethyl ester or 6-(2-furyl)-6-methyl-l-hepten-3-one; methacrylic acid (tetrahydropyran-2-yl) Methyl ester, 2,6-dimethyl-8-(tetrahydropyran-2-yloxy)-oct-1-en-3-one, 2-tetrahydropyran-2-yl methacrylate, Unsaturated compound containing tetrahydropyran skeleton such as 1-(tetrahydropyran-2-oxo)-butyl-3-en-2-one; 4-(1,4-dioxa-5-side oxygen -6-heptene)-6-methyl-2-pyran, 4-(1,5-dioxa-6-oxo-7-octene)-6-methyl-2-pyran Unsaturation of pyran skeleton Thereof.

Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (methyl). 2,3-dihydroxypropyl acrylate.

Examples of the aryl (meth)acrylate include phenyl (meth)acrylate and benzyl (meth)acrylate.

Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, and diethyl itaconate.

Examples of the maleinimide compound include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-(4-hydroxyphenyl). Maleimide, N-(4-hydroxybenzyl)maleimide, N-succinimido-3-maleimide benzoate, N-ammonium imino-4 - Malayan imidate, N-succinimide-6-maleimide caproate, N-succinimide-3-maleimide propionate, N- (9-Acridine) Maleimide and the like.

The content of the compound (iii) in the [A] copolymer is preferably 10% by mass to 70% by mass, and more preferably 15% by mass to 65% by mass. By setting the copolymerization ratio of the compound (iii) at 10% by mass to 70% by mass, the molecular weight of the copolymer can be easily controlled, and a radiation-sensitive resin which is optimized to a higher level such as developability, sensitivity, and adhesion can be obtained. Composition.

<[A] Synthesis Method of Copolymer>

The [A] copolymer can be synthesized by, for example, polymerizing the compound (i), the compound (ii) and, if necessary, the compound (iii) using a radical polymerization initiator in a solvent.

Examples of the solvent used in the polymerization reaction for producing the [A] copolymer include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, and propylene glycols. Alkyl ether, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether propionate, aromatic hydrocarbons, ketones, other esters, and the like.

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

Examples of the ethers include a cyclic ether, a glycol ether, an ethylene glycol alkyl ether acetate, a diethylene glycol alkyl ether, a propylene glycol monoalkyl ether, a propylene glycol monoalkyl ether acetate, and a propylene glycol monoalkyl group. Ether propionate and the like.

Examples of the cyclic ether include tetrahydrofuran and the like.

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

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

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

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

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

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

Examples of the aromatic hydrocarbons include toluene, xylene, and the like.

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

Examples of the other esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, and 2-hydroxy-2. -ethyl methacrylate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, 3-hydroxyl Ethyl propionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, A Propyl oxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, propoxy Ethyl acetate, propoxy propyl acetate, butyl propyl acetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, 2-methyl Methyl oxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-B Ethyl oxypropionate, propyl 2-ethoxypropionate Butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, Propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, Butyl 3-butoxypropionate and the like.

Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azo. Bis(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), dimethyl-2,2'-azobis (2 -Methylpropionate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and the like.

The radical polymerization initiator may be used alone or in combination of two or more. The amount of use of the radical polymerization initiator is usually preferably 0.1% by mass to 50% by mass, and more preferably 0.1% by mass based on 100% by mass based on the total of the compound (i), the compound (ii) and the compound (iii). ~20% by mass.

Further, in the above polymerization reaction, a molecular weight modifier for adjusting the molecular weight can be used. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tertiary dodecyl mercaptan, and thioglycolic acid; Such as thiol; dimethyl thioxanthine, diisopropyl dithioxanthine and other xanthan essence; terpinolene, α-methyl styrene dimer and the like.

The amount of use of the molecular weight modifier is usually 0.1% by mass to 50% by mass, preferably 0.2% by mass to 16% by mass based on 100% by mass of the total of the compound (i), the compound (ii) and the compound (iii). More preferably, it is 0.4% by mass to 8% by mass. The polymerization temperature is usually from 0 ° C to 150 ° C, preferably from 50 ° C to 120 ° C. The polymerization time is usually from 10 minutes to 20 hours, preferably from 30 minutes to 6 hours.

The polystyrene-equivalent weight average molecular weight (Mw) of the [A] copolymer is preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 5 × 10 ³ to 5 × 10 ⁴ . By setting the Mw of the [A] copolymer to 2 × 10 ³ or more, a sufficient development margin can be obtained in the radiation-sensitive resin composition, and the film residual ratio of the formed coating film can be prevented (the pattern-like film is appropriately left). The ratio) is too low, and the obtained insulating film can maintain a good pattern shape, heat resistance, and the like. On the other hand, by setting the Mw of the [A] copolymer to 1 × 10 ⁵ or less, it is possible to maintain a high degree of susceptibility to radiation and obtain a favorable pattern shape. Further, the molecular weight distribution (Mw/Mn) of the [A] copolymer is preferably 5.0 or less, more preferably 3.0 or less. By setting the Mw/Mn of the [A] copolymer to 5.0 or less, the obtained insulating film can be maintained in a good pattern shape. Further, the radiation-sensitive resin composition containing the [A] copolymer having Mw and Mw/Mn which are preferably in the above-described preferred range has high developability, so that development residue does not occur in the development step, and A predetermined pattern shape is easily formed.

The weight average molecular weight (Mw) of the copolymer was determined by gel permeation chromatography (GPC) based on the following apparatus and conditions.

Device: GPC-101 (Showa Denko Co., Ltd.)

Column: Connect GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804

Mobile phase: tetrahydrofuran

<[B] polymerizable compound>

[B] The polymerizable compound is a polymerizable compound having an ethylenically unsaturated bond. The polymerizable compound having an ethylenically unsaturated bond is not particularly limited, and examples thereof include ω-carboxypolycaprolactone mono(meth)acrylate and ethylene glycol (A). Acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene Alcohol di(meth) acrylate, polypropylene glycol di(meth) acrylate, diphenoxyethanol hydrazine di(meth) acrylate, dimethylol tricyclodecane di(meth) acrylate, A 2-hydroxy-3-(methyl)propenyl isopropyl acrylate, 2-(2'-vinyloxyethoxy)ethyl (meth) acrylate, trimethylolpropane tri(methyl) Acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(methyl) Acrylate, tris(2-(meth)acryloyloxyethyl)phosphate, ethylene oxide-modified dipentaerythritol hexaacrylate, succinic acid-modified neopentyl alcohol triacrylate, etc. Can be cited to have a straight chain extension a urethane obtained by reacting a compound having two or more isocyanate groups and having one or more hydroxyl groups in the molecule and having 3 to 5 (meth) acryloxy groups in the molecule ( A methyl acrylate compound or the like.

As a commercially available product of the above [B] polymerizable compound, for example, Aronix M-400, Aronix M-402, Aronix M-405, Aronix M-450, Aronix M-1310, Aronix M-1600, Aronix M-1960 can be cited. Aronix M-7100, Aronix M-8030, Aronix M-8060, Aronix M-8100, Aronix M-8530, Aronix M-8560, Aronix M-9050, Aronix TO-1450, Aronix TO-1382, Aronix TO-756 (above, East Asia Synthetic Company); KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD MAX-3510 (above, Nippon Kayaku Co., Ltd.); Viscoat 295, Viscoat 300, Viscoat 360, Viscoat GPT, Viscoat 3PA, Viscoat 400 (above, Osaka Organic Chemical Industry Co., Ltd.) as a urethane acrylate compound New Frontier R-1150 (First Industrial Pharmaceutical Company); KAYARAD DPHA-40H, UX -5000 (above, Nippon Kayaku Co., Ltd.); UN-9000H (Guanshang Industrial Co., Ltd.), Aronix M-5300, Aronix M-5600, Aronix M-5700, M-210, Aronix M-220, Aronix M-240, Aronix M-270, Aronix M-6200, Aronix M-305, Aronix M-309, Aronix M-310, Aronix M-315 (above, East) Synthetic company); KAYARAD HDDA, KAYARAD HX-220, KAYARAD HX-620, KAYARAD R-526, KAYARAD R-167, KAYARAD R-604, KAYARAD R-684, KAYARAD R-551, KAYARAD R-712, UX-2201 , UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (above, Nippon Chemical Co., Ltd.); Art resinUN-9000PEP, Art resinUN-9200A, Art resinUN-7600, Art resinUN-333, Art resinUN-1003, Art resinUN-1255, Art resinUN-6060PTM, Art resinUN-6060P (above, Roots Industrial Co., Ltd.); SH-500B Viscoat 260, Viscoat 312, Viscoat 335HP (above, Osaka Organic Chemical Industry Co., Ltd.), and the like.

