KR20110130347A - The radiation sensitive resin composition for cured film formation, the manufacturing method of the radiation sensitive resin composition for cured film formation, the formation method of a cured film, a cured film, and a display element - Google Patents

Abstract

(Object) The object of the present invention is a radiation-sensitive resin composition for forming a cured film that is compatible with storage stability and low temperature baking, and has sufficient radiation sensitivity, and a cured film excellent in heat resistance, chemical resistance, transmittance, flatness, and heat-resisting thermal expansion resistance. And a display element having an excellent voltage holding ratio.
(Solution means) The present invention provides a copolymer having a [A] (a1) carboxyl group-containing structural unit and (a2) an epoxy group-containing structural unit, a polymerizable compound having [B] ethylenically unsaturated bond, and [C] radiation It is a radiation sensitive resin composition for cured film formation which contains a polymerization polymerization initiator, the compound which has a [D] hydroxyl group or a carboxyl group, and a [E] amine compound, and whose viscosity in 25 degreeC is 1.0 mPa * s or more and 50 mPa * s or less.

Description

Radiation-sensitive resin composition for cured film formation, manufacturing method of radiation-sensitive resin composition for cured film formation, cured film, formation method of cured film, and display element TECHNICAL FIELD SENSITIVE RESIN COMPOSITION FOR FORMING CURED FILM, CURED FILM, METHOD FOR FORMING THE CURED FILM AND LIQUID CRYSTAL DISPLAY DEVICE}

This invention relates to the radiation sensitive resin composition for cured film formation, the manufacturing method of the radiation sensitive resin composition for cured film formation, the cured film, the formation method of a cured film, and a display element.

In an electronic component such as a thin film transistor (TFT) type liquid crystal display element, an interlayer insulating film is formed in order to insulate between wirings generally arranged in a layer shape. For example, a TFT type liquid crystal display element is manufactured through the process of forming a transparent electrode film on an interlayer insulation film, and forming a liquid crystal aligning film on it. Since such an interlayer insulating film is exposed to a high temperature condition and a stripping solution of a resist used for pattern formation of the electrode in the step of forming the transparent electrode film, sufficient heat resistance and chemical resistance to them are required. Moreover, the radiation sensitive resin composition used for formation of such a cured film requires shortening (that is, high radiation sensitivity) of radiation irradiation time and favorable storage stability.

In recent years, lightweight and compact flexible displays using TFT technology have been widely used. As a board | substrate of a flexible display, plastic board | substrates, such as polycarbonate, are examined. Plastic substrates have a problem of being elongated and contracted by heating, resulting in impaired display function. Therefore, the low temperature in the heating process of flexible display manufacture is examined. For example, Japanese Laid-Open Patent Publication No. 2009-4394 discloses a coating liquid for a gate insulating film for a flexible display containing a polyimide precursor that can be cured even at low temperature firing. However, since this coating liquid does not have the pattern formation ability by exposure development, fine pattern formation is impossible. Moreover, whether the progress of hardening reaction is due to insufficient point, the cured film obtained is not a satisfactory level in heat resistance, chemical resistance, transmittance | permeability, flatness, thermal-expansion resistance, etc.

Therefore, the method of advancing a crosslinking reaction by addition of the amine compound used as a hardening | curing agent of an epoxy type material even at low temperature can also be considered. However, addition of a general amine compound may cause reaction with time with the epoxy group which exists in a composition, and storage stability may fall.

From such a situation, it is excellent in heat resistance, chemical-resistance, transmittance, flatness, thermal-expansion resistance, etc. which are required characteristics as a cured film, the radiation sensitive resin composition for cured film formation which is compatible with storage stability and low temperature baking, and has sufficient radiation sensitivity. The development of a cured film is desired.

Japanese Laid-Open Patent Publication No. 2009-4394

This invention is made | formed based on the above circumstances, The objective is the radiation sensitive resin composition for cured film formation which is compatible with storage stability and low temperature baking, and has sufficient radiation sensitivity, heat resistance, chemical resistance, transmittance | permeability, flatness. And a cured film excellent in resistance to thermal expansion and a display element excellent in voltage retention.

The invention made to solve the above problems,

(A) (a1) A copolymer having 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] radiation sensitive polymerization initiator,

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

[E] amine compounds

It is a radiation sensitive resin composition for cured film formation which contains and is a viscosity in 25 degreeC 1.0 mPa * s or more and 50 mPa * s or less.

The said radiation sensitive resin composition contains the [A] copolymer, [B] polymeric compound, and [C] radiation sensitive polymerization initiator as alkali-soluble resin. The said radiation sensitive resin composition which is a photosensitive material can easily form a fine and sophisticated pattern by exposure and image development using radiation sensitivity, and has sufficient radiation sensitivity. Moreover, by containing a [D] compound and an [E] amine compound, the viscosity at 25 degrees C of the said radiation sensitive resin composition can be controlled to 1.0 mPa * s or more and 50 mPa * s or less, and storage stability and low temperature baking It is compatible.

It is preferable that [E] amine compound can be included in [D] compound. By making the amine compound [E] into an amine compound that can be included in the [D] compound, at least a part thereof forms a clathrate compound, and the radiation-sensitive resin composition may contain a clathrate compound, thereby achieving both storage stability and low temperature baking. can do. That is, at room temperature, the [E] amine compound which accelerates hardening is enclosed, hardening reaction of an epoxy group hardly advances, and the viscosity of a composition solution is not increased. Therefore, the said radiation sensitive resin composition becomes what is excellent in storage stability. On the other hand, when the radiation-sensitive resin composition is heated to a predetermined temperature or more, the inclusions collapse, the [E] amine compound is released, the epoxy group-containing resin crosslinks, and the curing reaction is accelerated. In addition, since the said radiation sensitive resin composition is normally used in a solution state, in order to ensure solubility, it is preferable to use a polar solvent. On the other hand, the clathrate compound is generally used as a solid powder, which is dispersed in a composition solution or the like because the clathrate may collapse when dissolved in a polar solvent such as an alcohol solvent or an ether solvent. However, in the radiation sensitive resin composition, it is thought that the collapse of the inclusions is suppressed by the interaction of the carboxyl group and the inclusion compound in the coexisting [A] copolymer, and a polar solvent can be used. In addition, it is thought that proton of a carboxyl group is added to imidazole by the said interaction, and a carboxyl group is anionized and a carbo anion is produced | generated. Since this carbo anion also has high nucleophilicity, it is thought that a clathrate compound also has the synergistic effect which accelerates hardening reaction of the epoxy group in a [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), respectively, wherein the [E] amine compound is an imidazole compound or a benzimidazole compound. desirable.

(In formula (1), X is a single bond, a methylene group, or a C2-C6 alkylene group, R <^1> -R <^8> is respectively independently a hydrogen atom, a C1-C12 alkyl group, a halogen atom, and C1-C1 It is a phenyl group which may have a -12 alkoxy group or a substituent;

In formula (2), R <^9> is a C1-C12 alkyl group, a C1-C12 alkoxy group, a nitro group, or a hydroxyl group.).

A clathrate compound can be formed efficiently by making [D] compound and [E] amine compound into the said specific compound, respectively.

It is preferable that the compound represented by said formula (1) is a compound represented by following formula (1-1).

(In formula (1-1), X and R <^1> -R <^8> is synonymous with said Formula (1).).

By making the compound represented by said Formula (1) into the compound represented by said Formula (1-1), storage stability can improve more and hardening at low temperature can also be accelerated | stimulated.

In the radiation sensitive resin composition, at least a part of the [E] amine compound is preferably contained in the [D] compound. In the radiation sensitive resin composition, at least a part of the [A] amine compound is included in the [D] compound to form a clathrate compound, whereby storage stability and low temperature baking can be achieved.

[C] The radiation sensitive polymerization initiator is preferably at least one selected from the group consisting of an acetophenone compound and an O-acyl oxime compound. By using the said specific compound as a radiation sensitive polymerization initiator (C), even if it is a low exposure amount, the required characteristic as a cured film, such as heat resistance, can be improved more.

It is preferable that the said radiation sensitive resin composition further contains at least 1 sort (s) of solvent chosen from the group which consists of an alcohol solvent and an ether solvent. By containing said polar solvent, the said radiation sensitive resin composition can be melt | dissolved easily, and in this invention, even if a polar solvent is used as mentioned above, the collapse of clathration is suppressed by interaction with a clathrate compound. I think you can.

The said radiation-sensitive resin composition whose viscosity in 25 degreeC is 1.0 mPa * s or more and 50 mPa * s or less is [A] copolymer and [B] superposition | polymerization of the clathrate compound in which the [E] amine compound was contained in the [D] compound. It is preferable to mix and prepare an soluble compound and a [C] radiation sensitive polymerization initiator. According to the said process, the said radiation sensitive resin composition containing a clathrate compound can be manufactured efficiently.

Formation method of the cured film of this invention,

(1) Process of forming the coating film of the said radiation sensitive resin composition on a board | substrate

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

(3) developing the coating film irradiated with the radiation;

(4) The process of baking the developed coating film

Respectively.

By the formation method of this invention using the said radiation sensitive resin composition, the cured film which satisfy | fills heat resistance, chemical-resistance, transmittance | permeability, flatness, and heat-resistant thermal expansion can be formed in a good balance.

It is preferable that the baking temperature of the said process (4) is 200 degrees C or less. As mentioned above, the said radiation sensitive resin composition realizes low temperature baking, compatible with storage stability, and has sufficient radiation sensitivity. Therefore, the said radiation sensitive resin composition is used suitably as a formation material of cured films, such as an interlayer insulation film, a protective film, and a spacer used for flexible displays etc. which low temperature baking is desired.

