KR101579775B1 - Radiation-sensitive resin composition, partition wall and insulating film, and method for forming the same - Google Patents

Abstract

<화학식 2>

<화학식 3>

It is an object of the present invention to provide a radiation-sensitive resin composition which has a sufficient resolution and a high resistance to a resist stripping liquid and the like, and which has excellent radiation sensitivity and high light-shielding property upon heating.
(A2) a phenol skeleton-containing unsaturated compound represented by the following general formula (1), a compound represented by the following general formula (2), and a compound represented by the following general formula And a monomer containing a compound selected from the group consisting of a compound represented by the formula (3), an alkali-soluble resin of a copolymer comprising a copolymer of a [B] 1,2- And a radiation-sensitive resin composition for forming an insulating film.
&Lt; Formula 1 >

(2)

(3)

Description

TECHNICAL FIELD [0001] The present invention relates to a radiation-sensitive resin composition, a barrier rib for an organic EL display device, an insulating film, and a method of forming the same.

The present invention relates to a radiation-sensitive resin composition for forming barrier ribs and an insulating film, a barrier rib for an organic EL display element, an insulating film, and a method for forming the same. More particularly, the present invention relates to a radiation-sensitive resin composition suitable for forming barrier ribs and insulating films using radiation such as ultraviolet rays, deep ultraviolet rays, and X-rays, barrier ribs and insulating films for organic EL display elements formed therefrom, And a method of forming the same.

Since the organic EL display device emits self-light, it has no dependency on the viewing angle, is excellent in impact resistance due to a solid device, has a low voltage driving, low power consumption and high operation stability in a low temperature range, There are several advantages. Since the organic EL display device has these advantages, there is a high expectation for application to mobile applications such as mobile terminals and vehicle-mounted devices, and active research has been conducted.

Such an organic EL display device is generally manufactured by the following method. First, a pattern of a transparent electrode (hole injection electrode) such as tin-doped indium oxide (ITO) and a hole transport layer is formed on a substrate. Subsequently, in the passive organic EL display device, after the pattern of the insulating film and the pattern of the negative electrode partitions are formed, the organic EL layer, the electron transport layer and the cathode (electron injection electrode) are patterned by vapor deposition. In the active-type organic EL display device, after the pattern of the insulating film, which is also the partition wall of the organic EL layer, is formed, the pattern of the organic EL layer is formed by the masking method or the ink-jet method, (Electron injection electrode). Here, as the organic EL layer, materials such as Alq ₃ and BeBq ₃ doped with quinacridone or coumarin are used, and as the cathode material, a metal having a low work function such as Mg or Ag is used as a main material Is generally used.

In recent years, in order to meet demands for high definition, an organic EL display device having a higher aperture ratio is being studied. However, due to the following reasons, there is a certain limit to the improvement of the aperture ratio. That is, in order to increase the aperture ratio in the passive type organic EL display device, it is necessary to reduce the pattern width of the insulating film and the negative electrode partition wall, but a certain strength is required for these parts and a limit to the reduction of the pattern width , A sufficiently high aperture ratio can not be obtained. Further, in the active type organic EL display device, since it is necessary to keep a constant interval between the pixels in order to avoid shorting of the ITO pattern for each pixel, improvement of the aperture ratio is limited.

In recent years, an active type organic EL display device having a structure capable of realizing a higher aperture ratio has been studied. Such an active type organic EL display device is manufactured, for example, by the following method. First, a driving terminal is formed on a substrate such as glass, and a first insulating film serving also as a flattening film is formed thereon. Subsequently, a pattern of a transparent electrode (hole injection electrode) such as ITO is formed thereon. The pattern formation at this time is usually performed by wet etching. Further, a pattern of the hole transporting layer is formed thereon by a masking method. Subsequently, a pattern of a second insulating film, which is also a partition wall of the ITO pattern and the organic EL layer, and a pattern of the organic EL layer are formed by a masking method, an inkjet method or the like, and then the electron transporting layer and the cathode . At this time, in order to conduct conduction between the ITO electrode (hole injection electrode) and the driving terminal, it is necessary to form a through hole or a U-shaped groove of about 1 to 15 mu m in the first insulating film.

However, it is known that the organic EL light-emitting layer deteriorates quickly when it comes in contact with moisture even if it is a low molecular weight light-emitting layer or a polymer light-emitting layer, and its light emission state is inhibited. It is considered that such moisture may enter the organic EL layer gradually in the case of intrusion from the environment and a small amount of moisture contained in the insulating film material in the form of adsorbed water or the like.

It has a sufficient resolution capable of forming a through hole or a C-shaped groove necessary for realizing a higher aperture ratio from the present to the present, has excellent planarization performance, and has a high resistance to a resist stripping solution used for forming a transparent electrode A material capable of forming an insulating film having resistance and preventing penetration of impurities (mainly moisture) which inhibits luminescence has not been proposed.

On the other hand, attempts have been made to provide a light shielding property at the base of an insulating film and / or a device isolation structure for the purpose of enhancing the contrast in a display device using an organic EL display device and improving the visibility (for example, Japanese Unexamined Patent Publication No. 11-273870 and Japanese Unexamined Patent Publication No. 2002-116536). However, in these radiation-sensitive resin compositions, it is necessary to use a considerable amount of colorant in order to sufficiently enhance the light shielding property of the light-shielding cured film or the black matrix. When such a large amount of coloring agent is used, since the exposed radiation is absorbed by the coloring agent, the effective intensity of the radiation in the coating film is lowered, and the radiation sensitivity (patterning sensitivity) for pattern formation is lowered .

As a specific method for imparting light shielding properties to the barrier ribs and the insulating film without lowering the radiation sensitivity, a positive resist containing an alkali-soluble resin such as a novolak resin and a diazoquinone is added to a heat-sensitive material and a color developer (See, for example, Japanese Unexamined Patent Application Publication No. 10-170715 and Japanese Unexamined Patent Application Publication No. 2008-122501). In this method, a positive radiation-sensitive resin composition in which a heat-sensitive material which develops black color upon application of heat and a coloring agent are internally added is used. In such a radiation-sensitive resin composition, since the thermosensitive material is not in black due to the unreacted state before exposure, the resin composition itself does not have shading properties and the radiation sensitivity is not deteriorated.

However, the pattern in the organic EL display element and the temperature required for forming the barrier rib or the insulating film are generally in the vicinity of 200 占 폚. For this reason, as the developer and the color developer disclosed in Japanese Patent Laid-Open Publication No. 10-170715 or Japanese Patent Application Laid-Open No. 2008-122501, heat resistance to this temperature is insufficient, and satisfactory light shielding property can not be obtained , And sublimation occurs at the time of pattern formation, and the risk of contamination of the firing furnace is pointed out.

Japanese Patent Application Laid-Open No. 11-273870 Japanese Patent Application Laid-Open No. 2002-116536 Japanese Patent Application Laid-Open No. 10-170715 Japanese Patent Application Laid-Open No. 2008-122501

SUMMARY OF THE INVENTION The present invention has been made based on the above-described circumstances, and an object of the present invention is to provide a semiconductor device having a sufficient resolution capable of forming a through-hole or a C-shaped groove in an insulating film and having excellent planarization performance, Radiation resistance resin composition for forming a barrier rib and an insulating film of an organic EL display device having high resistance to a liquid and having excellent radiation sensitivity and high light shielding property upon heating.

According to an aspect of the present invention,

(A2) at least one member selected from the group consisting of a phenol skeleton-containing unsaturated compound represented by the following formula (1), a compound represented by the following formula (2) and a compound represented by the following formula An alkali-soluble resin of a copolymer obtained by copolymerizing a monomer containing a compound selected from the group consisting of compounds represented by the general formula

[B] a 1,2-quinonediazide compound,

[C] Thermal dye

Sensitive resin composition.

(Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² to R ⁶ are the same or different and each is a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, B is a single bond, COO-, or -CONH-, and m is an integer of 0 to 3, provided that at least one of R ² to R ⁶ is a hydroxyl group, and R ¹ is a hydrogen atom or a Y ¹ and Y ² are the same or different and each is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; X ^{1 to} X ⁴ are the same or different and each is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom; Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Z is a single bond or -O (CH ₂ ) n -O- (CH ₂ ) _w - and w is an integer of 1 to 6, ) _w -, and w is an integer from 1 to 6.)

The barrier rib and the radiation sensitive resin composition for forming an insulating film contain a copolymer such as an unsaturated carboxylic acid or the like serving as both an alkali soluble resin and a color developing agent and an unsaturated compound containing a phenol skeleton and a thermal dye, Heat resistance to high temperature at the time of formation can be prevented, sublimation of the color developer can be prevented, and in addition to excellent radiation sensitivity and developability, high light shielding property at the time of heating can be obtained.

The alkali-soluble resin of the component [A] in the radiation-sensitive resin composition is preferably a copolymer obtained by copolymerizing (a3) a monomer containing an epoxy group-containing unsaturated compound in addition to the component (a1) and the component (a2) Do. By using such an epoxy group-containing unsaturated compound as a component of the copolymer which is an alkali-soluble resin of the component [A], heat resistance and surface hardness of the partition wall and the insulating film formed by the radiation-sensitive resin composition can be further increased.

 The alkali-soluble resin as the component (A) in the radiation-sensitive resin composition may further contain (a4) an unsaturated compound having a radically polymerizable property in addition to the component (a1), the component It is preferable that the copolymer is a copolymer formed by copolymerizing monomers.

The content of the thermosensitive coloring material of the [C] component in the radiation sensitive resin composition is preferably not less than 0.1 part by mass and not more than 30 parts by mass with respect to 100 parts by mass of the alkali-soluble resin of the component [A]. By setting the content of the thermosensitive coloring matter of the [C] component within this range, the absorption sensitivity to heat, radiation sensitivity, heat resistance, and solvent resistance can be maintained at appropriate levels.

The method for forming the barrier rib for the organic EL display element and the insulating film for the organic EL display element of the present invention includes the steps of (1) forming a coating film of the radiation-sensitive resin composition on a substrate,

(2) a step of irradiating at least a part of the coating film formed in the step (1)

(3) a step of developing the coated film irradiated with the radiation in the step (2)

(4) a step of heating the developed coating film in the step (3)

.

When the barrier ribs and the insulating film of the organic EL display device are produced by the above-described steps using the radiation sensitive resin composition, before the exposure, the heat-sensitive dye contained in the composition is in an unreacted state, However, when heated after exposure, a high light shielding property is exhibited, and the contrast of the display device provided with the organic EL display device having the barrier rib and the insulating film is improved.

INDUSTRIAL APPLICABILITY As described above, the radiation sensitive resin composition of the present invention has heat resistance against high temperatures at the time of forming barrier ribs and insulating films, and can prevent sublimation of the color developing agent because the radiation sensitive resin composition of the present invention uses an alkali- And in addition to excellent radiation sensitivity and developability, a high light shielding property at the time of heating can be obtained.

(Mode for carrying out the invention)

The barrier rib and the radiation-sensitive resin composition for forming an insulating film according to the present invention contain an alkali-soluble resin as the component [A], a 1,2-quinonediazide compound as the component [B], a heat dye as the component [C] &Lt; / RTI &gt; Each component will be described below.

Component [A]

The component (A) is at least one selected from (a1) an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and (a2) a phenol skeleton-containing unsaturated compound represented by the formula (1), a compound represented by the formula And a compound represented by the following general formula (1). Hereinafter, this copolymer is referred to as &quot; copolymer [A] &quot;. The copolymer [A] can be obtained by copolymerizing (a3) an epoxy group-containing unsaturated compound and / or (a4) an unsaturated (meth) acrylate having radical polymerizability other than these compounds (a1) Or a copolymer formed by copolymerizing a monomer containing a compound. The copolymer [A] is an alkali-soluble resin, but also functions as a developing agent in the radiation-sensitive resin composition. The radiation sensitive resin composition containing the copolymer [A] has excellent heat resistance, high radiation sensitivity and high developing performance at the time of forming barrier ribs and insulating films, Light is obtained.

The copolymer [A] can be produced by radical polymerization of the compounds (a1) and (a2) and the optional compounds (a3) and (a4) in a solvent in the presence of a polymerization initiator. The copolymer [A] is preferably a copolymer having a structural unit derived from the compound (a1) based on the total of the structural units derived from the compounds (a1), (a2), (a3) and (a4) By mass, particularly preferably 10 to 30% by mass. By using the structural unit derived from the compound (a1) at such a ratio, the solubility in the alkali aqueous solution in the developing step of the copolymer [A] can be controlled within an appropriate range.

The compound (a1) is an unsaturated carboxylic acid and / or an unsaturated carbonic anhydride having a radical polymerizable property. Examples of the compound (a1) include a mono [(meth) acryloyloxyalkyl] ester of a monocarboxylic acid, a dicarboxylic acid, an anhydride of a dicarboxylic acid, a polyvalent carboxylic acid, a compound having a carboxyl group and a hydroxyl group at both terminals Mono (meth) acrylate of a polymer, polycyclic compound having a carboxyl group, and anhydrides thereof.

Specific examples of these compounds (a1) include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid;

As the dicarboxylic acid, for example, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like;

As an anhydride of dicarboxylic acid, for example, an anhydride of the compound exemplified as dicarboxylic acid;

Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl] phthalate, Etc;

Mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals, for example,? -Carboxypolycaprolactone mono (meth) acrylate;

Examples of the polycyclic compound having a carboxyl group and anhydrides thereof include 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxycibiclo [2.2.1] hept- Carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept- 2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- Respectively.

Among these compounds (a1), a monocarbonic acid and an anhydride of a dicarboxylic acid are preferably used. Of these, acrylic acid, methacrylic acid and maleic anhydride are particularly preferably used in view of copolymerization reactivity with other compounds, solubility in an aqueous alkali solution, and availability. These compounds (a1) may be used alone or in combination.

The copolymer [A] is a copolymer having a structural unit derived from the compound (a2) based on the total of the structural units derived from the compounds (a1), (a2), (a3) and (a4) By mass, particularly preferably 3 to 40% by mass. By using the constituent unit derived from the compound (a2) in an amount of 1% by mass or more, the radiation sensitivity of the radiation sensitive resin composition can be improved. On the other hand, by setting the amount of the constituent unit to 50 mass% or less, it is possible to prevent the solubility in the alkali aqueous solution from becoming excessively large in the developing step for forming the partition wall and the insulating film.

The compound (a2) is a compound selected from the group consisting of the phenol skeleton-containing unsaturated compound represented by the formula (1), the compound represented by the formula (2), and the compound represented by the formula (3).

The phenol skeleton-containing unsaturated compound represented by the formula (1) can be classified into the compounds represented by the following formulas (4) to (8) by the definition of B and m.

(In the formula (4), n is an integer of 1 to 3, and the definitions of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as those of the formula (1)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the same meanings as defined above).

(Wherein p is an integer of 1 to 3, and the definitions of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as those of Formula 1).

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as in the above formula (1)).

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as in the above formula (1)).