[B] The polymerizable compound may be used alone or in combination of two or more. The content of the [B] polymerizable compound in the radiation sensitive resin composition is preferably 20 parts by mass to 200 parts by mass, more preferably 40 parts by mass to 160 parts by mass, per 100 parts by mass of the [A] copolymer. . When the content of the [B] polymerizable compound is in the above specific range, the radiation-sensitive resin composition is excellent in adhesion, and an interlayer insulating film, a protective film, and a separator having sufficient hardness can be obtained even at a low exposure amount. Such as hardened film.

<[C] sensitizing radiation polymerization initiator>

The [C] radiation-sensitive polymerization initiator contained in the radiation-sensitive resin composition is a component which is sensitive to radiation and which is capable of initiating polymerization of the [B] polymerizable compound. The [C] radiation-sensitive polymerization initiator is preferably at least one selected from the group consisting of an acetophenone compound and an O-mercaptopurine compound. By using the above specific compound as the [C] radiation-sensitive polymerization initiator, heat resistance and the like as desired properties of the cured film can be improved even at a low exposure amount.

The acetophenone compound may, for example, be an α-amino ketone compound or an α-hydroxy ketone compound.

As the α-amino ketone compound, for example, 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4- Physo-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methylthiophenyl)-2- Orolinyl propan-1-one and the like.

The α-hydroxyketone compound may, for example, be 1-phenyl-2-hydroxy-2-methylpropan-1-one or 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane. 1-ketone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, and the like.

Among these compounds, an α-amino ketone compound is preferred, and 2-benzyl-2-dimethylamino-1-(4-) is more preferred. Polinylphenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4- Physo-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methylthiophenyl)-2- Orolinyl propan-1-one.

As the O-indenyl ruthenium compound, for example, 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzamide)], ethanol-1-[9-B -6-(2-methylbenzimidyl)-9H-indazol-3-yl]-1-(O-acetamidine), 1-[9-ethyl-6-benzhydryl- 9H-carbazol-3-yl]-octane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole-3 -yl]-ethane-1-ketooxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzylidene)-9H-indazol-3-yl] -ethane-1-ketooxime-O-benzoate, ethanol-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzylidene)-9H-carbazole-3 -yl]-1-(O-acetamidine), ethanol-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzylidene)-9H-carbazole- 3-yl]-1-(O-acetamidine), ethanol-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzylidene)-9H-indazole-3- ]]-1-(O-acetamidine), ethanol-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolane Methyl methoxybenzimidyl}-9H-carbazol-3-yl]-1-(O-acetyl) and the like.

Among these compounds, 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzamide)], ethanol-1-[9-ethyl-6 is preferred. -(2-methylbenzimidyl)-9H-carbazol-3-yl]-1-(O-acetamidine), ethanol-1-[9-ethyl-6-(2-methyl- 4-tetrahydrofuranylmethoxybenzylidene)-9H-indazol-3-yl]-1-(O-acetamidine), ethanol-1-[9-ethyl-6-{2-methyl -4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene}-9H-indazol-3-yl]-1-(O-acetyl) .

The [C] radiation-sensitive polymerization initiator may be used alone or in combination of two or more. The content of the [C] radiation-sensitive polymerization initiator in the radiation-sensitive resin composition is preferably 1 part by mass to 40 parts by mass, more preferably 5 parts by mass, per 100 parts by mass of the [A] copolymer. ~30 parts by mass. By setting the content of the [C] radiation-sensitive polymerization initiator to the above specific range, the radiation-sensitive resin composition can form an interlayer insulating film having high hardness and adhesion even at a low exposure amount. A cured film such as a protective film or a separator.

<[D] compound>

The compound [D] is not particularly limited as long as it is a compound having a hydroxyl group or a carboxyl group. The compound [D] is preferably a compound capable of containing the [E] amine compound, and is preferably a compound represented by the above formula (1) and formula (2) from the viewpoint of appropriately forming a cage compound to be described later. At least one compound is selected from the group consisting of.

In the above formula (1), X is a single bond, a methylene group or an alkylene group having 2 to 6 carbon atoms. R ¹ to R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, an alkoxy group having 1 to 12 carbon atoms or a phenyl group which may have a substituent.

The alkylene group having 2 to 6 carbon atoms represented by the above X may, for example, be an extended ethyl group or a stretched propyl group. The alkyl group having 1 to 12 carbon atoms represented by the above R ¹ to R ⁸ and R ⁹ may, for example, be a methyl group, an ethyl group, a propyl group or a butyl group. The alkoxy group having 1 to 12 carbon atoms represented by the above R ¹ to R ⁸ and R ⁹ may, for example, be a methoxy group, an ethoxy group or a propoxy group.

The compound represented by the above formula (1) is preferably a compound represented by the above formula (1-1). By using the compound represented by the above formula (1) as the compound represented by the above formula (1-1), the storage stability can be further improved, and the low-temperature curing can be promoted.

Examples of the compound represented by the above formula (1-1) include 1,1,2,2-indenyl (4-hydroxyphenyl)ethane and 1,1,2,2-indole (3-methyl-4). -hydroxyphenyl)ethane, 1,1,2,2-indole (3,5-dimethyl-4-hydroxyphenyl)ethane, 1,1,2,2-indole (3-chloro-4 -hydroxyphenyl)ethane, 1,1,2,2-indole (3,5-dichloro-4-hydroxyphenyl)ethane, 1,1,2,2-indole (3-bromo-4- Hydroxyphenyl)ethane, 1,1,2,2-indole (3,5-dibromo-4-hydroxyphenyl)ethane, 1,1,2,2-indole (3-tertiary butyl- 4-hydroxyphenyl)ethane, 1,1,2,2-indole (3,5-ditributyl-4-hydroxyphenyl)ethane, 1,1,2,2-indole (3- Fluoro-4-hydroxyphenyl)ethane, 1,1,2,2-indole (3,5-difluoro-4-hydroxyphenyl)ethane, 1,1,2,2-indole (3-methyl Oxy-4-hydroxyphenyl)ethane, 1,1,2,2-indole (3,5-dimethoxy-4-hydroxyphenyl)ethane, 1,1,2,2-indole ( 3-chloro-5-methyl-4-hydroxyphenyl)ethane, 1,1,2,2-indole (3-bromo-5-methyl-4-hydroxyphenyl)ethane, 1,1, 2,2-indole (3-methoxy-5-methyl-4-hydroxyphenyl)ethane, 1,1,2,2-indole (3-tert-butyl-5-methyl-4- Hydroxyphenyl)ethane, 1,1,2,2-indole (3-chloro-5-bromo-4-hydroxyphenyl)ethane, 1,1,2,2-indole (3-chloro-5- Phenyl-4-hydroxyphenyl)ethane, 1,1,2,2-tetra[(4- 3-phenyl)phenyl]ethane, 1,1,3,3-indenyl (4-hydroxyphenyl)propane, 1,1,3,3-indole (3-methyl-4-hydroxybenzene) Propane, 1,1,3,3-indole (3,5-dimethyl-4-hydroxyphenyl)propane, 1,1,3,3-indole (3-chloro-4-hydroxyphenyl) Propane, 1,1,3,3-indole (3,5-dichloro-4-hydroxyphenyl)propane, 1,1,3,3-indole (3-bromo-4-hydroxyphenyl)propane, 1 1,3,3-肆(3,5-dibromo-4-hydroxyphenyl)propane, 1,1,3,3-indole (3-phenyl-4-hydroxyphenyl)propane, 1,1 , 3,3-肆(3,5-diphenyl-4-hydroxyphenyl)propane, 1,1,3,3-indole (3-methoxy-4-hydroxyphenyl)propane, 1,1 , 3,3-肆(3,5-dimethoxy-4-hydroxyphenyl)propane, 1,1,3,3-indole (3-tert-butyl-4-hydroxyphenyl)propane, 1 1,3,3-indole (3,5-ditributyl-4-hydroxyphenyl)propane, 1,1,4,4-indolyl (4-hydroxyphenyl)butane, 1,1, 4,4-肆(3-methyl-4-hydroxyphenyl)butane, 1,1,4,4-anthracene (3,5-dimethyl-4-hydroxyphenyl)butane, 1,1 , 4,4-肆(3-chloro-4-hydroxyphenyl)butane, 1,1,4,4-anthracene (3,5-dichloro-4-hydroxyphenyl)butane, 1,1, 4,4-肆(3-methoxy-4-hydroxyphenyl)butane, 1,1,4,4-anthracene (3,5-dimethoxy-4-hydroxyphenyl)butane, 1 1,4,4-anthracene (3-bromo-4-hydroxyphenyl) 1,1,4,4-anthracene (3,5-dibromo-4-hydroxyphenyl)butane, 1,1,4,4-anthracene (3-tert-butyl-4-hydroxyphenyl) Butane, 1,1,4,4-anthracene (3,5-ditributyl-4-hydroxyphenyl)butane, and the like.