The cured film as an interlayer insulation film, a protective film, or a spacer formed from the said radiation sensitive resin composition is also contained suitably for this invention. Moreover, the display element provided with this cured film is also suitably included in this invention, and can implement | achieve the outstanding voltage holding ratio.

In addition, "baking" as used in this specification means heating until the surface hardness calculated | required by cured films, such as an interlayer insulation film, a protective film, and a spacer, is obtained. In addition, a "clathrate compound" means the compound in which another guest molecule is enclosed by the molecular unit in the space which a host molecule forms. "Radiation" of "radiation-sensitive resin composition" is a concept including visible light, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like. In addition, the said viscosity measured the viscosity (mPa * s) of the said composition in 25 degreeC using the E-type viscosity meter (the Toki Sangyo Co., Ltd. make, VISCONIC ELD.R). Usually, an amine compound is known as a hardening accelerator for accelerating the crosslinking reaction of an epoxy compound. Also in the said composition, an [E] amine compound acts on the epoxy group in [A] component, and promotes the crosslinking reaction of an epoxy compound. In this case, the viscosity of the composition solution increases. When it becomes 50 mPa * s or more, film thickness control at the time of application | coating becomes difficult, and it cannot become applicable as a radiation sensitive resin composition for cured film formation.

In the composition of the present invention, the viscosity at 25 ° C. of the radiation-sensitive resin composition can be controlled to 1.0 mPa · s or more and 50 mPa · s or less by containing the [D] compound and the [E] amine compound. Firing can be compatible.

As described above, the radiation-sensitive resin composition for forming a cured film of the present invention can easily form a fine and sophisticated pattern, achieves both storage stability and low temperature baking, and has sufficient radiation sensitivity. Moreover, the cured film formed from the said radiation sensitive resin composition is excellent in heat resistance, chemical-resistance, transmittance | permeability, flatness, and heat-resistant thermal expansion property. Therefore, the said radiation sensitive resin composition is used suitably as a formation material of cured films, such as an interlayer insulation film, a protective film, and a spacer used for flexible displays etc. which low temperature baking is desired. Moreover, the display element provided with this cured film is also suitably included in this invention, and can implement | achieve the outstanding voltage holding ratio.

(Form to carry out invention)

<Radiation Resin Composition for Curing Film Formation>

The radiation sensitive resin composition for cured film formation of this invention contains a [A] copolymer, a [B] polymeric compound, a [C] radiation sensitive polymerization initiator, a [D] compound, and an [E] amine compound, The viscosity in 25 degreeC is 1.0 mPa * s or more and 50 mPa * s or less. Moreover, the said radiation sensitive resin composition may contain arbitrary components, unless the effect of this invention is impaired. Hereinafter, each component is explained in full detail.

<[A] copolymer>

[A] copolymer contained in the said radiation sensitive resin composition has (a1) carboxyl group containing structural unit and (a2) epoxy group containing structural unit. As the method for obtaining the copolymer (A), for example, (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride (hereinafter referred to as “compound (a)) which gives a carboxyl group-containing structural unit (the carboxyl group also includes an acid anhydride group). ) And (a2) a radically polymerizable compound having an epoxy group imparting an epoxy group-containing structural unit (hereinafter also referred to as "compound (ii)") is obtained by copolymerizing in a solvent using a polymerization initiator. In addition, as needed (a3), a radically polymerizable compound (hereinafter also referred to as "compound") such as (meth) acrylic acid alkyl ester is contained together with the compound (iii) and compound (ii) and copolymerized. It is good also as a [A] copolymer.

As the compound (i), for example

Acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid Monocarboxylic acids such as;

Dicarboxylic acids such as maleic acid, fumaric acid and citraconic acid;

And dicarboxylic acid anhydrides such as maleic anhydride.

Among these, acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, and maleic anhydride are preferable from the viewpoint of copolymerization reactivity and solubility of the resulting copolymer in an alkaline developer. .

In the copolymer (A), the compound (VII) can be used alone or in combination of two or more thereof. In the copolymer (A), the content of the compound (i) 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 rate of the compound (VIII) to 5% by mass to 40% by mass, a radiation sensitive resin composition in which properties such as radiation sensitivity, developability and storage stability are optimized to a higher level is obtained.

As a compound (ii), the radically polymerizable compound which has an epoxy group (oxyranyl group, oxetanyl group), etc. is mentioned. As a radically polymerizable compound which has an oxiranyl group, for example

Acrylic acid such as glycidyl acrylate, 2-methylglycidyl acrylate, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexylmethyl acrylate Epoxy alkyl esters;

Glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate, methacrylic acid Methacrylic acid epoxy alkyl esters such as acid 3,4-epoxycyclohexylmethyl;

α-alkyl acrylate epoxyalkyl esters such as α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl and α-ethyl acrylate 6,7-epoxyheptyl;

and glycidyl ethers such as o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether.

As a radically polymerizable compound which has an oxetanyl group, for example, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacrylo) Yloxymethyl) -2-methyloxetane, 3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (methacryl Loyloxyethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-methylox Cetane, 3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (acryloyloxyethyl) oxetane, 2- (meta Chryloyloxymethyl) oxetane, 2-methyl-2- (methacryloyloxymethyl) oxetane, 3-methyl-2- (methacryloyloxymethyl) oxetane, 4-methyl-2- ( Methacryloyloxymethyl) oxetane, 2- (2- (2-methyloxetanyl)) ethyl methacrylate, 2- (2- (3-methyloxetanyl)) ethyl methacrylate, 2- ( Tacryloyloxyethyl) -2-methyloxetane, 2- (methacryloyloxyethyl) -4-methyloxetane, 2- (acryloyloxymethyl) oxetane, 2-methyl-2- (acrylic Loyloxymethyl) oxetane, 3-methyl-2- (acryloyloxymethyl) oxetane, 4-methyl-2- (acryloyloxymethyl) oxetane, 2- (2- (2-methyljade Cetanyl)) ethyl methacrylate, 2- (2- (3-methyloxetanyl)) ethyl methacrylate, 2- (acryloyloxyethyl) -2-methyloxetane, 2- (acryloyl (Meth) acrylic acid ester, such as oxyethyl) -4-methyloxetane, is mentioned.

Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 3- (acryloyloxymethyl) oxetane, 3- (methacryloyloxy Methyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, and 2- (methacryloyloxymethyl) oxetane are obtained for substrates of cured films such as interlayer insulating films, protective films and spacers obtained. It is preferable at the point of adhesiveness being high, having high heat resistance, and improving the reliability in a display element.

In the copolymer (A), the compound (ii) can be used alone or in combination of two or more thereof. In the copolymer (A), the content of the compound (ii) is preferably 10% by mass to 70% by mass, and more preferably 15% by mass to 65% by mass. By setting the content rate of compound (ii) to 10 mass%-70 mass%, control of the molecular weight of a copolymer becomes easy and the radiation sensitive resin composition optimized to higher level of developability, a sensitivity, etc. is obtained.

As a compound (i), (meth) acrylic-acid alkylester, (meth) acrylic-acid alicyclic ester, unsaturated hetero 5-membered ring and 6-membered ring (meth) acrylic acid ester containing an oxygen atom, (meth) acrylic acid ester which has a hydroxyl group, (meth) Acrylic acid aryl ester, unsaturated dicarboxylic acid diester, maleimide compound, the hydroxyalkyl ester of (meth) acrylic acid, styrene, (alpha) -methylstyrene, 1, 3- butadiene are mentioned.

As the (meth) acrylic acid alkyl ester, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, and the like.

As a (meth) acrylic-acid alicyclic alkyl ester, methacrylic acid cyclopentyl, methacrylic acid dicyclopentanyl, methacrylic acid cyclohexyl, methacrylic acid 2-methylcyclohexyl, methacrylic acid tricyclodicyclopentanyl, 2-dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, cyclopentyl acrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclodicyclopentanyl acrylate, 2-dicyclopentanyloxyethyl acrylate, acrylic acid Isobornyl and the like.

As unsaturated hetero 5- and 6-membered methacrylic acid ester containing an oxygen atom, for example, tetrahydrofurfuryl (meth) acrylate, 2-methacryloyl-oxypropionic acid tetrahydrofurfuryl ester, 3- (meth) Unsaturated compounds containing tetrahydrofuran skeletons such as) acryloyloxytetrahydrofuran-2-one;

2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) 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-ene-3 Unsaturated compounds containing furan skeletons such as -one, acrylic acid-2-furan-2-yl-1-methyl-ethyl ester and 6- (2-furyl) -6-methyl-1-hepten-3-one;

(Tetrahydropyran-2-yl) methylmethacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -octo-1-en-3-one, 2-methacrylic acid tetrahydro Unsaturated compounds containing tetrahydropyran skeletons such as pyran-2-yl ester and 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one;

4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyran, 4- (1,5-dioxa-6-oxo-7-octenyl) -6- And unsaturated compounds containing pyran skeletons such as methyl-2-pyran.

Examples of the (meth) acrylic acid ester having a hydroxyl group include (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid-2, 3-dihydroxypropyl etc. are mentioned.

As (meth) acrylic-acid aryl ester, (meth) acrylic-acid phenyl, (meth) acrylic-acid benzyl, etc. are mentioned, for example.

As unsaturated dicarboxylic acid diester, diethyl maleate, diethyl fumarate, diethyl itaconic acid, etc. are mentioned, for example.

As a maleimide compound, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, for example , N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide pro Cypionate, N- (9-acridinyl) maleimide, etc. are mentioned.

In the copolymer (A), the content of the compound (i) is preferably 10% by mass to 70% by mass, and more preferably 15% by mass to 65% by mass. By controlling the copolymerization ratio of the compound (VIII) to 10% by mass to 70% by mass, the control of the molecular weight of the copolymer becomes easy, and a radiation sensitive resin composition in which developability, sensitivity, adhesiveness, and the like are optimized to a higher level is obtained. .