Among these phenol skeleton-containing unsaturated compounds, it is preferable to use at least one compound selected from the group consisting of N- (3,5-dimethyl-4-hydroxybenzyl) (meth) acrylamide, N- (4-hydroxyphenyl) (Meth) acrylate, 4-hydroxyphenyl (meth) acrylate, o-hydroxystyrene, m-hydroxystyrene, p- hydroxystyrene, Hydroxystyrene and? -Methyl-p-hydroxystyrene are used to increase the radiation sensitivity of the radiation-sensitive resin composition, to increase the development margin (allowable range of developing time), and to improve the heat resistance of the obtained partition wall and the insulating film Is preferably used.

The compound represented by Formula 2 is a compound having a polymerizable unsaturated group introduced into one of the hydroxyl groups of the bisphenol-type compound. Examples of the compound represented by Formula 2 include 4,4'-isopropylidene-diphenol, 4,4'-isopropylidenebis (2-chlorophenol), 4,4'-isopropylidenebis (2,6-dibromophenol), 4,4'-isopropylidenebis (2,6-dichlorophenol), 4,4'-isopropylidenebis Isopropylidenebis (2,6-dimethylphenol), 4,4'-isopropylidenebis (2-t-butylphenol), 4,4'-sec-butyryldiphenol, 4,4'-sec -Butylidene bis (2-methylphenol), and other compounds having a (meth) acryloyl group introduced into one of the hydroxyl groups of the bisphenol-type compound. Among them, a compound in which a (meth) acryloyl group is introduced into one of the hydroxyl groups of 4,4'-isopropylidene-diphenol is particularly preferable from the viewpoint of improving the developing performance of the compound [A] component to be formed.

The compound represented by Formula 3 is a compound in which a polymerizable unsaturated group is introduced into one hydroxyl group of naphthalenediol. The naphthalene diol may be any isomer of a 1,2-isomer, a 1,3-isomer, a 1,4-isomer, a 1,5-isomer, a 2,3-isomer and a 2,6- Or a mixture thereof. Specific examples of the compound represented by the general formula (3) include 1-acryloyloxy-4-naphthol, 1-acryloyloxy-5-naphthol, 2-acryloyloxy-6-naphthol, 1-methacryloyloxy 4-naphthol, 1-methacryloyloxy-5-naphthol, 2-methacryloyloxy-6-naphthol and the like. Of these compounds, 1-methacryloyloxy-4-naphthol is particularly preferable from the viewpoint of improving the color performance and copolymerization of the compound [A] to be formed.

The copolymer [A] is a copolymer obtained by copolymerizing a structural unit derived from a compound (a3) which is an epoxy group-containing unsaturated compound having a radical polymerizing property with a total of structural units derived from the compounds (a1), (a2), (a3) , Preferably 10 to 80 mass%, and particularly preferably 20 to 70 mass%, based on the total mass of the composition. When the amount of the structural unit derived from the compound (a3) is 10 mass% or more, heat resistance and surface hardness of the obtained partition wall and the insulating film are improved. On the other hand, when the amount of the constituent unit is 80 mass% or less, the storage stability of the radiation-sensitive resin composition can be kept high.

Examples of the compound (a3) include glycidyl acrylate, glycidyl methacrylate, glycidyl? -Ethyl acrylate, glycidyl? -N-propyl acrylate, glycidyl? -N-butyl acrylate, -3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, , o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and 3,4-epoxycyclohexyl methacrylate. Among these compounds (a3), glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p- Ether, 3,4-epoxycyclohexyl methacrylate and the like are preferably used in view of improving the copolymerization reactivity with other compounds and the heat resistance and surface hardness of the resulting barrier ribs and insulating films. These compounds (a3) are used alone or in combination.

The copolymer [A] is obtained by copolymerizing the constituent units derived from the compound (a4), which is an unsaturated compound having radical polymerizability other than the above-mentioned compounds (a1), (a2) and (a3) preferably 5 to 70% by mass, particularly preferably 5 to 50% by mass, based on the total amount of the structural units derived from the structural units (a3) and (a4). When the content of the constituent unit derived from the compound (a4) is 5% by mass or more, the storage stability of the radiation-sensitive resin composition can be improved. On the other hand, by setting the amount of the constituent unit to 70% by mass or less, the solubility of the composition in an aqueous alkali solution can be promoted in the developing step for forming the partition walls and the insulating film.

Examples of the compound (a4) include methacrylic acid chain alkyl esters, acrylic acid chain alkyl esters, methacrylic acid cyclic alkyl esters, hydroxyl group-containing methacrylic esters, acrylic acid cyclic alkyl esters, methacrylic acid aryl esters, acrylic acid aryl esters , Unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated dienes, unsaturated compounds having a tetrahydrofuran skeleton, unsaturated compounds having a furan skeleton, unsaturated compounds having a tetrahydropyran skeleton, , An unsaturated compound having a skeleton represented by the following formula (9), and other unsaturated compounds.

(In the formula (9), R ⁷ is a hydrogen atom or a methyl group, and q is an integer of 1 or more.)

Specific examples thereof include methacrylic acid chain alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2- ethyl Hexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate and the like;

As the acrylic acid chain alkyl ester, for example, methyl acrylate, isopropyl acrylate and the like;

As the methacrylic acid cyclic alkyl ester, for example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, tricyclo [5.2. 1.0 ^2,6 ] decane-8- ^yloxyethyl methacrylate, isobornyl methacrylate and the like;

As the methacrylic acid ester having a hydroxyl group, for example, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol mono Methacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethyl glycoside and the like;

As acrylic acid cyclic alkyl esters, for example, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, tricyclo [5.2.1.0 ^2,6 ] Decane-8-yloxyethyl acrylate, isobornyl acrylate and the like;

As the methacrylic acid aryl esters, for example, phenyl methacrylate, benzyl methacrylate and the like;

As the acrylic acid aryl esters, for example, phenyl acrylate, benzyl acrylate and the like;

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

2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept- Ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept- 2,6-di (t-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, ] Hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept- (Hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept- 6-di (2 -Hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept- [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene and the like;

Examples of the maleimide compound include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide , N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N- Pyranate, N- (9-acridinyl) maleimide, and the like;

As the unsaturated aromatic compound, for example, styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene and the like;

Examples of the conjugated dienes include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like;

Examples of the unsaturated compound having a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran Lt; / RTI &gt;

Examples of the unsaturated compound having a furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) Methyl-1-hexen-3-one, 6-furan-2-one, Methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-ene- Etc;

Examples of the unsaturated compound having a tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) En-3-one, 2-methacrylic acid tetrahydropyran-2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-

As an unsaturated compound having a pyran skeleton, for example, 4- (1, 4-dioxa-5-oxo-6-heptenyl) -6- -Oxo-7-octenyl) -6-methyl-2-pyran and the like;

Examples of the unsaturated compound having a skeleton represented by the above formula (9) include polyethylene glycol (n = 2 to 10) mono (meth) acrylate, polypropylene glycol (n = 2 to 10) mono (meth) acrylate and the like;

Examples of the other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide and vinyl acetate.

Among these compounds (a4), a methacrylic acid chain alkyl ester, a methacrylic acid cyclic alkyl ester, an acrylic acid cyclic alkyl ester, an unsaturated dicarboxylic acid diester, a bicyclo unsaturated compound, a maleimide compound, an unsaturated aromatic compound, a conjugated diene, An unsaturated compound having a furan skeleton, an unsaturated compound having a tetrahydropyran skeleton, and an unsaturated compound having a skeleton represented by the above formula (9) are preferably used. Among them, styrene, t-butyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, (N = 2-10) mono (meth) acrylate, 3- (meth) acryloyloxy (meth) acrylate, Tetrahydrofuran-2-one, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, furfuryl (meth) acrylate and N- cyclohexylmaleimide From the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution. These compounds (a4) are used alone or in combination.