Among these compounds, when the crystal cage compound described later is formed, the storage stability of the radiation-sensitive resin composition at room temperature is more excellent, and the curing accelerator is easily released upon heating, and is preferably 1 1,2,2-indole (4-hydroxyphenyl)ethane.

Examples of the compound represented by the above formula (2) include 5-nitroisophthalic acid, 5-hydroxyisophthalic acid, 5-methylisophthalic acid, and 5-methoxyisophthalic acid. -Nitroisophthalic acid, 4-hydroxyisophthalic acid, 4-methylisophthalic acid, 4-methoxyisophthalic acid, and the like. Among these compounds, 5-nitroisophthalic acid and 5-hydroxyisophthalic acid are preferred.

The compound [D] may be used alone or in combination of two or more. The content of the [D] compound in the radiation sensitive resin composition is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.2 parts by mass to 5 parts by mass, per 100 parts by mass of the [A] copolymer, and It is preferably about 1 to 2 times the amount of the [E] amine compound to be described later.

<[E]amine compound>

The [E] amine compound is not particularly limited, but is preferably an amine compound which can be contained in the [D] compound, more preferably an imidazole compound or a benzimidazole compound. Among these compounds, the imidazole compound is easily incorporated into the [D] compound, and the storage stability of the radiation sensitive resin composition at room temperature is improved. Further, since the imidazole compound is excellent in reactivity with an epoxy group, it contributes to low-temperature curing at 200 ° C or lower.

The imidazole compound may, for example, be a compound represented by the following formula (3).

In the above formula (3), R ¹⁰ to R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a naphthyl group, an anthracenyl group, a phenanthryl group, a 9-fluorenyl group, a halogen atom, and a carbon number. It is an alkyl group of 1 to 6, a phenyl group or a phenyl group which may be substituted by a halogen atom.

Examples of the imidazole compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-n-propylimidazole, 2-undecyl-1H-imidazole, and 2-seven. Alkyl-1H-imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methyl Imidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazolium Triphenyl acid salt, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-di Amino-6-[2'-methylimidazolyl-(1')]-ethyl-s-three 2,4-Diamino-6-(2'-undecylimidazolyl-)-ethyl-s-three 2,4-Diamino-6-[2'-ethyl-4-imidazolyl-(1')]-ethyl-s-three 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-three Isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2 -Phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-bis(2-cyanoethoxy)methylimidazole, 1-12 Alkyl-2-methyl-3-benzylimidazolium chloride, 1-benzyl-2-phenylimidazolium hydrochloride, 1-benzyl-2-phenylimidazolium trimellitate, and the like.

Among these compounds, an imidazole compound having one or more substituents having 1 to 6 carbon atoms is preferred. Since the imidazole compound can be stably contained, it does not adversely affect the storage stability of the radiation sensitive resin composition, and has a small steric hindrance, so that the reactivity is excellent, and the crystal cage can exhibit a low temperature when disintegrating. Hardenability.

The imidazole compound having one or more substituents having 1 to 6 carbon atoms may, for example, be an imidazole having one substituent having 1 to 6 carbon atoms such as 2-methylimidazole or 2-phenylimidazole. a compound; 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. having two carbon atoms of 1 to 6 Substituted imidazole compounds and the like.

Examples of the benzimidazole compound include a compound represented by the following formula (4).

In the above formula (4), R ¹⁴ to R ¹⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a naphthyl group, an anthracenyl group, a phenanthryl group, a 9-fluorenyl group, a halogen atom, and a carbon number. It is an alkyl group of 1 to 6, a phenyl group or a phenyl group which may be substituted by a halogen atom. m is an integer from 0 to 4. However, when a plurality of R ¹⁴ are present, the plurality of R ¹⁴ may be the same or different.

As the benzimidazole compound, for example, 2-methylbenzimidazole, 4-methylbenzimidazole, 5-methylbenzimidazole, 6-methylbenzimidazole, 7-methylbenzimidazole, 2 -methyl-6-methylbenzimidazole, 2-methyl-6-methylbenzimidazole, 2-methyl-5-methylbenzimidazole, 2-methyl-5-methylbenzimidazole 2-ethyl-6-methylbenzimidazole, 2-methyl-6-ethylbenzimidazole, 2-ethyl-5-methylbenzimidazole, 2-methyl-5-ethylbenzene And imidazole and the like.

Among these compounds, a benzimidazole compound having one or more substituents having 1 to 6 carbon atoms is preferred. Since the imidazole compound can be stably contained, it does not adversely affect the storage stability of the radiation sensitive resin composition, and has a small steric hindrance, so that the reactivity is excellent, and the crystal cage can exhibit a low temperature when disintegrating. Hardenability.

Examples of the benzimidazole compound having one or more substituents having 1 to 6 carbon atoms include benzimidazole having one substituent having 1 to 6 carbon atoms such as 2-methylbenzimidazole. a compound; a benzimidazole compound having two substituents having 1 to 6 carbon atoms such as 2-methyl-6-methylbenzimidazole or 2-methyl-5-methylbenzimidazole.

The [E] amine compound may be used alone or in combination of two or more. The content of the compound [E] in the radiation-sensitive resin composition is preferably 0.05 parts by mass to 5 parts by mass, more preferably 0.1 parts by mass to 2.5 parts by mass, per 100 parts by mass of the [A] copolymer, and It is preferably about 0.5 to 1 time relative to the [D] compound.

<Crystal compound>

For the radiation sensitive resin composition, at least a part of the [E] amine compound is preferably contained in the [D] compound. With respect to the radiation sensitive resin composition, by forming at least a part of the [E] amine compound in the [D] compound to form a crystal cage compound, storage stability and low-temperature baking can be simultaneously satisfied.

The method of encapsulating the [E] amine compound with the [D] compound is not particularly limited, and examples thereof include those described in JP-A-11-071449. The radiation sensitive resin composition having a viscosity at 25 ° C of 1.0 mPa ‧ s or more and 50 mPa ‧ s or less is preferably a crystal cage compound formed by encapsulating an [E] amine compound in the [D] compound and [ A] The copolymer, the [B] polymerizable compound, and the [C] radiation-sensitive polymerization initiator are mixed and prepared. By the above steps, the radiation sensitive resin composition containing the crystal cage compound can be efficiently produced.