<Synthesis method of [A] copolymer>

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

Examples of the solvent used for the polymerization reaction for producing the copolymer (A) include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, and propylene glycol mono Alkyl ether acetate, propylene glycol monoalkyl ether propionate, aromatic hydrocarbons, ketones, other esters, etc. are mentioned.

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

Examples of the ethers include cyclic ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, and propylene glycol monoalkyl ether propionates. have.

As cyclic ether, tetrahydrofuran etc. are mentioned, for example.

As glycol ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc. are mentioned, for example.

As ethylene glycol alkyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc. are mentioned, for example.

As diethylene glycol alkyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc. are mentioned, for example.

As propylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc. are mentioned, for example.

As propylene glycol monoalkyl ether acetate, a propylene glycol monomethyl ether acetate, a propylene glycol monoethyl ether acetate, a propylene glycol monopropyl ether acetate, a propylene glycol monobutyl ether acetate etc. are mentioned, for example.

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

As aromatic hydrocarbons, toluene, xylene, etc. are mentioned, for example.

As ketones, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl- 2-pentanone, etc. are mentioned, for example.

As other esters, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, and hydroxy Methyl hydroxyacetate, ethyl hydroxyacetate, hydroxyacetic acid butyl, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate ethyl, 3-hydroxypropionic acid propyl, 3-hydroxy Butyl oxypropionate, methyl 2-hydroxy-3-methylbutanoic acid, methyl methoxyacetic acid, ethyl methoxyacetic acid, methoxyacetic acid propyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, ethoxyacetic acid propyl Butyl ethoxy acetate, methyl propoxy acetate, ethyl acetate propoxyacetate Propyl acid, butyl propoxyacetic acid, methyl butoxyacetic acid, ethyl butoxyacetic acid, butoxyacetic acid propyl, butyl butoxyacetic acid, 2-methoxypropionate, ethyl 2-methoxypropionic acid, 2-methoxypropionic acid propyl, 2 Butyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2- Propyl butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionic acid, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-E Ethyl oxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionate Field, and 3-propoxy propionate, butyl propionate, methyl 3-butoxy, 3-butoxy-ethyl, 3-butoxy propyl propionate, butyl propionate, 3-butoxy.

As said radical polymerization initiator, it is 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- dimethylvaleronitrile), 2,2'- azobis- (4, for example. -Methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis (4-diaminovaleric acid), dimethyl-2,2'-azobis (2-methylpropionate), 2, 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc. are mentioned.

A radical polymerization initiator can be used individually or in mixture of 2 or more types. As the usage-amount of a radical polymerization initiator, 0.1 mass%-50 mass% are preferable normally with respect to 100 mass% of total of a compound (i), a compound (ii), and a compound (i), and 0.1 mass%-20 mass% More preferred.

In addition, in the said polymerization reaction, in order to adjust molecular weight, a molecular weight modifier can be used. As a molecular weight modifier, for example

Halogenated hydrocarbons such as chloroform and carbon tetrabromide;

mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and thioglycolic acid;

Xanthogens, such as dimethyl xanthogen sulfide and diisopropyl xanthogen disulfide;

Terpinolene, (alpha) -methylstyrene dimer, etc. are mentioned.

As the usage-amount of a molecular weight modifier, 0.1 mass%-50 mass%, 0.2 mass%-16 mass% are preferable normally with respect to 100 mass% of total of a compound (X), a compound (ii), and a compound (X), and are 0.4 mass % -8 mass% is more preferable. As polymerization temperature, 0 degreeC-150 degreeC and 50 degreeC-120 degreeC are preferable normally. As polymerization time, 10 minutes-20 hours, and 30 minutes-6 hours are preferable normally.

As polystyrene conversion weight average molecular weight (Mw) of the copolymer (A), 2x10 <^3> -1 * 10 <^5> is preferable and 5x10 <^3> -5 * 10 <^4> is more preferable. By setting Mw of the copolymer (A) to 2 × 10 ³ or more, a sufficient development margin of the radiation-sensitive resin composition is obtained, and a decrease in the remaining film ratio (a ratio at which the pattern-shaped thin film is properly retained) of the formed coating film is achieved. It can prevent and further maintain favorable the pattern shape, heat resistance, etc. of the insulating film obtained. On the other hand, by setting Mw of the [A] copolymer to 1 × 10 ⁵ or less, high radiation sensitivity is preserved and a good pattern shape is obtained. Moreover, as molecular weight distribution (Mw / Mn) of a [A] copolymer, 5.0 or less are preferable and 3.0 or less are more preferable. By setting Mw / Mn of the copolymer (A) to 5.0 or less, the pattern shape of the insulating film obtained can be favorably maintained. Moreover, since the radiation sensitive resin composition containing the [A] copolymer which has Mw and Mw / Mn of the preferable range as mentioned above has high developability, in a developing process, it does not generate | occur | produce a developing residue. The predetermined pattern shape can be easily formed.

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

Device: GPC-101 (Showa Denko KK)

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

Mobile phase: tetrahydrofuran

<[B] polymerizable compound>

The polymerizable compound [B] is a polymerizable compound having an ethylenically unsaturated bond. The polymerizable compound (B) is not particularly limited as long as it is a polymerizable compound having an ethylenically unsaturated bond, and for example, ω-carboxypolycaprolactone mono (meth) acrylate, ethylene glycol (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylic Latene, bisphenoxyethanol fluorenedi (meth) acrylate, dimethylol tricyclodecanedi (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, 2- ( 2'-vinyloxyethoxy) ethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Other (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloyloxyethyl) phosphate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol tree Compounds having a linear alkylene group and an alicyclic structure and having at least two isocyanate groups, such as acrylates, and at least one hydroxyl group in the molecule and having 3 to 5 (meth) acryloyloxy groups The urethane (meth) acrylate compound etc. which are obtained by making it react are mentioned.

As a commercial item of the said [B] polymeric compound, it is for example

ARONIX M-400, M-402, M-405, M-450, M-1310, M-1600, M-1960, M-7100, M- 8030, East M-8060, East M-8100, East M-8530, East M-8560, East M-9050, Aronix TO-1450, East TO-1382, East TO-756 (above, Toagose Corporation );

KAYARAD 'DPHA, East DPCA-20, East DPCA-30, East DPCA-60, East DPCA-120, East MAX-3510 (above, Nippon Kayaku Co., Ltd.);

VISCOAT 295, East 300, East 360, East GPT, East 3PA, East 400 (above, Osaka Yukikagaku Kyokyo Co., Ltd.)

NEW FRONTIER R-1150 (Daiichi Kogyo Seyaku Co., Ltd.) as a urethane acrylate compound;

KAYARAD 'DPHA-40H, UX-5000 (above Nippon Kayaku Co., Ltd.);

UN-9000H (Negami Kogyo Co., Ltd.),

Aronix M-5300, M-5600, M-5700, M-210, M-220, M-240, M-270, M-6200, M-305, M-309 , East M-310, East M-315 (above, Toagose Co., Ltd.);

KAYARAD HDDA, KAYARAD HX-220, HX-620, R-526, R-167, R-604, R-684, R-551, 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 Kayaku Co., Ltd.);

ARTRESIN UN-9000PEP, East UN-9200A, East UN-7600, East UN-333, East UN-1003, East UN-1255, East UN-6060PTM, East UN-6060P Shikiisha);

SH-500B biscot 260, 312, 335HP (above, Osaka Yukikagaku Kogyo Co., Ltd.) etc. are mentioned.

A polymerizable compound (B) can be used individually or in mixture of 2 or more types. As content of the [B] polymeric compound in the said radiation sensitive resin composition, 20 mass parts-200 mass parts are preferable with respect to 100 mass parts of [A] copolymers, and 40 mass parts-160 mass parts are more preferable. . By making content of a polymerizable compound (B) into the said specific range, cured films, such as an interlayer insulation film, a protective film, and a spacer, which are excellent in adhesiveness and have sufficient hardness also in low exposure amount, are obtained.

<[C] radiation sensitive polymerization initiator>

[C] The radiation sensitive polymerization initiator contained in the said radiation sensitive resin composition is a component which produces the active species which can start superposition | polymerization of a [B] polymeric compound in response to radiation. [C] The radiation sensitive polymerization initiator is preferably at least one selected from the group consisting of an acetophenone compound and an O-acyl oxime compound. By using the said specific compound as a radiation sensitive polymerization initiator (C), even if it is a low exposure amount, the required characteristic as a cured film, such as heat resistance, can be improved more.

As an acetophenone compound, the (alpha)-amino ketone compound, the (alpha)-hydroxy ketone compound, etc. are mentioned, for example.

As an α-amino ketone compound, for example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-dimethylamino-2- (4-methylbenzyl)- 1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, etc. are mentioned. .

As an alpha-hydroxy ketone compound, it is 1-phenyl- 2-hydroxy-2- methyl propane- 1-one, and 1- (4-i-propylphenyl) -2-hydroxy- 2-methyl propane-, for example. 1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, etc. are mentioned.

Of these, α-amino ketone compounds are preferable, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-dimethylamino-2- (4-methylbenzyl ) -1- (4-Morpholin-4-yl-phenyl) -butan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one are more preferable Do.

Examples of the O-acyl oxime compound include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] and ethanone-1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octane-1- Onoxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethane-1-onoxime-O-benzoate, 1- [9- n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2- Methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetra Hydropyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3- Dioxoranyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) etc. are mentioned. All.

Among them, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazole- 3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxoranyl) methoxy Benzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred.