In the copolymer [A] used in the present invention, preferred specific examples of the combination of the monomer groups are methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / methacrylic acid Glycidyl / 2-methylcyclohexyl acrylate / N- (3,5-dimethyl-4-hydroxybenzyl) methacrylamide copolymer, methacrylic acid / glycidyl methacrylate / 1- (tetrahydropyranyl) Methoxy-styrene / N- (3,5-dimethyl-4-hydroxybenzyl) methacrylamide copolymer, Methacrylic acid / glycidyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / styrene / N-phenylmaleimide / N- (4-hydroxyphenyl) methacrylamide Copolymer, methacrylic acid / glycidyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / n-lauryl methacrylate Methacryloyloxytetrahydrofuran-2-one / N- (4-hydroxyphenyl) methacrylamide copolymer, methacrylic acid / glycidyl methacrylate / tricyclo [5.2.1.0 ^{2 , 6} ] decan-8-yl methacrylate / p-methoxystyrene / 4-hydroxybenzyl methacrylate copolymer, methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decan- Methacrylic acid / glycidyl methacrylate / glycidyl methacrylate / glycidyl methacrylate / styrene / p-vinylbenzyl glycidyl ether / tetrahydrofurfuryl methacrylate / 4-hydroxyphenyl methacrylate copolymer, methacrylic acid / glycidyl methacrylate / Methacryloyloxytetrahydrofuran-2-one / tetrahydrofurfuryl methacrylate / 4-hydroxyphenyl methacrylate copolymer, methacrylic acid / glycidyl methacrylate Dl / tetrahydrofurfuryl methacrylate / N-phenylmale Mid / α- methyl -p- hydroxystyrene copolymer, methacrylic acid / glycidyl methacrylate / tricyclo [5.2.1.0 ^2,6] decane-8-yl methacrylate / N- cyclohexylmaleimide / -n-lauryl methacrylate /? -methyl-p-hydroxystyrene copolymer, methacrylic acid / glycidyl methacrylate / tetrahydrofurfuryl methacrylate / N-cyclohexylmaleimide / n- Methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / glycidyl methacrylate / 2-methyl A copolymer of a compound having a methacryloyl group introduced into one of the hydroxyl groups of cyclohexyl acrylate / 4,4'-isopropylidene-diphenol, a copolymer of methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decane-8 - one methacrylate / glycidyl methacrylate / 2-methylcyclohexyl acrylate / 1-meta Reel-yloxy-4-naphthol can be given to the copolymer.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") of the copolymer [A] is preferably 2 × 10 ^{3 to} 1 × 10 ⁵ , more preferably 5 × 10 ^{3 to} 5 × 10 ⁴ . By setting the Mw of the copolymer [A] to 2 x 10 ³ or more, a sufficient development margin of the radiation-sensitive resin composition is obtained, and a reduction in the residual film ratio (proportion of the patterned thin film remaining properly) It is possible to maintain the pattern shape and heat resistance of the obtained barrier rib and insulating film well. On the other hand, by setting the Mw of the copolymer [A] to 1 × 10 ⁵ or less, a high pattern sensitivity can be maintained and a favorable pattern shape can be obtained. The molecular weight distribution (hereinafter referred to as &quot; Mw / Mn &quot;) of the copolymer [A] is preferably 5.0 or less, more preferably 3.0 or less. By setting the Mw / Mn of the copolymer [A] to 5.0 or less, the pattern shape of the obtained partition wall and the insulating film can be well maintained. Further, the radiation-sensitive resin composition containing the copolymer [A] having the above-mentioned preferable ranges of Mw and Mw / Mn has a high developing property, and therefore, A predetermined pattern shape can be formed.

Examples of the solvent used in 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, propylene glycol mono Alkyl ether acetates, propylene glycol monoalkyl ether propionates, aromatic hydrocarbons, ketones, and other esters.

Examples of the solvent include alcohols such as methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol and the like;

As the ethers, for example, tetrahydrofuran and the like;

As the glycol ether, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like;

As the ethylene glycol alkyl ether acetate, for example, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate and the like;

As the diethylene glycol alkyl ether, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and the like;

As the propylene glycol monoalkyl ether, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like;

As the propylene glycol monoalkyl ether acetate, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate and the like;

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

As the aromatic hydrocarbons, for example, toluene, xylene and the like;

As the ketone, for example, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and the like;

Examples of other esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy- Hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxypropionate, propyl 3-hydroxypropionate, propyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, Propyl methoxyacetate, propyl methoxy propionate, butyl 2-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate, , Butyl ethoxyacetate, methyl propoxyacetate, propoxyacetate Butoxy propionate, ethyl 2-methoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl methoxypropionate, Ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxyethoxypropionate, propyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-methoxypropionate, Methyl propionate, ethyl propionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, Methyl, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3-propoxypropionic acid Propoxy propionate, ethyl 3-propoxy propionate, propyl 3-butoxy propionate, butyl 3-butoxy propionate, etc. And the like.

Of these solvents, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers and propylene glycol alkyl ether acetates are preferable, and in particular, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl Ether, and propylene glycol monomethyl ether acetate are preferable.

As the polymerization initiator used in the polymerization reaction for producing the copolymer [A], those known as radical polymerization initiators can be used. Azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy- , 4-dimethylvaleronitrile), and the like; Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxy pivalate, 1,1'-bis- (t-butylperoxy) cyclohexane; And hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used as a redox type initiator together with a reducing agent.

In the polymerization reaction for producing the copolymer [A], a molecular weight regulator may be used to adjust the molecular weight. Specific examples of the molecular weight regulator include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexylmercaptan, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan and thioglycolic acid; Xantogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide; Terpinolene, alpha -methylstyrene dimer, and the like.

Component [B]

The component [B] used in the radiation-sensitive resin composition of the present invention is a 1,2-quinonediazide compound which generates carbonic acid upon irradiation with radiation. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as &quot; mother nucleus &quot;) and 1,2-naphthoquinone diazidesulfonic acid halide can be used.

Examples of the above-mentioned mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other parent nuclei.

Examples of the mother nucleus include trihydroxybenzophenone, such as 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone and the like;

As the tetrahydroxybenzophenone, for example, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'- Tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone and the like;

As the pentahydroxybenzophenone, for example, 2,3,4,2 ', 6'-pentahydroxybenzophenone and the like;

As the hexahydroxybenzophenone, for example, 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone Phenon and the like;

(P-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, 1,1,1 (p-hydroxyphenyl) Tri (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 4-hydroxyphenyl) -3-phenylpropane, 4,4 '- [1- [4- [1- [4- hydroxyphenyl] -1- methylethyl] phenyl] (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene- , 6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan and the like;

As other nuclei, for example, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7- Methyl] phenyl} methyl], 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl ) -1- methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene.

Among them, 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tri (p-hydroxyphenyl) ethane, 4,4 '- [1- [4- [1- [ 4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferable.

As the 1,2-naphthoquinonediazidesulfonic acid halide, 1,2-naphthoquinonediazidesulfonic acid chloride is preferable. Specific examples of 1,2-naphthoquinonediazidesulfonic acid chloride include 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 1,2-naphthoquinonediazide-5-sulfonic acid chloride. Among them, it is particularly preferable to use 1,2-naphthoquinonediazide-5-sulfonic acid chloride.