When the crystal cage compound is formed in advance and is contained in the radiation sensitive resin composition, the content of the cage compound in the radiation sensitive resin composition is preferably 0.1% by mass based on 100 parts by mass of the [A] copolymer. The mass portion is -10 parts by mass, more preferably 0.2 parts by mass to 5 parts by mass. By setting the content ratio of the crystal cage compound to 0.1 part by mass to 10 parts by mass, the radiation-sensitive resin composition can satisfy the storage stability and the hardening promotion of the cured film at a high level, and the obtained protective film can be provided. The voltage holding ratio of the display element of the cured film such as the interlayer insulating film or the spacer is maintained at a high level.

<arbitrary component>

As the radiation sensitive resin composition, in addition to the above [A] copolymer, [B] polymerizable compound, [C] radiation sensitive polymerization initiator, [D] compound, and [E] amine compound, if necessary, Any component containing a compound containing two or more oxirane groups per molecule, a bonding aid, a surfactant, a storage stabilizer, and a heat resistance improving agent is contained within a range that does not impair the intended effect. These optional components may be used alone or in combination of two or more. The various components are described in detail below.

[Compounds containing two or more oxirane groups per molecule]

A compound containing two or more oxirane groups per molecule may be added in order to further increase the hardness of the obtained cured film. Examples of such a compound include a compound containing two or more 3,4-epoxycyclohexyl groups per molecule.

Examples of the compound containing two or more 3,4-epoxycyclohexyl groups per molecule include, for example, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-inter , bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6 -Methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadienyl dicyclopentadienyl Bis(3,4-epoxycyclohexylmethyl)ether of ethylene, ethylene glycol, ethyl bis(3,4-epoxycyclohexanecarboxylate), lactone modified 3,4-epoxy Cyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, and the like.

Examples of the other compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, and hydrogenation. Diglycidyl ether of bisphenol compounds such as bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether; 1, 4 - Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol dihydrate a polyglycidyl ether of a polyether polyol obtained by adding one or two or more kinds of alkylene oxides to an aliphatic polyol such as ethylene glycol, propylene glycol or glycerin; Phenolic novolac type epoxy resin; cresol novolak type epoxy resin; polyphenol type epoxy resin; cyclic aliphatic epoxy resin; diglycidyl ester of aliphatic long-chain dibasic acid; glycidol of higher fatty acid Ester; epoxidized soybean oil, epoxidized linen Oil and so on. Among these compounds, a phenol novolac type epoxy resin and a polyphenol type epoxy resin are preferable.

Examples of the commercially available product of these materials include EPICOTE 1001, EPICOTE 1002, EPICOTE 1003, EPICOTE 1004, EPICOTE 1007, EPICOTE 1009, EPICOTE 1010, EPICOTE 828 (above, Japan Epoxy Resin Co., Ltd.), which are bisphenol A type epoxy resins, and the like, and bisphenol F type. EPICOTE 807 (Japan Epoxy Resin Co., Ltd.) of epoxy resin; EPICOTE 152, EPICOTE 154, EPICOTE 157S65 (above, Japan Epoxy Resin Co., Ltd.), EPPN201, EPPN 202 (above, Nippon Kayaku Co., Ltd.) as a phenol novolak type epoxy resin; EOCN102, EOCN103S, EOCN104S, 1020, 1025, 1027 (above, Nippon Chemical Co., Ltd.) and EPICOTE 180S75 (Japan Epoxy Resin Co., Ltd.) as cresol novolak type epoxy resin; EPICOTE1032H60, EPICOTEXY as polyphenol type epoxy resin -4000 (above, Japan Epoxy Resin Co., Ltd.); CY-175, CY-177, CY-179, Araldite CY-182, Araldite CY-192, Araldite CY-184 as a cyclic aliphatic epoxy resin (above, Ciba Specialty Chemicals, ERL-4234, ERL-4299, ERL-4221, ERL-4206 (above, UCC), Shodyne509 (Showa Denko) EPICLON 200, EPICLON 400 (above, Dainippon Ink Co., Ltd.), EPICOTE 871, EPICOTE 872 (above, Japan Epoxy Resin Co., Ltd.), ED-5661, ED-5662 (above, Celanese coating Co., Ltd.), etc.; as an aliphatic polyglycidyl ether EPOLIGHT 100MF (Kyoei Chemical Co., Ltd.), EPIOL TMP (Japan Oil Company), etc.

The amount of the compound containing two or more oxirane groups per molecule is preferably 50 parts by mass or less, more preferably 2 parts by mass to 50 parts by mass, per 100 parts by mass of the [A] copolymer. Preferably, it is 5 parts by mass to 30 parts by mass. By using the compound having two or more oxirane groups per molecule in the above specific range, it is possible to further improve the cured film such as the interlayer insulating film, the separator or the protective film without impairing the developability. hardness.

[Adhesive Aid]

The adhesion aid is used to further improve the adhesion between the obtained interlayer insulating film, the cured film such as a separator or a protective film, and the substrate. As such an adhesion aid, a functional decane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group or an oxirane group is preferable, and for example, trimethoxy group is mentioned.矽alkyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, γ-isocyanate propyl triethoxy decane, γ-ring Oxypropoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like.

The amount of use as the adhesion aid is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less based on 100 parts by mass of the [A] copolymer. If the amount of the adhesion aid used exceeds 20 parts by mass, development residue tends to occur.

[Surfactant]

The surfactant is used to further improve the coating film formability of the radiation-sensitive resin composition. Examples of the surfactant include a fluorine-based surfactant, an organic silicone resin surfactant, and other surfactants.

The fluorine-based surfactant is preferably a compound having a fluoroalkyl group and/or a fluorine-extended alkyl group in at least one of a terminal, a main chain and a side chain, and examples thereof include 1,1,2,2-tetrafluoro. - n-octyl (1,1,2,2-tetrafluoro-n-propyl)ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl)ether, hexaethylene glycol bis (1, 1,2,2,3,3-hexafluoro-n-pentyl)ether, octaethylene glycol bis(1,1,2,2-tetrafluoro-n-butyl)ether, hexapropanediol bis (1,1, 2,2,3,3-hexafluoro-n-pentyl)ether, octapropylene glycol bis(1,1,2,2-tetrafluoro-n-butyl)ether, perfluoro-n-dodecanesulfonate sodium, 1 , 1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane, and fluoroalkylbenzenesulfonate Sodium, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerol tetrakis(fluoroalkylpolyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, other fluoroalkyl polyoxyethylene ether , perfluoroalkyl polyhydroxyethanol, perfluoroalkyl alkoxide, fluoroalkyl carboxylate, and the like.

Examples of the commercially available product of the fluorine-based surfactant include BM-1000, BM-1100 (above, BM CHEMIE), MEGAFAC F142D, MEGAFAC F172, MEGAFAC F173, MEGAFAC F183, MEGAFAC F178, MEGAFAC F191, and MEGAFAC F471. MEGAFAC F476 (above, Dainippon Ink Chemical Industry Co., Ltd.), FRORAID FC-170C, FRORAID FC-171, FRORAID FC-430, FRORAID FC-431 (above, Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 ( Above, Asahi Glass Co., Ltd., EFTOP EF301, EFTOP EF 303, EFTOP EF 352 (above, New Akita Chemical Co., Ltd.), FTERGENT FT-100, FTERGENT FT-110, FTERGENT FT-140A, FTERGENT FT-150, FTERGENT FT-250, FTERGENT FT-251, FTERGENT FT-300, FTERGENT FT-310, FTERGENT FT-400S, FTERGENT FTX-218, FTERGENT FTX-251 (above, NEOS).

Commercially available products of organic silicone resin surfactants include, for example, Toray Silicone DC3PA, Toray Silicone DC7PA, Toray Silicone SH11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH-190, Toray Silicone SH-193, Toray Silicone S Z -6032, Toray Silicone SF-8428, Toray Silicone DC-57, Toray Silicone DC-190 (above, Toray‧Dow Corning‧Silicone), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF -4452 (above, GE Toshiba Organic Silicone Resin Co., Ltd.), organic alkane polymer KP341 (Shin-Etsu Chemical Co., Ltd.), and the like.