(C) A radiation sensitive polymerization initiator can be used individually or in mixture of 2 or more types. As content of the [C] radiation sensitive polymerization initiator in the said radiation sensitive resin composition, 1 mass part-40 mass parts are preferable with respect to 100 mass parts of [A] copolymers, and 5 mass parts-30 mass parts are more desirable. By making content of a radiation sensitive polymerization initiator into the said specific range, the said radiation sensitive resin composition can form cured films, such as an interlayer insulation film, a protective film, and a spacer, which have high hardness and adhesiveness even in the case of low exposure amount. .

<[D] compound>

The compound [D] is not particularly limited as long as it is a compound having a hydroxyl group or a carboxyl group. As the compound [D], a compound capable of encapsulating the [E] amine compound is preferable, and the group consisting of the compounds represented by the formulas (1) and (2), respectively, from the viewpoint of suitably forming the inclusion compound described later. It is preferable that it is at least 1 sort (s) of compound chosen from.

In said formula (1), X is a single bond, a methylene group, or a C2-C6 alkylene group. 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.

As a C2-C6 alkylene group represented by said X, an ethylene group, a propylene group, etc. are mentioned, for example. R ¹ to R ⁸ As a C1-C12 alkyl group represented by R <^9> , a methyl group, an ethyl group, a propyl group, a butyl group, etc. are mentioned, for example. As a C1-C12 alkoxy group represented by said R <^1> -R <^8> and R <^9> , a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned, for example.

It is preferable that the compound represented by said formula (1) is a compound represented by said formula (1-1). By making the compound represented by said Formula (1) into the compound represented by said Formula (1-1), storage stability can improve more and hardening at low temperature can also be accelerated | stimulated.

As a compound represented by said Formula (1-1), it is 1,1,2,2- tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2- tetrakis (3-methyl-4, for example. -Hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-4-hydroxy Oxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dichloro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-bromo-4-hydroxy Phenyl) ethane, 1,1,2,2-tetrakis (3,5-dibromo-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-t-butyl-4- Hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-di-t-butyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-fluoro 4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-difluoro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-meth Methoxy-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethoxy-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro -5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-bromo-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetra Kis (3-methoxy-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-t-butyl-5-methyl-4-hydroxyphenyl) ethane, 1, 1,2,2-tetrakis (3-chloro-5-bromo-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-5-phenyl-4-hydroxyphenyl ) Ethane, 1,1,2,2-tetrakis ((4-hydroxy-3-phenyl) phenyl] ethane, 1,1,3,3-tetrakis (4-hydroxyphenyl) propane, 1,1 , 3,3-tetrakis (3-methyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1,3 , 3-tetrakis (3-chloro-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dichloro-4-hydroxyphenyl) propane, 1,1,3,3 Tetrakis (3-bromo-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dibromo-4-hydroxyphenyl) propane, 1,1,3, 3- Tetrakis (3-phenyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-diphenyl-4-hydroxyphenyl) propane, 1,1,3,3-tetra Kis (3-methoxy-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dimethoxy-4-hydroxyphenyl) propane, 1,1,3,3-tetra Kis (3-t-butyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-di-t-butyl-4-hydroxyphenyl) propane, 1,1,4 , 4-tetrakis (4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-methyl-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3, 5-dimethyl-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-chloro-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5- Dichloro-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-methoxy-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-dimeth Methoxy-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-bromo-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-di Lomo-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-t-butyl-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5- Di-t-butyl-4-hydroxyphenyl) butane and the like.

Among these, when the clathrate compound mentioned later is formed, 1,1,2,2- since the said radiation sensitive resin composition is more excellent in storage stability at room temperature, and a hardening accelerator is easy to be released at the time of heating. Tetrakis (4-hydroxyphenyl) ethane is preferred.

As a compound represented by the said Formula (2), for example, 5-nitroisophthalic acid, 5-hydroxyisophthalic acid, 5-methylisophthalic acid, 5-methoxyisophthalic acid, 4-nitroisophthalic acid, 4-hydroxyiso Phthalic acid, 4-methylisophthalic acid, 4-methoxyisophthalic acid, and the like. Among these, 5-nitroisophthalic acid and 5-hydroxyisophthalic acid are preferable.

A compound [D] can be used individually or in mixture of 2 or more types. As content of the [D] compound in the said radiation sensitive resin composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] copolymers, 0.2 mass part-5 mass parts are more preferable, and It is preferable to set it as about 1 time-about 2 time with respect to the [E] amine compound mentioned later.

<[E] amine compound>

Although it does not specifically limit as an [E] amine compound, It is preferable that it is an amine compound which can be included in a compound [D], and it is more preferable that it is an imidazole compound or a benzoimidazole compound. Among these, since an imidazole compound is easy to be surrounded by a [D] compound, the storage stability at room temperature of the said radiation sensitive resin composition improves. Moreover, since an imidazole compound is excellent in reactivity with an epoxy group, it contributes to low temperature hardening of 200 degrees C or less.

As an imidazole compound, the compound etc. which are represented by following formula (3) are mentioned, for example.

In said formula (3), R <^10> -R <^13> is respectively independently a hydrogen atom, a C1-C6 alkyl group, a naphthyl group, an anthryl group, a phenanthryl group, a 9-fluorenyl group, a halogen atom, C1-C13 It is a phenyl group which may be substituted by the alkyl group of 6, a phenyl group, or a halogen atom.

As an imidazole compound, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-n-propylimidazole, 2-undecyl-1H-imid Dazole, 2-heptadecyl-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 -Methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazolium tri Mellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methyl Imidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2 , 4-Diamino-6- [2'-ethyl-4-imidazolyl- (1 ')]-ethyl-s-t Azine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazineisocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct , 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-sia Noethyl-2-phenyl-4,5-di (2-cyanoethoxy) methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1-benzyl-2-phenyl Midazole hydrochloride, 1-benzyl-2-phenylimidazolium trimellitate, and the like.

Among these, the imidazole compound which has 1 or more of C1-C6 substituents is preferable. Since such an imidazole compound is stably contained, it does not adversely affect the storage stability of the radiation-sensitive resin composition, and since the steric hindrance is small, it is excellent in reactivity and exhibits low temperature curability when the inclusions collapse. have.

As an imidazole compound which has 1 or more of said C1-C6 substituents, it is, for example

Imidazole compounds having one substituent having 1 to 6 carbon atoms such as 2-methylimidazole and 2-phenylimidazole;

Imidazoles having two substituents having 1 to 6 carbon atoms, such as 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole Compounds and the like.

As a benzimidazole compound, the compound etc. which are represented by following formula (4) are mentioned, for example.

In said formula (4), R <^14> -R <^16> is respectively independently a hydrogen atom, a C1-C6 alkyl group, a naphthyl group, an anthryl group, a phenanthryl group, a 9-fluorenyl group, a halogen atom, C1-C16 It is a phenyl group which may be substituted by the alkyl group of 6, a phenyl group, or a halogen atom. m is an integer of 0-4. However, when R <^14> is plurality, some R <^14> may be same or different.

As a benzoimidazole compound, for example, 2-methylbenzoimidazole, 4-methylbenzoimidazole, 5-methylbenzoimidazole, 6-methylbenzoimidazole, 7-methylbenzoimidazole, 2-methyl-6- Methylbenzoimidazole, 2-methyl-5-methylbenzoimidazole, 2-ethyl-6-methylbenzoimidazole, 2-methyl-6-ethylbenzoimidazole, 2-ethyl-5-methylbenzoimidazole, 2 -Methyl-5-ethylbenzoimidazole etc. are mentioned.

Among these, the benzoimidazole compound which has one or more substituents of C1-C6 is preferable. Since such an imidazole compound is stably contained, it does not adversely affect the storage stability of the radiation-sensitive resin composition, and since the steric hindrance is small, it is excellent in reactivity and exhibits low temperature curability when the inclusions collapse. have.

As a benzoimidazole compound which has 1 or more of said C1-C6 substituents, it is, for example

Benzoimidazole compound which has one C1-C6 substituents, such as 2-methylbenzoimidazole;

The benzoimidazole compound which has two C1-C6 substituents, such as 2-methyl-6-methylbenzoimidazole and 2-methyl-5-methylbenzoimidazole, etc. are mentioned.

[E] The amine compound can be used alone or in combination of two or more thereof. As content of the [E] compound in the said radiation sensitive resin composition, 0.05 mass parts-5 mass parts are preferable with respect to 100 mass parts of [A] copolymers, 0.1 mass part-2.5 mass parts are more preferable, and It is preferable to set it as about 0.5 to 1 time with respect to the compound [D].

<Clathrate compound>

In the radiation sensitive resin composition, at least a part of the [E] amine compound is preferably contained in the [D] compound. In the radiation sensitive resin composition, at least a part of the [A] amine compound is included in the [D] compound to form a clathrate compound, whereby storage stability and low temperature baking can be achieved.

The method of encapsulating the [E] amine compound with the [D] compound is not particularly limited, and examples thereof include the method described in JP-A-11-071449. The said radiation-sensitive resin composition whose viscosity in 25 degreeC is 1.0 mPa * s or more and 50 mPa * s or less is [A] copolymer and [B] superposition | polymerization of the clathrate compound in which the [E] amine compound was contained in the [D] compound. It is preferable to mix and prepare an soluble compound and a [C] radiation sensitive polymerization initiator. According to the said process, the said radiation sensitive resin composition containing a clathrate compound can be manufactured efficiently.

When a clathrate compound is formed beforehand and it contains in the said radiation sensitive resin composition, as content of the clathrate compound in the said radiation sensitive resin composition, it is 0.1 mass part-10 mass mass with respect to 100 mass parts of [A] copolymers. Addition is preferable and 0.2 mass part-5 mass parts are more preferable. By setting the content ratio of the clathrate compound to 0.1 parts by mass to 10 parts by mass, the storage stability of the radiation-sensitive resin composition and the curing acceleration of the cured film can be made compatible at a high level, and the resulting cured film such as a protective film, an interlayer insulating film, or a spacer The voltage holding ratio of the provided display element can be maintained at a high level.