In the condensation reaction of the phenolic compound or the alcoholic compound (mother nucleus) with 1,2-naphthoquinonediazide sulfonic acid halide, the condensation reaction is preferably carried out in an amount of 30 to 85 mol%, more preferably 30 to 85 mol%, based on the number of OH groups in the phenolic compound or the alcoholic compound 1,2-naphthoquinonediazidesulfonic acid halide equivalent to 50 to 70 mol% is preferably used. The condensation reaction can be carried out by a known method.

Examples of the 1,2-quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the above-mentioned mother nucleus is changed to an amide bond, for example, 2,3,4-trihydroxy Benzophenone-1,2-naphthoquinonediazide-4-sulfonic acid amide and the like are also suitably used.

These [B] components may be used alone or in combination of two or more. The proportion of the [B] component in the radiation-sensitive resin composition is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts by mass, per 100 parts by mass of the copolymer [A]. When the proportion of the [B] component in the radiation-sensitive resin composition is 5 parts by mass or more, the difference in solubility between the irradiated portion of the aqueous alkali solution and the unirradiated portion of the developer becomes large, The heat resistance and the solvent resistance of the obtained barrier rib and the insulating film are satisfactorily maintained. On the other hand, when the ratio of the [B] component is 100 parts by mass or less, the solubility in the alkali aqueous solution in the irradiated portion is maintained at a sufficiently high level, and the development can be easily performed.

Component [C]

The component [C] is a heat dye. As used herein, the term &quot; thermochromic dye &quot; means a compound having a property of color development by heating in a state in which an electron-accepting compound (for example, a proton such as an acid) is accommodated. The heat-sensitive dye is preferably a colorless compound having a partial skeleton such as lactone, lactam, salton, spiropyran, ester, amide and the like and rapidly opening these partial skeletons upon contact with an electron-accepting compound.

Examples of such heat dye include 3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide (referred to as "crystal violet lactone"), 3,3-bis (4-dimethylaminophenyl) phthalide 3- (4-dimethylaminophenyl) -3- (4-dimethylaminophenyl) -6-dimethylaminopyrimidine, 3- Dimethyl indol-3-yl) phthalide, 3- (4-dimethylaminophenyl) -3- 3-yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3 (2-phenylindol-3-yl) -6-dimethylaminopyrimidine, 3- (4-dimethylaminophenyl) -3- -Methylpyrrol-3-yl) -6-dimethylaminophthalide,

Bis [1,1-bis (4-dimethylaminophenyl) ethylene-2-yl] -4,5,6,7-tetrachlorophthalide, 3,3-bis [ (4-pyrrolidinophenyl) ethylene-2-yl] -4,5,6,7-tetrabromophthalide, 3,3-bis [1- Methoxyphenyl) ethylene-2-yl] -4,5,6,7-tetrachlorophthalide, 3,3-bis [1- (4-pyrrolidinophenyl) ) Ethylene-2-yl] -4,5,6,7-tetrachlorophthalide, 3- [1,1-di (1-ethyl- 3- (4-diethylaminophenyl) phthalide, 3- [1,1-di (1-ethyl- Ethyl-N-phenylaminophenyl) phthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- , 3-bis (1-n-octyl-2-methylindol-3-yl ) -Phthalide, phthalides such as 3- (2-methyl-4-diethylaminophenyl) -3- (1-n-octyl-

4,4-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leucoauramine, N-2,4,5-trichlorophenylleucooramine, rhodamine-B-anilinolactam, rhodamine- (4-nitroanilino) lactam, rhodamine-B- (4-chloroanilino) lactam, 3,7-bis (diethylamino) -10- benzoylphenoxazine, benzoyllocomethylene blue, blue,

3-diethylamino-7-methoxyfluoran, 3-diethylamino-7-methoxyfluoran, 3-diethylamino-6-methoxyfluoran, 3-diethylamino-6-methylfluorene, ethylamino-7-chlorofluorane, 3-diethylamino- 3-diethylamino-7-di-n-hexylamino-7-dibenzylaminofluoran, 3-diethylamino- (2'-fluorophenylamino) fluororan, 3-diethylamino-7- (2'-chlorophenyl) Amino) fluorane, 3-diethylamino-7- (3'-chlorophenylamino) fluorane, 3-diethylamino- (2'-fluorophenylamino) fluorane, 3-di-n-butylamino-7 (2'-chlorophenylamino) fluororan, 3-N-isopentyl-N-ethylamino-

3-N-n-hexyl-N-ethylamino-7- (2'-chlorophenylamino) fluorane, 3-diethylamino-6-chloro-7-anilinofluoran, Amino-6-chloro-7-anilinofluoran, 3-diethylamino-6-methoxy-7-anilinofluoran, 3- 6-methyl-7-anilinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, 3- 6-methyl-7-anilinofluoran, 3-dimethylamino-6-methyl-7-anilinofluoran, 3-diethylamino- Anilinofluoran, 3-di-n-pentylamino-6-methyl-7-anilinofluoran, 3- N-propyl-N-methylamino-6- Methyl-7-anilinofluoran, 3-N-butyl-N-methylamino-6-methyl- 3-N-butyl-N-ethylamino-6-methyl-7-anilinofluoran, 3-N-isobutyl-N-methylamino- Amino-6-methyl-7-anilinofluoran, 3-N-isopentyl-N-ethylamino- 3-N-n-hexyl-N-methylamino-6-methyl-7-anilinofluoran, 3-N-cyclohexyl- -Cyclohexyl-N-n-propylamino-6-methyl-7-anilinofluoran, 3-N-cyclohexyl- -Cyclohexyl-N-n-hexylamino-6 Methyl-7-anilinofluoran, 3-cyclohexyl-N- -N-n- octyl-6-methyl-7-anilinofluoran,

3-N- (2'-methoxyethyl) -N-ethylamino-6-methyl-7-anilinofluoran 3-N- (2'-ethoxyethyl) -7-anilinofluoran, 3-N- N-methylamino-6-methyl-7-anilinofluoran, 3-N- (2'- (3'-methoxypropyl) -N-methylamino-6-methyl-7-anilinofluorane, 3-N- Amino-6-methyl-7-anilinofluoran, 3-N- (3'-ethoxypropyl) -N-ethylamino Methyl-7-anilinofluoran, 3-N- (2'-tetrahydrofurfuryl) -N-ethylamino- Anilinofluoran, 3-diethylamino-6-ethyl-7-anilinofluoran, 3-di Diethylamino-6-methyl-7- (2 ', 6'-dimethylphenylamino) fluororan, 3-di-n- (2 ', 6'-dimethylphenylamino) fluororan, 2-tert-butylamino-7- , 2-bis [4 '- (3-N-cyclohexyl-N-methylamino-6-methylfluororan) Phenyl] amino-6-methyl-7-chlorofluorane, and 3- [4 '- (dimethylaminophenyl)] amino-5,7-dimethylfluororan;

3- (2-methyl-4-diethylaminophenyl) -3- (1-ethyl- Propylaminophenyl) -3- (1-ethyl-2-methylindole-3-yl) -4- azaphthalide, 3- 3- (2-methyl-4-di-n-hexylaminophenyl) -3- (1- 3-yl) -4,7-diazaphthalide, 3,3-bis (2-ethoxy-4-diethylaminophenyl) (1-n-octyl-2-methylindole-3-yl) -4-azaphthalide, 3- (2-ethoxy- 3- (1-octyl-2-methylindol-3-yl) -4-methylthiomorpholin- 7-azap Ethyl-2-methylindol-3-yl) -4 or 7-azaphthalide, 3- (2-hexyloxycarbonyl) Diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4- or 7- azaphthalaldehyde, 3- (2-ethoxy- 3- (1-ethyl-2-phenylindol-3-yl) -4 or 7-azaphthalide, 3- (2-butoxy- 3-ethyl-spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthol, 3-methyl-spiro-dinaphthopyran, 3-methyl-naphtho (3-methoxybenzo) spiropyran, 3-propyl-spiro-dibenzopyran-3,6-bis (dimethylamino) -9-spiro-3 '- (6'-dimethylamino) phthalide, 3,6 Bis (diethylamino) fluorene-9-spiro-3 '- (6'-dimethylamino) spiropyran acids such as butylphthalide,

(3H), 9 '- (9H) xanthene] -3' - (3-methylpyridazinone) (3H), 9 '-( 9H) xanthene, 2'-anilino-6 '-( N- ethyl- ] -3-one, 3'-N, N-dibenzylamino-6'-N, N-diethylaminospiro [isobenzofuran- (3H), 9 '-( 9H) -quinolinone &lt; / RTI &gt; Xanthene] -3-one.