Examples of the other surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene-n-octylphenyl ether; a polyoxyethylene aryl ether such as oxyethylene-n-decylphenyl ether; a nonionic surfactant such as polyoxyethylene dialkyl ester such as polyoxyethylene dilaurate or polyoxyethylene distearate; Methyl)acrylic copolymer Polyflo No. 57, Polyflo No. 95 (above, Co., Ltd.).

The amount of the surfactant to be used is preferably 1.0 part by mass or less, and more preferably 0.5 part by mass or less based on 100 parts by mass of the [A] copolymer. If the amount of the surfactant used exceeds 1.0 part by mass, the film is likely to be uneven.

[Storage Stabilizer]

Examples of the storage stabilizer include sulfur, anthracene, hydroquinone, polyoxy compound, amine, nitronitroso compound, and the like, and more specifically, 4-methoxyphenol and N-Asia. Nitro-N-phenylhydroxylamine aluminum and the like.

The amount of the storage stabilizer to be used is preferably 3.0 parts by mass or less, more preferably 0.5 parts by mass or less, based on 100 parts by mass of the [A] copolymer. If the blending amount of the storage stabilizer exceeds 3.0 parts by mass, the sensitivity of the radiation sensitive resin composition is deteriorated, which may cause deterioration of the pattern shape.

[heat resistance improver]

Examples of the heat resistance improving agent include an N-(alkoxymethyl)glycol compound, an N-(alkoxymethyl)melamine compound, and the like.

As the N-(alkoxymethyl)glycoluric compound, for example, N,N,N',N'-fluorene (methoxymethyl)glycoluril, N,N,N',N'-肆 ( Ethoxymethyl)glycoluril, N,N,N',N'-indole (n-propoxymethyl)glycoluril, N,N,N',N'-indole (isopropoxymethyl) Glycoluril, N, N, N', N'-肆 (n-butoxymethyl) glycoluril, N, N', N", N'''-肆 (tertiary butoxymethyl) glycoluril Among these compounds, N, N, N', N'-fluorene (methoxymethyl) glycoluril is preferred.

As the N-(alkoxymethyl)melamine compound, for example, N,N,N',N',N",N"-lu (methoxymethyl)melamine, N,N,N',N can be cited. ',N",N"-lu (ethoxymethyl)melamine, N,N,N',N',N",N"-lu (n-propoxymethyl)melamine, N,N,N ',N',N",N"-lu (isopropoxymethyl)melamine, N,N,N',N',N",N"-lu (n-butoxymethyl)melamine, N , N, N', N', N", N"-lu (tertiary butoxymethyl) melamine and the like. Among these compounds, N, N, N', N', N", N"-lu (methoxymethyl) melamine is preferred. Examples of the commercially available product include NIKALACN-2702, NIKALACMW-30M (above, Sanwa Chemical Co., Ltd.) and the like.

The amount of use of the heat resistance improving agent is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less based on 100 parts by mass of the [A] copolymer. If the blending amount of the heat resistance improving agent exceeds 50 parts by mass, the sensitivity of the radiation sensitive linear resin composition is deteriorated, which may cause deterioration of the pattern shape.

<Preparation method of radiation sensitive resin composition>

The radiation sensitive resin composition for forming a cured film of the present invention is, in addition to the [A] copolymer, the [B] polymerizable compound, the [C] radiation sensitive polymerization initiator, the [D] compound, and the [E] amine compound. If necessary, the ingredients may be mixed in a predetermined ratio within a range that does not impair the intended effect, thereby being formulated. The radiation sensitive resin composition having a viscosity at 25 ° C of 1.0 mPa ‧ s or more and 50 mPa ‧ s or less is preferably a crystal cage compound formed by encapsulating the [E] amine compound in the [D] compound It is prepared by mixing with [A] copolymer, [B] polymerizable compound, and [C] radiation sensitive polymerization initiator.

As the solvent used in the preparation of the radiation-sensitive resin composition, a solvent which uniformly dissolves or disperses various components and does not react with various components can be used. As such a solvent, a solvent exemplified as a solvent which can be used for the synthesis of the above [A] copolymer is used.

The solvent preferably contains at least one solvent selected from the group consisting of an alcohol solvent and an ether solvent. It is considered that the radiation sensitive resin composition can be easily dissolved by containing the above polar solvent, and for the present invention, as described above, even in the case of using a polar solvent, the cage compounds can be mutually The action inhibits the disintegration of the cage. The solvent may be used alone or in combination of two or more.

Further, in addition to the above solvent, in order to increase the uniformity of the film thickness in the plane, a high boiling point solvent may be used in combination. Examples of the high boiling point solvent include N-methylpyrrolidone, N,N-dimethylacetamide, benzyl ethyl ether, dihexyl ether, hexanedione, 1-octanol, and 1-nonanol. , benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, propylene carbonate and the like. Among these solvents, N-methylpyrrolidone, γ-butyrolactone, and N,N-dimethylacetamide are preferred.

The solvent used as the radiation-sensitive resin composition is preferably used in an amount of 50% by mass or less, more preferably 40% by mass or less, even more preferably 30%, based on the total amount of the solvent. Below mass%. When the amount of the high boiling point solvent used is 50% by mass or less, the film thickness uniformity, sensitivity, and film residual ratio of the coating film are good.

When the radiation-sensitive resin composition is in a solution state, the solid content concentration (component other than the solvent present in the composition solution) can be set to any concentration (for example, 5 mass depending on the purpose of use or the value of the desired film thickness). %~50% by mass). The more preferable solid content concentration varies depending on the method of forming a coating film on the substrate, which will be described later. The composition solution thus prepared can be used by filtration using a micropore filter having a pore diameter of about 0.5 μm or the like.

<Method of Forming Cured Film>

The present invention is also preferably a cured film comprising an interlayer insulating film, a protective film or a separator formed of the radiation sensitive resin composition. The method for forming a cured film of the present invention comprises:

(1) a step of forming a coating film of the radiation sensitive resin composition on a substrate;

(2) a step of irradiating at least a part of the coating film with radiation;

(3) a step of developing a coating film irradiated with the above radiation; and

(4) A step of firing the coating film subjected to the above development.

According to the formation method of the present invention using the radiation-sensitive resin composition, it is possible to form a cured film in which heat resistance, chemical resistance, light transmittance, flatness, and linear thermal expansion resistance are satisfactorily satisfied. Each step will be described in detail below.

[step 1)]

In this step, a transparent conductive film is formed on one surface of a transparent substrate, and a coating film of a radiation-sensitive resin composition is formed on the transparent conductive film. Examples of the transparent substrate include glass substrates such as soda lime glass and alkali-free glass, and are selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, and polyphthalamide. A resin substrate made of a plastic such as an amine.

Examples of the transparent conductive film provided on one surface of the transparent substrate include a NESA film composed of tin oxide (SnO ₂ ) (registered trademark of PPG Corporation), and composed of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ). ITO film, etc.

When the coating film is formed by a coating method, after applying the solution of the radiation-sensitive resin composition on the transparent conductive film, it is preferred to pre-baking the coated surface to form a coating film. The solid content concentration of the composition solution used in the coating method is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, particularly preferably 15% by mass to 35% by mass. Examples of the coating method include a spray coating method, a roll coating method, a spin coating method (spin coating method), a slit coating method (slot die coating method), a bar coating method, and an inkjet coating method. Among these methods, a spin coating method or a slit coating method is preferred.

The pre-baking conditions are preferably from 70 ° C to 120 ° C, more preferably from about 1 to 15 minutes, depending on the type of the various components, the blending ratio, and the like. The film thickness after pre-baking of the coating film is preferably from 0.5 μm to 10 μm, more preferably from 1.0 μm to 7.0 μm.