<Optional ingredient>

The radiation sensitive resin composition, in addition to the above-mentioned [A] copolymer, [B] polymerizable compound, [C] radiation sensitive polymerization initiator, [D] compound and [E] amine compound, impairs the desired effect. As long as it is not needed, you may contain arbitrary components, such as a compound which has two or more oxiranyl groups in one molecule, an adhesion | attachment adjuvant, surfactant, a storage stabilizer, and a heat resistance improving agent. These arbitrary components may be used independently, or may mix and use 2 or more types. Hereinafter, each component is explained in full detail.

[Compound having two or more oxiranyl groups in one molecule]

The compound which has two or more oxiranyl groups in 1 molecule can be added in order to improve the hardness of the cured film obtained further. As such a compound, the compound etc. which have 2 or more 3, 4- epoxycyclohexyl group in 1 molecule are mentioned, for example.

As a compound which has two or more 3, 4- epoxy cyclohexyl groups in 1 molecule, it is 3, 4- epoxy cyclohexyl methyl-3 ', 4'- epoxy cyclohexane carboxylate, 2- (3, 4- epoxy, for example. Cyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meth-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexyl Methyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene Epoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), lactone modified 3,4-epoxycyclohexylmethyl-3 ', 4' -Epoxycyclohexane carboxylate, etc. are mentioned.

As other compounds, for example

Bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, Bisphenol S diglycidyl ether, Hydrogenated bisphenol A diglycidyl ether, Hydrogenated bisphenol F diglycidyl ether, Hydrogenated bisphenol AD diglycol Diglycidyl ethers of bisphenol compounds such as cydyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol S diglycidyl ether;

1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol digly Polyglycidyl ethers of polyhydric alcohols such as cydyl ether;

Polyglycidyl ethers of polyether polyols obtained by adding one or two or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;

Phenol novolac type epoxy resin;

Cresol novolac type epoxy resin;

Polyphenol type epoxy resin;

Cyclic aliphatic epoxy resins;

Diglycidyl ester of aliphatic long chain dibasic acid;

Glycidyl esters of higher fatty acids;

Epoxidized soybean oil, epoxidized linseed oil, etc. are mentioned. Among these, phenol novolak-type epoxy resins and polyphenol-type epoxy resins are preferable.

As these commercial items, for example

EPICOAT 1001, copper 1002, copper 1003, copper 1004, copper 1007, copper 1009, copper 1010, copper 828 (above, Japan Epoxy Resin Co., Ltd.) as bisphenol-A epoxy resin;

Epicoat 807 (Japan Epoxy Resin Co., Ltd.) as a bisphenol F type epoxy resin;

Epicoat 152, Copper 154, Copper 157S65 (above, Japan Epoxy Resin Co., Ltd.), EPPN 201, Copper 202 (above, Nippon Kayaku Co., Ltd.) as a phenol novolak-type epoxy resin;

EOCN 102, copper 103S, copper 104S, copper 1020, copper 1025, copper 1027 (above, Nippon Kayaku Co., Ltd.), epicoat 180S75 (Japan Epoxy Resin Co., Ltd.) as a cresol novolak-type epoxy resin;

Epicoat 1032H60 as a polyphenol type epoxy resin, XY-4000 (above, Japan Epoxy Resin Co., Ltd.);

CY-175, copper 177, copper 179, ARALDITE CY-182, copper 192, copper 184 (above, Chiba Specialty Chemicals Co., Ltd.), ERL-4234, copper 4299 as cyclic aliphatic epoxy resin , East 4221, East 4206 (above, UCC), Shodyne 509 (Showa Denko), Epiclon (EPICLON) 200, East 400 (above, Dainippon Inkie) 871, East 872 (above, Japan Epoxy Resin Co., Ltd.), ED-5661, East 5662 (above, Ceranie Coating Co., Ltd.);

EPORITE 100MF (Kyoeisha Kagaku Co., Ltd.), Epiol TMP (Nihon Yushi Co., Ltd.), etc. as aliphatic polyglycidyl ether are mentioned.

As a usage-amount of the compound which has two or more oxiranyl groups in 1 molecule, 50 mass parts or less are preferable with respect to 100 mass parts of [A] copolymers, 2 mass parts-50 mass parts are more preferable, 5 mass parts-30 Part by mass is particularly preferred. By making the usage-amount of the compound which has two or more oxiranyl groups in 1 molecule into the said specific range, the hardness of cured films, such as an interlayer insulation film, a spacer, or a protective film, can be improved more without impairing developability.

[Adhesive preparation]

An adhesion | attachment adjuvant can be used in order to improve the adhesiveness of cured films, such as an interlayer insulation film, a spacer, or a protective film obtained, and a board | substrate further. As this adhesion | attachment adjuvant, the functional silane coupling agent which has reactive functional groups, such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, an oxiranyl group, is preferable, For example, trimethoxysilyl benzoic acid, (gamma) -methacryl Oxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, and the like.

As the usage-amount of an adhesion | attachment adjuvant, 20 mass parts or less are preferable with respect to 100 mass parts of [A] copolymers, and 15 mass parts or less are more preferable. When the usage-amount of an adhesion | attachment adjuvant exceeds 20 mass parts, there exists a tendency which becomes easy to generate | occur | produce a developing residue.

[Surfactants]

Surfactant can be used in order to improve the coating film formability of the said radiation sensitive resin composition further. As surfactant, a fluorochemical surfactant, silicone type surfactant, other surfactant, etc. are mentioned, for example.

As a fluorine type surfactant, the compound which has a fluoroalkyl group and / or a fluoroalkylene group in at least any part of a terminal, a main chain, and a side chain is preferable, For example, 1,1,2,2- tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol di (1,1, 2,2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1 , 2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycoldi (1,1,2,2-tetrafluoro-n-butyl) ether, perfluoro-n-dodecanesulfonic acid Sodium, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane Or sodium fluoroalkylbenzenesulfonate, sodium fluoroalkyl phosphate, sodium fluoroalkyl carbonate, diglycerin tetrakis (fluoroalkylpol Reoxyethylene ether), fluoroalkyl ammonium iodine, fluoroalkyl betaine, other fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, carboxylic acid fluoroalkyl ester, etc. Can be mentioned.

As a commercial item of a fluorine-type surfactant, BM-1000, copper 1100 (above, BM CHEMIE company), Megapack (MEGAFAC) 142D, copper F172, copper F173, copper F183, copper F178, copper F191, copper F471, copper F476 (above, Dai Nippon Inkaki Kagaku Kogyo Co., Ltd.), Fluorad (FLUORAD) FC-170C, east 171, east 430, east 431 (above, Sumitomo 3M Kabuki Kaisha), SURFLON S-112 , East 113, East 131, East 141, East 145, East 382, Suflon SC-101, East 102, East 103, East 104, East 105, East 106 (above, Asahi Glass Co., Ltd.), F-Top ( EFTOP) EF301, East 303, East 352 (above, Shin Akita Kasei Co., Ltd.), FTERGENT FT-100, East 110, East 140A, East 150, East 250, East 251, East 300, East 310, Copper 400S, aftergent FTX-218, copper 251 (above, neos).

As a commercial item of a silicone type surfactant, for example, TORAY SILICON DC3PA, copper DC7PA, copper SH11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH-190, copper SH-193, copper SZ-6032 , SF-8428, DC-57, DC-190 (above, Torre Dow Corning Silicon Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF -4452 (above, GE Toshiba Silicone Co., Ltd.), organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.), etc. are mentioned.

As other surfactant, For example, polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene-n-octylphenyl ether and polyoxyethylene-n-nonylphenyl ether; Nonionic surfactants, such as polyoxyethylene dialkyl esters, such as a polyoxyethylene dilaurate and polyoxyethylene distearate, (meth) acrylic-acid copolymer polyflow (POLYFLOW) No. 57, copper 95 (or more, Kyoeisha Kagaku Kabushiki Kaisha) etc. are mentioned.

As the usage-amount of surfactant, 1.0 mass part or less is preferable with respect to 100 mass parts of [A] copolymers, and 0.5 mass part or less is more preferable. When the usage-amount of surfactant exceeds 1.0 mass part, it will become easy to produce a film nonuniformity.

[Storage Stabilizer]

Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitronitroso compounds, and the like. More specifically, 4-methoxyphenol and N-nitroso-N- Phenyl hydroxyl amine aluminum etc. are mentioned.

As the usage-amount of a storage stabilizer, 3.0 mass parts or less are preferable with respect to 100 mass parts of [A] copolymers, and 0.5 mass parts or less are more preferable. When the compounding quantity of a storage stabilizer exceeds 3.0 mass parts, the sensitivity of the said radiation sensitive resin composition may fall and a pattern shape may deteriorate.

[Heat resistance improver]

Examples of the heat resistance improver include N- (alkoxymethyl) glycoluril compounds, N- (alkoxymethyl) melamine compounds, and the like.

Examples of the N- (alkoxymethyl) glycoluril compound include N, N, N ', N'-tetra (methoxymethyl) glycoluril, N, N, N', N'-tetra (ethoxymethyl) glycol Uryl, N, N, N ', N'-tetra (n-propoxymethyl) glycoluril, N, N, N', N'-tetra (i-propoxymethyl) glycoluril, N, N, N ' , N'-tetra (n-butoxymethyl) glycoluril, N, N ', N ", N"'-tetra (t-butoxymethyl) glycoluril, etc. are mentioned. Among these, N, N, N ', N'-tetra (methoxymethyl) glycoluril is preferable.