As commercial products of these thermosensitive dyes, ETAC, RED500, RED520, CVL, S-205, BLACK305, BLACK400, BLACK100, BLACK500, H-7001, GREEN300, NIR BLACK78, BLUE220, H-3035, BLUE203, ATP, H- DCF, BLMB, CVL, GREEN-DCF, TH-107 (manufactured by Hodogaya Chemical Industries, Ltd.), H-2114 (manufactured by Yamada Kakako Kogyo Co., Ltd.), ORANGE-DCF, Vermilion- And the like. Of these commercially available products, the visible light of the film on which ETAC, S-205, BLACK305, BLACK400, BLACK100, BLACK500, H-7001, GREEN300, NIR BLACK78, H-3035, ATP, H- It is preferable because the water absorption is good.

These thermosensitive dyes may be used in combination of two or more kinds of components in accordance with the visible light spectrum required for the partition walls and the insulating film. The proportion of the [C] component in the radiation-sensitive resin composition is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, based on 100 parts by mass of the copolymer [A]. By setting the proportion of the [C] component to 0.1 part by mass or more, the desired light can be efficiently absorbed and the light shielding property can be exhibited. On the other hand, by setting the proportion of the [C] component to 30 parts by mass or less, the radiation sensitivity of the radiation sensitive resin composition and the solvent resistance and heat resistance of the obtained partition wall and insulating film can be satisfactorily maintained.

Other optional components

The radiation-sensitive resin composition of the present invention contains the above components [A], [B] and [C] as essential components, The polymerizable compound having two ethylenically unsaturated double bonds, the epoxy resin other than the [F] copolymer [A], the [G] surfactant, and the [H] adhesion aid.

 The thermosensitive acid-generating compound of the component [D] can be used for improving the heat resistance and surface hardness of the partition wall and the insulating film to be obtained. Examples of thermosensitive acid-generating compounds include onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts and phosphonium salts.

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

As these sulfonium salts,

As the alkylsulfonium salt, for example, 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenyl (Benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro -4-acetoxyphenylsulfonium hexafluoroantimonate and the like;

As the benzylsulfonium salt, for example, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylsulfonium hexafluoro Benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4 -Hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate and the like;

As the dibenzylsulfonium salt, for example, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium Dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3- Methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate and the like;

As the substituted benzylsulfonium salts, for example, p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p -Chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl- Hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and the like.

Examples of the benzothiazonium salts include,

3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-methoxybenzyl) benzothiazonium hexafluoro 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, and the like.

Of these heat-sensitive acid-generating compounds, sulfonium salts and benzothiazonium salts are preferably used. Among these, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, 4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, and 3-benzylbenzothiazonium hexafluoroantimonate are preferably used. do.

Examples of commercially available products of these thermosensitive acid-generating compounds include SANEIDES SI-L85, SI-L110, SI-L145, SI-L150 and SI-L160 (manufactured by Sanzuka Chemical Industries Co., Ltd.) .

The proportion of the [D] component in the radiation-sensitive resin composition is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the copolymer [A]. By setting the compounding amount of the [D] component to 0.1 to 20 parts by mass, it is possible to form a cured film having sufficient strength, and it is possible to prevent the occurrence of precipitates in the film forming step.

 Examples of the polymerizable compound having at least one ethylenic unsaturated double bond as the [E] component include monofunctional (meth) acrylate, bifunctional (meth) acrylate and trifunctional or more (meth) acrylate Can be used.

Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl And 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate. Examples of commercially available products of these monofunctional (meth) acrylates include Aronix M-101, M-111, M-114 (trade name, manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, (Manufactured by Nippon Kayaku Co., Ltd.), Viscot 158 and 2311 (manufactured by Osaka Yuki Kagakuko Kogyo Co., Ltd.).

Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol fluorenedi (meth) acrylate, and the like. Examples of commercially available products of these bifunctional (meth) acrylates include Aronix M-210, M-240, M-6200 (manufactured by Toagosei Kogyo Co., Ltd.), KAYARAD HDDA, R-604 (manufactured by Nippon Kayaku Co., Ltd.), Viscot 260, Copper 312 and Copper 335HP (manufactured by Osaka Yuki Kagakukogyo Co., Ltd.).

Examples of the trifunctional or more (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Examples of commercial products of these trifunctional or more (meth) acrylates include Aronix M-309, M-400, M-405, M-450, M-7100, M- 20, DPCA-30, DPCA-60 and DPCA-120 (all manufactured by Nippon Kayaku Co., Ltd.), bis (2-ethylhexyl) Viscoat 295, Copper 300, Copper 360, Copper GPT, Copper 3PA, Copper 400 (manufactured by Osaka Yuki Kagakukogyo Co., Ltd.) and the like.

Among these meta (acrylates), trifunctional or more (meth) acrylates are preferably used from the viewpoints of improving the heat resistance and surface hardness of the partition walls and the insulating film to be formed. Among them, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate are particularly preferable. These monofunctional, bifunctional or trifunctional (meth) acrylates are used singly or in combination.

The proportion of the [E] component in the radiation-sensitive resin composition is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, based on 100 parts by mass of the copolymer [A]. When the amount of the component [E] is from 1 to 50 parts by mass, heat resistance and surface hardness of the obtained partition walls and the insulating film can be improved, and the occurrence of film roughening in the coating film forming step on the substrate can be suppressed Lt; / RTI &gt;

The epoxy resin other than the copolymer [A] as the [F] component is not particularly limited as long as it does not adversely affect the compatibility with each component contained in the radiation-sensitive resin composition. Examples of such epoxy resins are preferably bisphenol A type epoxy resins, phenol novolac type epoxy resins, cresol novolak type epoxy resins, cyclic aliphatic epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins A resin obtained by (co) polymerization of a resin, a heterocyclic epoxy resin, and glycidyl methacrylate. Among them, bisphenol A type epoxy resin, cresol novolak type epoxy resin, glycidyl ester type epoxy resin and the like are particularly preferable.

The proportion of the [F] component in the radiation-sensitive resin composition is preferably 30 parts by mass or less based on 100 parts by mass of the copolymer [A]. By using the [F] component in such a ratio, the heat resistance and surface hardness of the partition wall and the insulating film obtained from the radiation sensitive resin composition can be further improved, and when the coating film of the radiation sensitive resin composition is formed on the substrate A high film thickness uniformity can be obtained. The copolymer [A] may also be referred to as an &quot; epoxy resin &quot;, but differs from the [F] component in that it has an alkali solubility. The [F] component is alkali-insoluble.

In the radiation-sensitive resin composition, a surfactant may be used as the [G] component in order to further improve the coating property at the time of forming a coating film. Examples of the surfactant that can be preferably used include a fluorine surfactant, a silicone surfactant, and a nonionic surfactant.