[Step (2)]

This step is to irradiate at least a part of the formed coating film with radiation. In this case, when only a part of the coating film is irradiated, for example, a method of irradiating through a mask having a predetermined pattern may be employed. Examples of the radiation used in the irradiation include visible light, ultraviolet light, and far ultraviolet light. Among them, radiation having a wavelength in the range of 250 nm to 550 nm is preferable, and radiation containing ultraviolet rays of 365 nm is more preferable.

For radiation exposure (exposure), as a luminometer (OAI model 356, Optical Associates Inc. Company) irradiation was measured radiation intensity values wavelength of 365nm, preferably ^{100J / m 2 ~ 5,000J / m} 2, more Good for 200J/m2~3,000J/m ² .

Compared with the conventionally known composition, the radiation-sensitive resin composition has the following advantages: high sensitivity of the radiation, the radiation ² or less even if the irradiation amount of 700J / m, even 600J / m ² or less, can be obtained having A cured film such as an interlayer insulating film, a protective film or a separator having a film thickness, a good shape, excellent adhesion, and high hardness is expected.

[Step (3)]

In this step, the coating film irradiated with the above-described radiation is developed to remove unnecessary portions, thereby forming a predetermined pattern.

Examples of the developer to be used for the development include an inorganic base such as sodium hydroxide, potassium hydroxide or sodium carbonate, an aqueous solution of a basic compound such as a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide, or the like. A water-soluble organic solvent such as methanol or ethanol and/or a surfactant may be added to an aqueous solution of the above basic compound in an appropriate amount.

Examples of the development method include a paddle method, a immersion method, a shower method, and the like. The development time is preferably about 10 seconds to 180 seconds at normal temperature. After the development treatment, for example, running water washing is carried out for 30 seconds to 90 seconds, and then air-dried by compressed air or compressed nitrogen to obtain a desired pattern.

[Step (4)]

In this step, the obtained pattern-like coating film is fired (post-baking) by a suitable heating means such as a hot plate or an oven. The firing temperature is preferably from 100 ° C to 200 ° C, more preferably from 150 ° C to 180 ° C. The radiation sensitive resin composition has both storage stability and sufficient radiation sensitivity while achieving low-temperature firing as described above. Therefore, the radiation sensitive resin composition is suitably used as a material for forming a cured film such as an interlayer insulating film, a protective film, or a separator which is used for a flexible display or the like which is desired to be fired at a low temperature. The firing time is, for example, preferably 5 minutes to 30 minutes on a hot plate and 30 minutes to 180 minutes in an oven.

<Method of Manufacturing Display Element>

The present invention preferably includes a display element including the cured film. The display element can achieve excellent voltage holding ratio.

As a method of manufacturing the display element, first, a pair of (two sheets) transparent substrates having a transparent conductive film (electrode) on one surface are prepared, and the radiation-sensitive resin composition is used on the transparent conductive film of one of the substrates, according to the above The method forms a separator or a protective film or both. Next, an alignment film having a liquid crystal alignment ability is formed on the transparent conductive film and the spacer or the protective film on the substrates. The substrates are arranged to face each other in such a manner that the surface on which the alignment film is formed faces inward, and the liquid crystal alignment directions of the respective alignment films are orthogonal or antiparallel, and are disposed opposite each other with a certain gap (cell gap). The liquid crystal is filled in the cell gap defined by the substrate surface (alignment film) and the spacer, and the filling hole is sealed to constitute a liquid crystal cell. The display of the present invention can be obtained by bonding a polarizing plate to the two outer surfaces of the liquid crystal cell such that the polarizing direction of the polarizing plate is aligned or orthogonal to the alignment direction of the liquid crystal of the alignment film formed on one surface of the substrate. element.

As another method, a pair of transparent substrates in which a transparent conductive film, an interlayer insulating film, a protective film or a spacer, or both, and an alignment film are formed are prepared in the same manner as the above method. Along the rear end of the substrate, an ultraviolet curable sealant was applied using a distributor, and then liquid crystal was dripped in a fine droplet form using a liquid crystal distributor, and the two substrates were bonded under vacuum. For the above sealant portion, ultraviolet rays were irradiated with a high pressure mercury lamp to seal the two substrates. Finally, a polarizing plate is adhered to the two outer surfaces of the liquid crystal cell, thereby obtaining the display element of the present invention.

Examples of the liquid crystal used in the above various methods include a nematic liquid crystal, a smectic liquid crystal, and the like. In addition, as a polarizing plate to be used for the outer side of the liquid crystal cell, a polarizing film called "H film" which is formed by absorbing iodine while stretching the polyvinyl alcohol is sandwiched between the cellulose acetate protective film. The obtained polarizing plate or a polarizing plate composed of the H film itself or the like.

Example

Hereinafter, the present invention will be described in detail based on examples, but this example is not intended to limit the invention.

<[A] Synthesis of Copolymer> [Synthesis Example 1]

In a flask equipped with a condenser and a stirrer, 5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were added. Next, 20 parts by mass of styrene, 12 parts by mass of methacrylic acid, 28 parts by mass of dicyclopentyl methacrylate, and 40 parts by mass of glycidyl methacrylate were added, and the temperature of the solution was slowly stirred while being replaced with nitrogen. The temperature was raised to 70 ° C, and the temperature was maintained for 5 hours to carry out polymerization to obtain a solution containing the copolymer (A-1). The solid content concentration of the obtained copolymer solution was 31.3%, and the Mw of the copolymer (A-1) was 12,000. Also, the solid content concentration means the ratio of the copolymer to the total mass of the copolymer solution.

[Synthesis Example 2]

In a flask equipped with a condenser and a stirrer, 5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were added. Next, 10 parts by mass of styrene, 12 parts by mass of methacrylic acid, 23 parts by mass of tricyclodicyclopentyl methacrylate, 20 parts by mass of glycidyl methacrylate, and 20 parts by mass of 2-methyl methacrylate were added. Glyceride, 10 parts by mass of tetrahydrofurfuryl methacrylate, after replacing with nitrogen, 5 parts by mass of 1,3-butadiene was added, and the temperature of the solution was raised to 70 ° C while slowly stirring, and the temperature was raised. The polymerization was carried out for 5 hours to obtain a solution containing the copolymer (A-2). The obtained copolymer solution had a solid content concentration of 31.5%, and the copolymer (A-2) had a Mw of 10,100.

[Synthesis Example 3]

In a flask equipped with a condenser and a stirrer, 5 parts by mass of 2,2'-azobis(isobutyronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were added. Next, 15 parts by mass of styrene, 30 parts by mass of n-butyl methacrylate, 30 parts by mass of benzyl methacrylate, and 25 parts by mass of glycidyl methacrylate were added, and the temperature of the solution was raised to 80 while stirring slowly. At ° C, the temperature was maintained for 5 hours to carry out polymerization to obtain a solution containing the copolymer (A-3). The solid content concentration of the obtained copolymer solution was 31.0%, and the Mw of the copolymer (A-3) was 10,000.

<Preparation of a radiation sensitive resin composition for forming a cured film>

The details of the various components used in the preparation of each of the radiation sensitive resin compositions are as follows.

[B] Polymeric compound

B-1: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Kayaku Co., Ltd.)

B-2: Mixture of multifunctional acrylate compounds (KAYARAD DPHA-40H, Nippon Kayaku Co., Ltd.)