Examples of N- (alkoxymethyl) melamine compounds include N, N, N ', N', N ", N" -hexa (methoxymethyl) melamine, N, N, N ', N', N ", N "-hexa (ethoxymethyl) melamine, N, N, N ', N', N", N "-hexa (n-propoxymethyl) melamine, N, N, N ', N', N", N "-hexa (i-propoxymethyl) melamine, N, N, N ', N', N", N "-hexa (n-butoxymethyl) melamine, N, N, N ', N', N ", N" -hexa (t-butoxymethyl) melamine and the like can be given. Among these, N, N, N ', N', N ", N" -hexa (methoxymethyl) melamine is preferable. As a commercial item, NIKALAC N-2702, MW-30M (above, Sanwa Chemical), etc. are mentioned, for example.

As a usage-amount of a heat resistance improving agent, 50 mass parts or less are preferable with respect to 100 mass parts of [A] copolymers, and 30 mass parts or less are more preferable. When the compounding quantity of a heat resistance improving agent exceeds 50 mass parts, the sensitivity of the said radiation sensitive resin composition may fall and a pattern shape may deteriorate.

<Preparation method of a radiation sensitive resin composition>

The radiation sensitive resin composition for forming a cured film of the present invention is a scavenger in addition to the [A] copolymer, the [B] polymerizable compound, the [C] radiation sensitive polymerization initiator, the [D] compound, and the [E] amine compound. It is prepared by mixing arbitrary components in predetermined ratio as needed in the range which does not impair the effect of. The said radiation sensitive resin composition whose viscosity in 25 degreeC is 1.0 mPa * s or more and 50 mPa * s or less is [A] copolymer and [B] superposition | polymerization of the clathrate compound in which the [E] amine compound was enclosed in the [D] compound. It is preferable to mix and prepare an soluble compound and a [C] radiation sensitive polymerization initiator.

As a solvent used for preparation of the said radiation sensitive resin composition, what melt | dissolves or disperse | distributes each component uniformly, and what does not react with each component is used. As such a solvent, what was illustrated as a solvent which can be used for synthesize | combining the above-mentioned [A] copolymer is applicable.

It is preferable that the solvent contains at least one solvent selected from the group consisting of alcohol solvents and ether solvents. By containing said polar solvent, the said radiation sensitive resin composition can be melt | dissolved easily, and in this invention, even if a polar solvent is used as mentioned above, the collapse of clathration is suppressed by interaction with a clathrate compound. I think you can. A solvent can be used individually or in mixture of 2 or more types.

Moreover, in order to raise the in-plane uniformity of a film thickness with the said solvent, a high boiling point solvent can be used together. As the high boiling point solvent, for example, N-methylpyrrolidone, N, N-dimethylacetamide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate And diethyl oxalate, diethyl maleate, γ-butyrolactone, and propylene carbonate. Among these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.

When using a high boiling point solvent together as a solvent of the said radiation sensitive resin composition, as the usage-amount, 50 mass% or less is preferable with respect to the total amount of solvent, 40 mass% or less is more preferable, and 30 mass% or less Particularly preferred. When the usage-amount of a high boiling point solvent is 50 mass% or less, the film thickness uniformity, a sensitivity, and a residual film ratio of a coating film become favorable.

When preparing the radiation-sensitive resin composition in a solution state, the solid content concentration (components other than the solvent occupied in the composition solution) is any concentration (for example, 5% by mass to 50 mass%). As a more preferable solid content concentration, although it changes with the formation method of the coating film on a board | substrate, it mentions later. The composition solution thus prepared can be used for use after being filtered using a Millipore filter or the like having a pore size of about 0.5 µm.

<Formation method of hardened film>

The cured film as an interlayer insulation film, a protective film, or a spacer formed from the said radiation sensitive resin composition is also contained suitably for this invention. Formation method of the cured film of this invention,

(1) Process of forming the coating film of the said radiation sensitive resin composition on a board | substrate

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

(3) developing the coating film irradiated with the radiation;

(4) The process of baking the developed coating film

Respectively.

By the formation method of this invention using the said radiation sensitive resin composition, the cured film which satisfy | fills heat resistance, chemical-resistance, transmittance | permeability, flatness, and heat-resistance thermal expansion balance can be formed in good balance. Hereinafter, each process is explained in full detail.

[Step (1)]

This process forms a transparent conductive film in the single side | surface of a transparent substrate, and forms the coating film of a radiation sensitive resin composition on this transparent conductive film. As a transparent substrate, the resin substrate which consists of plastics, such as glass substrates, such as a soda-lime glass and an alkali free glass, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and polyimide, etc. are mentioned, for example. .

Examples of the transparent conductive film formed on one surface of the transparent substrate include an NESA film made of tin oxide (SnO ₂ ) (PPG, registered trademark), an ITO film made of indium tin oxide (In ₂ O ₃ -SnO ₂ ), and the like. Can be mentioned.

When forming a coating film by the apply | coating method, after apply | coating the solution of the said radiation sensitive resin composition on the said transparent conductive film, Preferably, a coating film can be formed by prebaking an application surface. As solid content concentration of the composition solution used for a coating method, 5 mass%-50 mass% are preferable, 10 mass%-40 mass% are more preferable, 15 mass%-35 mass% are especially preferable. As a coating method, the spray method, the roll coating method, the rotary coating method (spin coating method), the slit coating method (slit die coating method), the bar coating method, the inkjet coating method, etc. are mentioned, for example. Among these, the spin coating method and the slit coating method are preferable.

As conditions for prebaking, although it changes with the kind, compounding ratio, etc. of each component, 70 degreeC-120 degreeC is preferable and it is about 1 to 15 minutes. 0.5 micrometer-10 micrometers are preferable, and, as for the film thickness after prebaking of a coating film, 1.0 micrometer-7.0 micrometers are more preferable.

[Step (2)]

This process chart irradiates at least a part of the formed coating film with radiation. At this time, when irradiating only a part of coating film, it can be based on the method of irradiating through the photomask which has a predetermined pattern, for example. As radiation used for irradiation, a visible ray, an ultraviolet-ray, an ultraviolet ray, etc. are mentioned, for example. Among these, the radiation whose wavelength is in the range of 250 nm-550 nm is preferable, and the radiation which contains the ultraviolet-ray of 365 nm is more preferable.

The radiation dose (exposure dose) is a value measured by an illuminometer (OAI Model 356, Optical Associates Inc.) of the intensity of the irradiated radiation at a wavelength of 365 nm, preferably 100 J / m 2 to 5,000 J / m 2, and 200 J / M <2> -3,000 J / m <2> is more preferable.

The radiation-sensitive resin composition has a higher radiation sensitivity than the conventionally known composition, and has a desired film thickness, good shape, excellent adhesion, and high hardness even when the radiation dose is 700 J / m 2 or less, or even 600 J / m 2 or less. It has the advantage that a cured film, such as an interlayer insulation film, a protective film, or a spacer, can be obtained.

[Step (3)]

This process develops the coating film irradiated with the said radiation, removes an unnecessary part, and forms a predetermined pattern.

As a developing solution used for image development, aqueous solution of alkaline compounds, such as inorganic alkali, such as sodium hydroxide, potassium hydroxide, sodium carbonate, quaternary ammonium salts, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, etc. are mentioned, for example. Can be. Aqueous amounts of water-soluble organic solvents such as methanol and ethanol and / or surfactants may be added to the aqueous solution of the alkaline compound and used.

As a developing method, a puddle method, the dipping method, the shower method, etc. are mentioned, for example. As image development time, about 10 second-180 second are preferable at normal temperature. After the development treatment, for example, flowing water washing is performed for 30 seconds to 90 seconds, and then a desired pattern can be obtained by air drying with compressed air or compressed nitrogen.

[Step (4)]

This process bakes (postbakes) the obtained pattern shape coating film by suitable heating apparatuses, such as a hotplate and oven. As baking temperature, 100 degreeC-200 degreeC is preferable, and 150 degreeC-180 degreeC is more preferable. As mentioned above, the said radiation sensitive resin composition realizes low temperature baking, compatible with storage stability, and has sufficient radiation sensitivity. Therefore, the said radiation sensitive resin composition is used suitably as a formation material of cured films, such as an interlayer insulation film, a protective film, and a spacer used for flexible displays etc. which low temperature baking is desired. As baking time, for example, 5 minutes-30 minutes are preferable on a hotplate, and 30 minutes-180 minutes are preferable in an oven.

<Method for Manufacturing Display Element>

In this invention, the display element provided with the said cured film is also suitably included in this invention. The display element can realize an excellent voltage holding ratio.

As a manufacturing method of a display element, first, a pair (two sheets) of transparent substrates which have a transparent conductive film (electrode) on one side are prepared, and the said radiation-sensitive resin composition is prepared on the transparent conductive film of one board | substrate in it. By using the above-described method, a spacer or a protective film or both thereof is formed. Subsequently, an alignment film having liquid crystal alignment capability is formed on the transparent conductive film and the spacer or the protective film of these substrates. These board | substrates are arrange | positioned facing the surface of the side in which the orientation film was formed inward, and through the constant gap (cell gap) so that the liquid crystal aligning direction of each alignment film may be orthogonal or antiparallel, and the surface (alignment film) of a board | substrate, and The liquid crystal is filled in the cell gap partitioned by the spacer, and the filling hole is sealed to form a liquid crystal cell. And the display element of this invention is obtained by bonding a polarizing plate to both outer surfaces of a liquid crystal cell so that the polarization direction may coincide with or perpendicular to the liquid crystal aligning direction of the alignment film formed in one surface of the said board | substrate.