Examples of the fluorine-based surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octa Ethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di , 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, and other fluoroethers; Sodium perfluorododecylsulfonate; Fluoroalkanes such as 1,1,2,2,8,8,9,9,10,10-decafluorododecane and 1,1,2,2,3,3-hexafluorodecane; Sodium fluoroalkylbenzenesulfonate; Fluoroalkyloxyethylene ethers; Fluoroalkylammonium iodides; Fluoroalkyl polyoxyethylene ethers;

Perfluoroalkyl polyoxyethanols; Perfluoroalkyl alkoxylates; Fluorine-based alkyl esters and the like.

(Commercially available from BM Chemie), Megaface F142D, Copper F172, Copper F173, Copper F183, Copper F178, Copper F191, Copper F471 (commercially available from BM Chemie) Fluorad FC-170C, FC-171, FC-430 and FC-431 (manufactured by Sumitomo 3M Limited), Surflon S (manufactured by Dainippon Ink and Chemicals, Incorporated) -112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC- -105, copper SC-106 (manufactured by Asahi Glass Co., Ltd.), Eftop EF301, copper 303 and copper 352 (manufactured by Shin-Aikita Kasei Kogyo Co., Ltd.).

Specific examples of the silicone surfactant include commercially available products such as DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH- TSF-4440, TSF-4445, TSF-4460, and TSF-4452 (manufactured by GE Toshiba Silicones Co., Ltd.)), and the like .

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; (Meth) acrylic acid-based copolymer. Polyflow No.57 and 95 (manufactured by Kyoeisha Chemical Co., Ltd.) can be exemplified as typical commercially available nonionic surfactants. These surfactants may be used alone or in combination of two or more.

In the radiation-sensitive resin composition, the surfactant of the [G] component is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, based on 100 parts by mass of the copolymer [A]. When the blending amount of the surfactant is 0.01 to 5 parts by mass, occurrence of film roughening at the time of forming a coating film on the substrate can be suppressed.

In the radiation sensitive resin composition of the present invention, an adhesion auxiliary agent as the [H] component may be used in order to improve the adhesion with the substrate. As such an adhesion auxiliary agent, a functional silane coupling agent is preferably used. Examples of the functional silane coupling agent include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group or an epoxy group. Specific examples of the functional silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. In the radiation-sensitive resin composition, the amount of the adhesion aid is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 25 parts by mass, based on 100 parts by mass of the copolymer [A]. When the blending amount of the adhesion auxiliary agent for the [H] component is set to 0.1 to 30 parts by mass, sufficient adhesion to the substrate is exhibited without causing development residue in the development step, and a pattern can be easily formed.

Sensitizing radiation property  Resin composition

The radiation sensitive resin composition of the present invention is prepared by uniformly mixing the above components [A], [B] and [C] and optional components (components [D] to [H]). Usually, the radiation-sensitive resin composition is preferably used after being dissolved in a suitable solvent and stored in a solution state. For example, a solution of a radiation-sensitive resin composition in a solution state can be prepared by mixing the components [A], [B] and [C] and optional components in a predetermined ratio in a solvent.

As the solvent used for preparing the radiation-sensitive resin composition, it is necessary to uniformly dissolve each of the components [A], [B] and [C] and the optional components (components [D] to [ And is not particularly limited as long as it does not react with each component. Examples of the solvent include the same solvents as those exemplified as the solvents that can be used for producing the copolymer [A].

Among these solvents, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters and diethylene glycol alkyl ethers are preferably used from the viewpoints of solubility of each component, non-reactivity with each component, ease of forming a film, and the like .

Among these solvents, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, di Ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2- or 3-methoxypropionate and ethyl 2- or 3-ethoxypropionate are particularly preferably used.

In addition, in order to increase the in-plane uniformity of the film thickness of the formed coating film, a high boiling point solvent may be used together with the above solvent. Examples of the high boiling point solvents that can be used in combination include N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, Butanol, ethyl benzoate, diethyl oxalate, maleic anhydride, maleic anhydride, benzoic acid, benzoic acid, benzoic acid, benzoic acid, Propylene carbonate, phenyl cellosolve acetate, and the like can be given. Of these high boiling solvents, N-methylpyrrolidone,? -Butyrolactone and N, N-dimethylacetamide are preferable.

When a high-boiling solvent is used as a solvent in the radiation-sensitive resin composition, the amount thereof is preferably 1 to 40 mass%, more preferably 3 to 30 mass%, based on the total amount of the solvent. When the content is 1 to 40% by mass, the coating property at the time of coating film formation can be improved, and the radiation sensitivity and the residual film ratio can be suppressed from decreasing.

When the radiation-sensitive resin composition is prepared in the form of a solution, the ratio of the components other than the solvent (that is, the total amount of the copolymer [A], [B] and [C] But it is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 35% by mass. The solution of the radiation sensitive resin composition thus prepared may be filtered after using a millipore filter having a pore diameter of about 0.2 탆 or the like to be used for use.

Formation of barrier ribs and insulating films

Next, a method of forming the barrier rib and the insulating film of the present invention using the above radiation sensitive resin composition will be described. The method includes the following steps in the sequence described below.

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

(2) a step of irradiating at least a part of the coating film formed in the step (1)

(3) a step of developing the coated film irradiated with the radiation in the step (2)

(4) A step of heating the developed coating film in the step (3).

(One) Sensitizing radiation property  A step of forming a coating film of the resin composition on a substrate

In the step (1), the solution of the radiation sensitive resin composition of the present invention is applied to the surface of the substrate, preferably by prebaking to remove the solvent to form a coating film of the radiation sensitive resin composition. Examples of the types of substrates that can be used include glass substrates, silicon wafers, and substrates on which various metals are formed.

The coating method of the composition solution is not particularly limited and suitable methods such as spraying, roll coating, spin coating (coating method), slit die coating, bar coating, inkjet . Among these coating methods, a spin coating method and a slit die coating method are particularly preferable. The conditions for the prebaking may vary depending on the kind of each component, the use ratio, and the like, and may be, for example, about 60 seconds to about 110 占 폚 for about 30 seconds to about 15 minutes. The film thickness of the formed coating film may be 3 to 6 占 퐉 after prebaking.

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

In the step (2), the formed coating film is irradiated with a radiation through a mask having a predetermined pattern. Examples of the radiation used at this time include ultraviolet rays, deep ultraviolet rays, X-rays, charged particle rays, and the like.

Examples of the ultraviolet ray include g-line (wavelength: 436 nm) and i-line (wavelength: 365 nm). Examples of the far ultraviolet ray include a KrF excimer laser. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include electron beams and the like. Among these radiation, ultraviolet rays are preferable, and radiation including g line and / or i line among ultraviolet rays is particularly preferable. The exposure dose is preferably 50 to 1,500 J / m 2.

(3) Development process

(3) In the developing process, the coating film irradiated with the radiation in the step (2) may be developed to remove the irradiated portion of the radiation to form a desired pattern. Examples of the developing solution used in the developing treatment include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, But are not limited to, ethylamine, propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [ , 0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane, and the like can be used. An aqueous solution containing an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant, or an aqueous alkali solution containing a small amount of various organic solvents capable of dissolving the radiation-sensitive resin composition may be used as the developer. As the developing method, an appropriate method such as a puddle method, a dipping method, a swing dipping method, or a shower method can be used. The developing time varies depending on the composition of the radiation sensitive resin composition, but may be, for example, 30 to 120 seconds.

Further, in the conventionally known radiation-sensitive resin composition, when the development time exceeds 20 to 25 seconds from the optimum value, peeling occurs in the formed pattern, so that the development time must be strictly controlled. On the other hand, the radiation-sensitive resin composition of the present invention has a high developing margin, so that even when the excess time from the optimal developing time exceeds 30 seconds, a good pattern can be formed, which has a great advantage in terms of product yield.