B-3: 1,9-nonanediol diacrylate

B-4: Neopentyltetraol tetraacrylate

B-5: Trimethylolpropane triacrylate

B-6: ω-carboxypolycaprolactone monoacrylate (ARONIXM-5300, East Asia Synthetic Company)

B-7: Succinic acid-modified neopentyl alcohol triacrylate (ARONIXTO-756, East Asia Synthetic Company)

B-8: Ethylene oxide modified dipentaerythritol hexaacrylate [C] radiation sensitive polymerization initiator

C-1:1,2-octanedione-1-[4-(phenylthio)-2-(O-benzamide)] (IRGACURE OXE01, Ciba Specialty Chemicals)

C-2: ethanol-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-acetamidine) (IRGACURE OXE02, Ciba Specialty Chemicals)

C-3: 2-methyl-1-(4-methylthiophenyl)-2- Orolinyl propan-1-one (IRGACURE 907, Ciba Specialty Chemicals)

C-4: 2-dimethylamino-2-(4-methylbenzyl)-1-(4- Polin-4-yl-phenyl)-butan-1-one (IRGACURE 379, Ciba Specialty Chemicals

[D] compound

D-1: 5-nitroisophthalic acid represented by the following formula

D-2: 5-hydroxyisophthalic acid represented by the following formula

D-3: 1,1,2,2-anthracene (4-hydroxyphenyl)ethane represented by the following formula

[E]amine compound

E-1: 2-phenyl-4-methyl-5-hydroxymethylimidazole

E-2: 2-methylimidazole

E-3: 2-ethyl-4-methylimidazole

E-4: 2-methylbenzimidazole

Crystal cage compound

F-1 to F-10 which are the crystal cage compounds shown below are compounds which are formed by including the [E] amine compound in the above compound [D] as the main compound.

F-1: 0.67 parts by mass of D-1 and 0.33 parts by mass of E-1 (2:1)

F-2: 0.67 parts by mass of D-2 and 0.33 parts by mass of E-1 (2:1)

F-3: 0.67 parts by mass of D-3 and 0.33 parts by mass of E-1 (2:1)

F-4: 0.67 parts by mass of D-1 and 0.33 parts by mass of E-2 (2:1)

F-5: 0.67 parts by mass of D-2 and 0.33 parts by mass of E-2 (2:1)

F-6: 0, 67 parts by mass of D-3 and 0.33 parts by mass of E-2 (2: 1)

F-7: 0.67 parts by mass of D-1 and 0.33 parts by mass of E-3 (2:1)

F-8: 0.67 parts by mass of D-2 and 0.33 parts by mass of E-3 (2:1)

F-9: 0.67 parts by mass of D-3 and 0.33 parts by mass of E-3 (2:1)

F-10: 0.50 parts by mass of D-3 and 0.50 parts by mass of E-4 (1:1)

Solvent

S-1: propylene glycol monomethyl ether acetate

S-2: propylene glycol monomethyl ether

[Examples 1 to 15 and Comparative Examples 1 to 4]

The [A] copolymer, the [B] polymerizable compound, the [C] polymerization initiator, the crystal cage compound or the [E] amine compound of the type and amount shown in Table 1 were mixed, and 5 parts by mass as an optional component were mixed. Additive (γ-glycidoxypropyltrimethoxydecane), 0.5 part by mass of surfactant (FTX-218, NEOS) and 0.5 part by mass of storage stabilizer (4-methoxyphenol), added After the solvent (S-1), it was filtered through a micropore filter having a pore size of 0.5 μm to prepare a radiation-sensitive resin composition having a viscosity of 16 mPa·s. Also, the "-" in the column indicates that the component is not used. Further, the results of viscosity measurement of each of the radiation sensitive resin compositions at 25 ° C are collectively listed.

<evaluation>

The following evaluation was carried out using the radiation sensitive resin composition. The results are shown in Table 2.

[Storage stability (%)]

Each of the radiation sensitive resin compositions was allowed to stand in an oven at 40 ° C for one week, and the viscosity before and after the oven was placed was measured to determine the viscosity change rate (%) as the storage stability (%). When the storage stability was 5% or less, it was judged that the storage stability was good, and when it exceeded 5%, it was judged that the storage stability was not good. Further, the viscosity was measured at 25 ° C using an E-type viscometer (VISCONIC ELD.R, Toki Sangyo Co., Ltd.).

[Sensitivity (J/m ² )]

Each of the radiation sensitive resin compositions was applied onto an alkali-free glass substrate by a spin coater, and then prebaked on a hot plate at 100 ° C for 2 minutes to form a film having a film thickness of 4.0 μm. Next, the obtained coating film through a reticle having a plurality of circular diameter of the remaining patterns of different sizes in the range 8μm ~ 15μm, and a high pressure mercury lamp as an exposure amount in the range of ² 200J / m ² ~ 1,000J / m The variable illuminates the radiation. Then, the development time was used as a variable at 25 ° C using a 0.40% by mass aqueous solution of tetramethylammonium hydroxide, and after development by a liquid-holding method, it was washed with pure water for 1 minute. It was post-baked in an oven at 180 ° C for 60 minutes to form a cured film having a circular residual pattern. The height of the circular residual pattern before and after development was measured with a laser microscope (VK-8500, Keyence Corporation). The film residual ratio (%) was determined from this value and the following formula.

Film residual ratio (%) = (height after development / height before development) × 100

The exposure amount of the film residual ratio of 90% or more was taken as the sensitivity (J/m ² ). When the exposure amount was 750 J/m ² or less, it was judged that the sensitivity was good. Further, in Comparative Example 4, a pattern could not be formed (indicated as "-" in Table 2).

[heat resistance (%)]

In the above-described cured film forming step, the coating film obtained by exposing at a exposure amount of 700 J/m ² without passing through a photomask was further heated in an oven at 230 ° C for 20 minutes, using a stylus type film thickness measuring machine ( Alpha-Step IQ, KLATencor, Inc.) measured the film thickness before and after heating. From this value and the following formula, the film residual ratio (%) was determined as heat resistance (%).

Heat resistance (%) = (film thickness after treatment / film thickness before treatment) × 100

[Chemical resistance (%)]

In the above-described cured film forming step, the coating film obtained by exposure at an exposure amount of 700 J/m ² without passing through a photomask was subjected to an alignment film peeling liquid CHEMICLEANTS-204 (Sanyo Chemical Industry Co., Ltd.) heated to 60 ° C. After immersion for 15 minutes, after washing with water, it was dried in an oven at 120 ° C for 15 minutes. The film thickness before and after the treatment was measured by a stylus type film thickness measuring machine (Alpha-Step IQ, KLA Tencor Co.), and the film residual ratio (%) was calculated and used as chemical resistance (%).

[Transmittance(%)]

In the above-described cured film forming step, the coating film obtained by exposure at an exposure amount of 700 J/m ² without passing through a photomask was measured at a wavelength of 400 nm using a spectrophotometer (150-20 type double beam, Hitachi, Ltd.). Light transmittance (%). When the value is 90% or more, it is judged that the transparency (%) is good.

[flatness (nm)]

On a SiO ₂ -impregnated glass substrate, a pigment-based color resist (JCR RED 689, JCR GREEN 706, and CR 8200B, the above JSR Corporation) was used to form strip-shaped color filters of red, green, and blue colors as follows. sheet. Specifically, one of the above-described color resists was applied onto a SiO ₂ -impregnated glass substrate using a spin coater, and prebaked on a hot plate at 90 ° C for 150 seconds to form a coating film. Then, using an exposure machine (Canon PLA501F, canon), the ghi line was irradiated with an exposure amount of 2,000 J/m ² in an i-line through a mask of a predetermined pattern (intensity ratio of wavelength 436 nm, 405 nm, 365 nm = 2.7: 2.5). :4.8), development was carried out using a 0.05% by mass aqueous potassium hydroxide solution, and rinsed with ultrapure water for 60 seconds. Subsequently, heat treatment was further carried out in an oven at 230 ° C for 30 minutes to form a monochromatic strip-shaped color filter. This operation was repeated in three colors to form strip-shaped color filters of three colors of red, green, and blue (bar width: 200 μm). According to the measurement of the length of 2,000 μm, the measurement range of 2,000 μm side square, the measurement direction of the red, green, and blue directions of the short-axis direction of the strip line and the red, green, green, blue, blue, and the same color strip line long axis When the number of measurement points in the two directions and the directions is n=5 (the total number of n is 10), when the surface unevenness of the color filter substrate is measured by the contact film thickness measuring device (Alpha-Step KLA Tencor Co., Ltd.), 1.0 μm. On the substrate on which the color filter is formed, each thermosetting resin composition is coated with a spin coater, and then pre-baked on a hot plate at 90 ° C for 5 minutes to form a coating film, and then in a cleaning oven at 180 ° C. The film was baked for 60 minutes to form a protective film having a film thickness of about 2.0 μm with respect to the upper surface of the color filter. With respect to the substrate having the protective film on the color filter thus formed, the surface unevenness of the protective film was measured by a contact film thickness measuring device (Alpha-Step KLATencor Co., Ltd.). The measurement is a square with a length of 2,000 μm and a measurement range of 2,000 μm, a short-axis direction of the strip line in the measurement direction of red, green, and blue, and a same color strip of red, green, green, and blue. In the two directions of the long axis direction of the line, the number of measurement points in each direction is n=5 (the total number of n is 10), and the height difference (nm) of the highest part and the bottom part of each measurement is obtained 10 times. The average value is taken as flatness (nm). When the value is 200 nm or less, it is judged that the flatness is good.