As another method, a transparent conductive film, an interlayer insulating film, a protective film or a spacer, or both, and a pair of transparent substrates on which an alignment film is formed are prepared in the same manner as the above method. Then, the ultraviolet curable sealing compound is apply | coated using a dispenser along the edge part of one board | substrate, Then, a liquid crystal is dripped in the shape of a micro droplet using a liquid crystal dispenser, and bonding of both board | substrates under vacuum is carried out. Do it. And the said sealing agent is irradiated with an ultraviolet-ray using a high pressure mercury lamp, and both board | substrates are sealed. Finally, the display element of this invention is obtained by bonding a polarizing plate to both outer surfaces of a liquid crystal cell.

As a liquid crystal used in each said method, a nematic liquid crystal, a smectic liquid crystal, etc. are mentioned, for example. Moreover, as a polarizing plate used on the outer side of a liquid crystal cell, the polarizing plate which inserted the polarizing film called "H film | membrane" which absorbed iodine into the cellulose-acetic acid protective film, or extending | stretching polyvinyl alcohol, the polarizing plate which consists of H film itself, etc. are mentioned. Can be.

(Example)

Hereinafter, although this invention is explained based on an Example, this invention is not interpreted limitedly to this Example.

<Synthesis of [A] Copolymer>

Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methylethyl ether were placed. Subsequently, 20 parts by mass of styrene, 12 parts by mass of methacrylic acid, 28 parts by mass of dicyclopentanyl methacrylate, and 40 parts by mass of glycidyl methacrylate were added thereto, nitrogen-substituted, and the stirring was continued gently. The solution containing the copolymer (A-1) was obtained by raising it to 70 degreeC and preserving and polymerizing this temperature for 5 hours. Solid content concentration of the obtained copolymer solution was 31.3%, and Mw of the copolymer (A-1) was 12,000. In addition, solid content concentration means the ratio of the copolymer mass to the total mass of a copolymer solution.

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methylethyl ether were placed. Subsequently, 10 parts by mass of styrene, 12 parts by mass of methacrylic acid, 23 parts by mass of methacrylic acid tricyclodicyclopentanyl, 20 parts by mass of glycidyl methacrylate, 20 parts by mass of 2-methylglycidyl methacrylate, and meta After adding 10 parts by mass of tetrahydrofurfuryl acrylate and replacing with nitrogen, 5 parts by mass of 1,3-butadiene was further added, while stirring was continued gently, the temperature of the solution was raised to 70 ° C, and this temperature was increased for 5 hours. By preservation and superposition | polymerization, the solution containing copolymer (A-2) was obtained. Solid content concentration of the obtained copolymer solution was 31.5%, and Mw of the copolymer (A-2) was 10,100.

Synthesis Example 3

5 mass parts of 2,2'- azobis (isobutylonitrile) and 220 mass parts of diethylene glycol methyl ethyl ether were put into the flask provided with a cooling tube and the stirrer. Subsequently, 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 thereto, and the temperature of the solution was kept at 80 ° C. with gentle stirring. The solution containing the copolymer (A-3) was obtained by raising and preserving and polymerizing this temperature for 5 hours. Solid content concentration of the obtained copolymer solution was 31.0%, and Mw of the copolymer (A-3) was 10,000.

<Preparation of the radiation sensitive resin composition for hardening film formation>

The detailed description of each component used for preparation of each radiation sensitive resin composition is shown below.

[B] Polymerizable Compound

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

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

B-3: 1,9-nonanediol diacrylate

B-4: pentaerythritol tetraacrylate

B-5: trimethylolpropane triacrylate

B-6: ω-carboxylepolycaprolactone monoacrylate (Aronix M-5300, Toagose Co., Ltd.)

B-7: succinic acid modified pentaerythritol triacrylate (aronix TO-756, Toagose Co., Ltd.)

B-8: ethylene oxide modified dipentaerythritol hexaacrylate

[C] radiation sensitive polymerization initiator

C-1: 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (irgacure (OXGACURE) OXE01, Chiba Specialty Chemicals Co., Ltd.)

C-2: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (irgacure OXE02, Chiba specialty Chemicals Co., Ltd.

C-3: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (irgacure 907, Chiba Specialty Chemicals Co., Ltd.)

C-4: 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (irgacure 379, Chiba specialty chemicals) Kabushi Kaisha)

[D] compound

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

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

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

[E] amine compounds

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

E-2: 2-methylimidazole

E-3: 2-ethyl-4-methylimidazole

E-4: 2-methylbenzoimidazole

Clathrate compound

F-1 to F-10 as clathrate compounds shown below are compounds in which the [E] amine compound was clad in the said [D] compound as a host compound, respectively.

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

F-2: 0.62 parts by mass of D-2 and 0.33 parts by mass of E-1 (2: 1)

F-3: 0.6-3 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: 0.62 parts by mass of D-2 and 0.33 parts by mass of E-2 (2: 1)

F-6: D-3 0.67 parts by mass and E-2 0.33 parts by mass (2: 1)

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

F-8: 0.6-2 parts by mass of D-2 and 0.33 parts by mass of E-3 (2: 1)

F-9: 0.6-3 parts by mass of D-3 and 0.33 parts by mass of E-3 (2: 1)

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

menstruum

S-1: Propylene Glycol Monomethyl Ether Acetate

S-2: Propylene Glycol Monomethyl Ether

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

The kind shown in Table 1, the [A] copolymer, the [B] polymerizable compound, the [C] polymerization initiator, and the clathrate compound, or the [E] amine compound of the usage amount are mixed, and also an adhesion | attachment adjuvant as an arbitrary component ((gamma-gly) 5 parts by mass of cydoxypropyltrimethoxysilane), 0.5 parts by mass of surfactant (FTX-218, Neos), and 0.5 parts by mass of storage stabilizer (4-methoxyphenol) were added, and a solvent was added, followed by a pore size of 0.5. Each radiation-sensitive resin composition was prepared by filtration with a millimeter pore filter. The viscosity was 16 mPa · s. In addition, "-" in a column shows that the corresponding component was not used. Moreover, it shows also about the measurement result of the viscosity in 25 degreeC of each radiation sensitive resin composition.

<evaluation>

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

[Storage Stability (%)]

Each radiation-sensitive resin composition was left to stand in 40 degreeC oven for 1 week, the viscosity before and after putting into oven, the viscosity change rate (%) was calculated | required, and it was set as storage stability (%). When the viscosity change rate was 5% or less, it was judged that storage stability is favorable, and when the viscosity change rate exceeds 5%, it was judged that storage stability is poor. In addition, the viscosity was measured at 25 degreeC using the E-type viscosity meter (VISCONIC® ELD.R, Toki Sangyo Co., Ltd.).

[Sensitivity (J / m2)]

After apply | coating each radiation sensitive resin composition with a spinner on the alkali free glass substrate, the film of 4.0 micrometers in thickness was formed by prebaking for 2 minutes on a 100 degreeC hotplate. Subsequently, in the obtained film, the exposure amount was varied in the range of 200 J / m 2 to 1,000 J / m 2 using a high-pressure mercury lamp via a photomask having a plurality of annular residue patterns of different sizes having a diameter of 8 μm to 15 μm. Irradiation was performed. Thereafter, using a 0.40 mass% tetramethylammonium hydroxide aqueous solution, development was carried out at 25 ° C. as a variable, and developed by the puddle method, followed by pure water washing for 1 minute. Furthermore, the cured film which has an annular residue pattern was formed by post-baking at 180 degreeC for 60 minutes in oven. The height before and after image development of the cyclic | annular residue pattern was measured using the laser microscope (VK-8500, Keyence Corporation). Residual film ratio (%) was calculated | required from this value and the following formula.

Residual film ratio (%) = (height after development / height before development) x 100

The exposure amount which a residual film ratio becomes 90% or more was made into the sensitivity (J / m <2>). When the exposure amount was 750 J / m 2 or less, it was judged that the sensitivity was good. In addition, in the comparative example 4, the pattern was not able to be formed (it shows with "-" in Table 2).

[Heat resistance (%)]

In the above-mentioned cured film formation process, about the coating film obtained by exposing at the exposure amount of 700 J / m <2> without a photomask, the film thickness before and behind heating for 20 minutes at 230 degreeC in oven is further provided. It measured with the measuring instrument (alpha step IQ, KLA Tenco Corporation). Residual film ratio (%) was calculated | required from this value and following formula, and it was set as heat resistance (%).

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

[Chemical resistance (%)]

In the cured film forming step described above, the alignment film release liquid Chemiclean TS-204 (Sanyo Kasei Co., Ltd.) heated at 60 ° C with respect to a coating film obtained by exposing at an exposure dose of 700 J / m 2 without interposing a photomask. After immersing in water for 15 minutes and washing with water, it was further dried in an oven for 15 minutes at 120 degreeC. The film thickness before and after this treatment was measured with a stylus film thickness gauge (alpha step IQ, KLA Tenco Co., Ltd.), the said residual film ratio (%) was computed, and this was made into chemical resistance (%).

Transmittance (%)

In the cured film forming step described above, a transmittance (%) at a wavelength of 400 nm is determined using a spectrophotometer (150-20 type double beam, provisional) with respect to the coating film obtained by exposing at an exposure dose of 700 J / m 2 without interposing a photomask. It was measured using Shichigaisha Hitachi Seisakusho. When this value is 90% or more, it was judged that transparency (%) was favorable.

[Flatness (nm)]

On the SiO ₂ dip glass substrate, a red, green and blue three-color stripe-shaped color filter was applied using a pigment-based color resist (JCR RED 689, JCR GREEN 706 and CR 8200B, or more JSR). Formed. Specifically, using spinner, one color of the color resist is SiO ₂ It applied to the dip glass substrate, prebaked at 90 degreeC for 150 second on the hotplate, and formed the coating film. Subsequently, i-line conversion of the ghi line (wavelength 436 nm, 405 nm, 365 nm intensity ratio = 2.7: 2.5: 4.8) through a predetermined pattern mask using an exposure machine (Canon PLA501F, Canon Corporation). The solution was irradiated at an exposure dose of 2,000 J / m 2, and then developed using 0.05 mass% potassium hydroxide aqueous solution, followed by rinsing with ultrapure water for 60 seconds. Subsequently, heat treatment was further performed at 230 degreeC for 30 minutes in oven, and the monochromatic stripe-shaped color filter was formed. By repeating this operation for three colors, red, green, and blue three-color striped color filters (stripe width of 200 mu m) were formed. Measurement length 2,000 µm, measuring range 2,000 µm Angle, measuring direction in red, green, blue direction of the stripe line short axis and red, red, green, green, blue, blue color direction As a result of measuring the unevenness | corrugation of the surface of a color filter board | substrate with the measurement score n = 5 (n number of totals is 10) about each direction by the contact type film thickness measuring apparatus (alpha step, KLA Tenco Corporation), 1.0 micrometer. After each thermosetting resin composition was apply | coated to the board | substrate with this color filter by a spinner, it prebaked at 90 degreeC for 5 minutes on a hotplate, and formed a coating film, and posts further at 180 degreeC for 60 minutes in a clean oven. By baking, the protective film with a film thickness of about 2.0 micrometers from the upper surface of a color filter was formed. About the board | substrate which has a protective film on the color filter formed in this way, the unevenness | corrugation of the surface of a protective film was measured with the contact type film thickness measuring apparatus (alpha-step, KLA Tenco Corporation). The measurement is performed by measuring the length of 2,000 μm, the measuring range of 2,000 μm, the direction of measurement of the stripe line short axis in the red, green, and blue directions, and the stripe line in the long axis direction of the same color of red, red, green, green, and blue. In each direction, the measurement score n = 5 (n number of totals is 10) was used for each direction, and the average value of ten times of the height difference (nm) of the highest part and the lowest part of each measurement was obtained to obtain flatness (nm). When this value was 200 nm or less, it was judged that flatness was favorable.

[Coefficient of Thermal Expansion (ppm / ° C)]

In the said cured film formation process, it exposed by the exposure amount of 700 J / m <2> without interposing a photomask, and formed the coating film. Then, the coating film for a measurement was formed by heat-processing and hardening | curing at 180 degreeC for 60 minutes in oven. Subsequently, with this ellipsometer (DVA-36LH, Mizoji Riko Gakukojojo Co., Ltd.) provided with a temperature variable device, the temperature increase rate at the time of measurement in nitrogen atmosphere was 10 degreeC / min, The measurement temperature range is 20 ° C to 200 ° C, the amount of change in the film thickness at each measurement temperature is measured, plotted against temperature, the slope b is obtained from the linear approximation, and the linear thermal expansion coefficient a ) (ppm / ° C) was obtained. T represents the initial film thickness.

a = b / T

When the coefficient of linear thermal expansion was 200 ppm / ° C. or less, it was judged that the coefficient of linear thermal expansion was low and a cured film having sufficient curability could be formed even by postbaking at 180 ° C.

[Voltage maintenance rate (%)]

On the surface, the SiO ₂ film | membrane which prevents elution of sodium ion is formed, and each radiation-sensitive resin composition is spin-coated on the soda glass substrate which deposited the ITO (indium-tin oxide alloy) electrode in the predetermined shape. Thereafter, prebaking was performed in a clean oven at 90 ° C. for 10 minutes to form a coating film having a thickness of 2.0 μm. Subsequently, it exposed to the coating film by the exposure amount of 500 J / m <2> without interposing a photomask. Then, this board | substrate is immersed in the developing solution which consists of a 0.04 mass% potassium hydroxide aqueous solution at 23 degreeC for 1 minute, and after developing, it wash | cleaned with ultrapure water, air-dried, and post-baked at 180 degreeC for 60 minutes, hardening a coating film To form a permanent cured film. Subsequently, after bonding the board | substrate which formed this pixel and the board | substrate which only deposited the ITO electrode to a predetermined shape with the sealing compound which mixed 0.8 mm glass beads, the liquid crystal cell made by Merck (MLC 6608) is inject | poured, and the liquid crystal cell is Made. Subsequently, the liquid crystal cell was put into the 60 degreeC constant temperature layer, and the voltage holding ratio (%) of the liquid crystal cell was measured by the liquid crystal voltage holding ratio measurement system (VHR-1A type, Toyo Technica). The applied voltage at this time was a square wave of 5.5 V, and the measurement frequency was 60 Hz. Voltage retention was calculated | required from the following formula.

Voltage retention rate (%) = (voltage applied by liquid crystal cell potential difference / 0 millisecond after 16.7 milliseconds) x 100

When the voltage holding ratio is 90% or less, the liquid crystal cell cannot keep the applied voltage at a predetermined level for a time of 16.7 milliseconds, which means that the liquid crystal cannot be oriented sufficiently, causing "burn in" such as afterimages. Concerns are high.

From the result of Table 2, it turned out that the said radiation sensitive resin composition of Examples 1-15 has the favorable storage stability and radiation sensitivity compared with the composition of Comparative Examples 1-4. Moreover, although the cured film formed from the said radiation sensitive resin composition was formed by low temperature baking of 200 degrees C or less, it turned out that it is excellent in heat resistance, chemical-resistance, transmittance | permeability, flatness, and thermal-expansion resistance. Moreover, it turned out that it is favorable also about the voltage holding ratio of the display element provided with the said cured film.

The radiation-sensitive resin composition for forming a cured film of the present invention can easily form a fine and sophisticated pattern, is compatible with storage stability and low temperature baking, and has sufficient radiation sensitivity. Moreover, the cured film formed from the said radiation sensitive resin composition is excellent in heat resistance, chemical-resistance, transmittance | permeability, flatness, and heat-resistant thermal expansion property. Therefore, the said radiation sensitive resin composition is used suitably as a formation material of cured films, such as an interlayer insulation film, a protective film, and a spacer used for flexible displays etc. which low temperature baking is desired. Moreover, the display element provided with this cured film is also suitably included in this invention, and can implement | achieve the outstanding voltage holding ratio.

Claims (13)

(A) a copolymer having (a1) a carboxyl group-containing structural unit and (a2) an epoxy group-containing structural unit,
[B] a polymerizable compound having an ethylenically unsaturated bond,
[C] radiation sensitive polymerization initiator,
[D] a compound having a hydroxyl group or a carboxyl group, and
[E] amine compounds
And the radiation sensitive resin composition for cured film formation whose viscosity in 25 degreeC is 1.0 mPa * s or more and 50 mPa * s or less. The method of claim 1,
The radiation sensitive resin composition for cured film formation which an [E] amine compound can be included in a compound [D]. The method of claim 1,
The compound [D] is at least one compound selected from the group consisting of compounds represented by the following formulas (1) and (2), respectively, and the [E] amine compound is an imidazole compound or a benzimidazole compound, Radiation-sensitive resin composition for forming a cured film:

(In formula (1), X is a single bond, a methylene group, or a C2-C6 alkylene group, R <^1> -R <^8> is respectively independently a hydrogen atom, a C1-C12 alkyl group, a halogen atom, and C1-C1 It is a phenyl group which may have a -12 alkoxy group or a substituent;
In formula (2), R <^9> is a C1-C12 alkyl group, a C1-C12 alkoxy group, a nitro group, or a hydroxyl group.). The method of claim 3,
The radiation sensitive resin composition for cured film formation whose compound represented by said formula (1) is a compound represented by following formula (1-1).

(In formula (1-1), X and R <^1> -R <^8> is synonymous with said Formula (1).). The method of claim 1,
The radiation sensitive resin composition for cured film formation in which at least one part of the [E] amine compound is included in the [D] compound. The method of claim 1,
[C] The radiation sensitive resin composition for forming a cured film, wherein the radiation sensitive polymerization initiator is at least one selected from the group consisting of an acetophenone compound and an O-acyl oxime compound. The method of claim 1,
The radiation sensitive resin composition for cured film formation which further contains at least 1 sort (s) of solvent chosen from the group which consists of an alcohol solvent and an ether solvent. The method according to any one of claims 1 to 7,
A clathrate compound in which the [E] amine compound is embedded in the [D] compound is mixed with a [A] copolymer, a [B] polymerizable compound and a [C] radiation sensitive polymerization initiator to prepare a viscosity at 25 ° C. The radiation sensitive resin composition for cured film formation whose is 1.0 mPa * s or more and 50 mPa * s or less. [D] A copolymer having a clathrate compound wherein [E] an amine compound is embedded in a compound having a hydroxyl group or a carboxyl group, a copolymer having [A] (a1) a carboxyl group-containing structural unit and (a2) an epoxy group-containing structural unit, [B] ethylene Persimmon for cured film formation which has the process of mixing so that it may become a polymeric compound which has a unsaturated unsaturated bond, and a [C] radiation sensitive polymerization initiator, and will become a viscosity in 25 degreeC from 1.0 mPa * s or more and 50 mPa * s or less. The manufacturing method of a radioactive resin composition. (1) Process of forming the coating film of the radiation sensitive resin composition for cured film formation as described in any one of Claims 1-7 on a board | substrate,
(2) irradiating at least a part of the coating film with radiation;
(3) developing the coating film irradiated with the radiation;
(4) The process of baking the developed coating film
The formation method of the cured film which has. The method of claim 10,
The formation method of the cured film whose baking temperature of the said process (4) is 200 degrees C or less. The cured film as an interlayer insulation film, a protective film, or a spacer formed from the radiation sensitive resin composition for cured film formation in any one of Claims 1-7. The display element provided with the cured film of Claim 12.