[Line thermal expansion coefficient (ppm / ° C)]

In the above-described cured film forming step, the coating film was formed by exposing at a exposure amount of 700 J/m ² without passing through a photomask. Then, it was hardened by heat-treating at 180 ° C for 60 minutes in an oven to form a coating film for measurement. Then, an ellipsometer (DVA-36LH, Gully Optical Industry Co., Ltd.) equipped with a temperature changing device was used to adjust the temperature rise rate during the measurement to 10 ° C / min in a nitrogen atmosphere. The amount of change in film thickness at each measurement temperature was measured at 20 ° C to 200 ° C, and the temperature was plotted. The slope b was obtained from the approximate straight line, and the linear thermal expansion coefficient a (ppm / ° C) was obtained by the following formula. T represents the initial film thickness.

a=b/T

When the linear thermal expansion coefficient is 200 ppm/° C. or less, it can be determined that the linear thermal expansion coefficient is low, and a cured film having sufficient curability can be formed even after post-baking at 180° C.

[Voltage retention rate (%)]

An SiO ₂ film that prevents precipitation of sodium ions is formed on the surface, and a sodium glass substrate on which an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape is spin-coated with each of the radiation-sensitive resin compositions at 90 ° C. The prebaking was carried out for 10 minutes in a cleaning oven to form a coating film having a film thickness of 2.0 μm. Then, the coating film was exposed to an exposure amount of 500 J/m ² without passing through a photomask. Then, the substrate was immersed in a developing solution composed of a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C for 1 minute, developed, washed with ultrapure water, and then baked at 180 ° C for 60 minutes to be coated. The film hardens to form a permanent cured film. Then, the substrate on which the pixel was formed and the substrate on which the ITO electrode was deposited only in a predetermined shape were bonded by a sealant in which glass beads of 0.8 mm were mixed, and then liquid crystal (MLC6608) manufactured by Merck was injected to prepare a liquid crystal cell. Then, the liquid crystal cell was placed in a constant temperature layer at 60 ° C, and the voltage holding ratio (%) of the liquid crystal cell was measured by a liquid crystal voltage retention ratio measurement system (VHR-1A type, TOYO Technica Co., Ltd.). The voltage applied at this time was a square wave of 5.5 V, and the measurement frequency was 60 Hz. The voltage holding ratio was obtained by the following formula.

Voltage holding ratio (%) = (liquid crystal cell potential difference after 16.7 ms / voltage applied at 0 msec) × 100

When the voltage holding ratio is 90% or less, it means that the liquid crystal cell cannot maintain the applied voltage at a predetermined level for a period of 16.7 milliseconds, and the liquid crystal cannot be sufficiently aligned, which may cause a "burn in" of residual image or the like.

As is clear from the results of Table 2, the radiation sensitive resin compositions of Examples 1 to 15 had better storage stability and radiation sensitivity than the compositions of Comparative Examples 1 to 4. Further, it is understood that the cured film formed of the radiation-sensitive resin composition has excellent heat resistance, chemical resistance, light transmittance, flatness, and linear thermal expansion resistance even when it is formed by firing at a low temperature of 200 ° C or lower. Sex. Further, it is understood that the voltage holding ratio of the display element including the cured film is also good.

Industrial applicability

The radiation-sensitive resin composition for forming a cured film of the present invention can easily form a fine and delicate pattern while satisfying storage stability and low-temperature firing, and having sufficient radiation sensitivity. Further, the cured film formed of the radiation sensitive resin composition is excellent in heat resistance, chemical resistance, light transmittance, flatness, and linear thermal expansion resistance. Therefore, the radiation sensitive resin composition is suitably used as a material for forming a cured film such as an interlayer insulating film, a protective film, and a separator which are used in a flexible display or the like which is desired to be fired at a low temperature. Further, a display element including the cured film is also preferably included in the present invention, and an excellent voltage holding ratio can be achieved.

Claims (9)

A radiation sensitive resin composition for forming a cured film, comprising: [A] a copolymer having (a1) a carboxyl group-containing structural unit and (a2) an epoxy group-containing structural unit, [B] having ethylenic unsaturation a polymerizable compound of a bond, a [C] radiation sensitive polymerization initiator, [D] a compound having a hydroxyl group or a carboxyl group, an [E] amine compound, and at least one solvent selected from the group consisting of an alcohol solvent and an ether solvent. And the viscosity at 25 ° C is 1.0 mPa ‧ s or more and 50 mPa ‧ s or less, wherein the [D] compound is at least one selected from the group consisting of compounds represented by the following formulas (1) and (2) a compound, the [E]amine compound is an imidazole compound or a benzimidazole compound, and at least a part thereof is encapsulated in the [D] compound, In the formula (1), X is a single bond, a methylene group or an alkylene group having 2 to 6 carbon atoms, and each of R ¹ to R ^{8 is} independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. a halogen atom or an alkoxy group having 1 to 12 carbon atoms or a phenyl group; and in the formula (2), R ⁹ is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms; Nitro or hydroxy. The radiation-sensitive resin composition for forming a cured film according to the first aspect of the invention, wherein the compound represented by the above formula (1) is a compound represented by the following formula (1-1). In the formula (1-1), X and R ¹ to R ⁸ have the same meanings as in the above formula (1). The radiation sensitive resin composition for forming a cured film according to claim 1 or 2, wherein the [C] radiation sensitive polymerization initiator is selected from the group consisting of an acetophenone compound and an O-indenyl compound. At least one. The radiation sensitive resin composition for forming a cured film according to claim 1 or 2, wherein the crystal cage compound obtained by including the [E] amine compound in the [D] compound is mixed into the [A] copolymer, The [B] polymerizable compound and the [C] radiation-sensitive polymerization initiator are prepared by setting the viscosity at 25 ° C to 1.0 mPa ‧ s or more and 50 mPa ‧ s or less. A method for producing a radiation sensitive linear resin composition for forming a cured film according to the first aspect of the invention, which comprises the inclusion of the [D] compound The crystal cage compound obtained by the [E] amine compound is mixed into the [A] copolymer, the [B] polymerizable compound, and the [C] radiation-sensitive polymerization initiator to prepare a viscosity of 1.0 mPa·s or more at 25 ° C. Steps below 50mPa‧s. A method for forming a cured film, comprising: (1) a step of forming a coating film of a radiation sensitive resin composition for forming a cured film according to any one of claims 1 to 4 on a substrate; (2) a step of irradiating at least a part of the coating film with radiation; (3) a step of developing a coating film irradiated with the radiation; and (4) a step of firing the coating film subjected to the development. The baking method of the above step (4) is 200 ° C or lower, as in the method of forming the sixth item of the patent application. A cured film which is formed as an interlayer insulating film, a protective film or a separator, which is formed of a radiation sensitive resin composition for forming a cured film according to any one of claims 1 to 4. A display element having a cured film as in item 8 of the patent application.