(4) Heating process

(4) In the heating step, after the developing step (3), the patterned thin film is preferably subjected to a rinsing treatment by water washing, and then, preferably, a radiation of high pressure mercury lamp or the like is applied to the entire surface ) (After exposure) to decompose the 1,2-quinonediazide compound remaining in the thin film. Subsequently, a heating apparatus such as a hot plate or an oven is used, and the thin film is subjected to a heat treatment (post-baking treatment) to perform a curing treatment of the thin film. The exposure dose in the above-described post exposure is preferably about 2,000 to 5,000 J / m 2. The firing temperature in this curing treatment is, for example, 120 to 250 캜. The heating time varies depending on the type of the heating apparatus. For example, the heating time may be 5 to 30 minutes in the case of performing heat treatment on the hot plate, and 30 to 90 minutes in the case of performing heat treatment in the oven. At this time, a step baking method in which two or more heating steps are performed may be used. In this manner, the patterned thin film corresponding to the target partition wall or the insulating film can be formed on the surface of the substrate.

The barrier rib or the insulating film formed as described above can be used as a barrier rib or an insulating film having a radiation sensitivity, a development margin (a measure of developability), a solvent resistance, a heat resistance, a total light transmittance Scale), it exhibits excellent characteristics.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited to the following Examples.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the copolymer obtained from each of the following synthesis examples and comparative synthesis examples were measured by gel permeation chromatography (GPC) according to the following specifications.

Apparatus: GPC-101 (manufactured by Showa Denko Kabushiki Kaisha)

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 (manufactured by Showa Denko Kabushiki Kaisha)

Mobile phase: tetrahydrofuran containing 0.5% by mass of phosphoric acid

Copolymer Synthetic example

[Synthesis Example 1]

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 14 parts by mass of methacrylic acid, 16 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 20 parts by mass of 2-methylcyclohexyl acrylate, 40 parts by mass of glycidyl methacrylate , 10 parts by mass of N- (3,5-dimethyl-4-hydroxybenzyl) methacrylamide and 3 parts by mass of? -Methylstyrene dimer were purged with nitrogen, and then gently stirred. The temperature of the solution was raised to 70 캜 and maintained at this temperature for 4 hours to obtain a polymer solution containing the copolymer [A-1]. The polystyrene reduced weight average molecular weight (Mw) of this copolymer (A-1) was 8,000 and the molecular weight distribution (Mw / Mn) was 2.3. The solid concentration of the polymer solution obtained here was 34.4% by mass.

[Synthesis Example 2]

A cooling tube and a stirrer, 9 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 12 mass parts of methacrylic acid, 12 mass parts of p-methoxystyrene, 15 mass parts of 1- (tetrahydropyran-2-oxy) -butyl-3-en- 10 parts by mass of N-cyclohexylmaleimide, 10 parts by mass of N- (3,5-dimethyl-4-hydroxybenzyl) methacrylamide and 3 parts by mass of? -Methylstyrene dimer were charged, The stirring began slowly. The temperature of the solution was raised to 70 캜 and maintained at this temperature for 4 hours to obtain a polymer solution containing the copolymer [A-2]. The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-2] was 8,100 and the molecular weight distribution (Mw / Mn) was 2.4. The solid concentration of the polymer solution obtained here was 32.7% by mass.

[Synthesis Example 3]

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 14 parts by mass of methacrylic acid, 16 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 10 parts by mass of p-methoxystyrene, 40 parts by mass of glycidyl methacrylate, -Hydroxybenzyl methacrylate (20 parts by mass) and? -Methylstyrene dimer (3 parts by mass) were purged with nitrogen, and then gently stirred. The temperature of the solution was raised to 70 캜 and maintained at this temperature for 4 hours to obtain a polymer solution containing the copolymer [A-3]. The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-3] was 8,500 and the molecular weight distribution (Mw / Mn) was 2.3. The solid concentration of the polymer solution obtained here was 34.1 mass%.

[Synthesis Example 4]

A cooling tube and a flask equipped with a stirrer were charged with 8 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 11 mass parts of methacrylic acid, 12 mass parts of tetrahydrofurfuryl methacrylate, 40 mass parts of glycidyl methacrylate, 15 mass parts of N-cyclohexylmaleimide, 10 mass parts of n-lauryl methacrylate, 10 parts by mass of? -methyl-p-hydroxystyrene and 3 parts by mass of? -methylstyrene dimer were put, and after nitrogen substitution, gentle stirring was started. The temperature of the solution was raised to 70 캜 and maintained at this temperature for 5 hours to obtain a polymer solution containing the copolymer [A-4]. The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-4] was 8,000 and the molecular weight distribution (Mw / Mn) was 2.3. The polymer solution thus obtained had a solid content concentration of 31.9% by mass.

[Synthesis Example 5]

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 14 parts by mass of methacrylic acid, 16 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 20 parts by mass of 2-methylcyclohexyl acrylate, 40 parts by mass of glycidyl methacrylate , 10 parts by mass of a compound having a methacryloyl group introduced into one of the hydroxyl groups of 4,4'-isopropylidene-diphenol and 3 parts by mass of -methylstyrene dimer were charged, and after nitrogen replacement, gentle stirring was started . The temperature of the solution was raised to 70 캜 and maintained at this temperature for 4 hours to obtain a polymer solution containing the copolymer [A-5]. The polystyrene reduced weight average molecular weight (Mw) of this copolymer [A-5] was 7,000 and the molecular weight distribution (Mw / Mn) was 2.5. The solid solution concentration of the polymer solution obtained here was 34.8 mass%.

[Synthesis Example 6]

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 14 parts by mass of methacrylic acid, 16 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 20 parts by mass of 2-methylcyclohexyl acrylate, 40 parts by mass of glycidyl methacrylate 10 parts by mass of 1-methacryloyloxy-4-naphthol and 3 parts by mass of? -Methylstyrene dimer were put into the flask and purged with nitrogen, followed by gentle stirring. The temperature of the solution was raised to 70 캜 and maintained at this temperature for 4 hours to obtain a polymer solution containing the copolymer [A-6]. The polystyrene reduced weight average molecular weight (Mw) of this copolymer [A-6] was 8,000 and the molecular weight distribution (Mw / Mn) was 2.5. The polymer solution thus obtained had a solid content concentration of 34.6 mass%.

[Comparative Synthesis Example 1]

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis- (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 12 parts by mass of methacrylic acid, 12 parts by mass of p-methoxystyrene, 15 parts by mass of 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, 40 parts by mass of glycidyl methacrylate , 10 parts by mass of N-cyclohexylmaleimide, 10 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, and 3 parts by mass of? -Methylstyrene dimer were charged, The stirring began slowly. The temperature of the solution was raised to 70 캜 and maintained at this temperature for 4 hours to obtain a polymer solution containing the copolymer [a-1]. The polystyrene reduced weight average molecular weight (Mw) of the copolymer [a-1] was 8,900 and the molecular weight distribution (Mw / Mn) was 2.5. The solid concentration of the polymer solution obtained here was 32.9 mass%.

&Lt; Preparation of radiation-sensitive resin composition &gt;

[Example 1]

A solution containing the copolymer [A-1] of Synthesis Example 1 as the component [A] was used in an amount corresponding to 100 parts by mass (solid content) of the copolymer and an amount corresponding to 4,4 '- [1- [ A condensate of 4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride 30 parts by mass of the compound (B-1) and 30 parts by mass of 2'-anilino-6 '- (N-ethyl-N-isopentyl) amino-3'- methyl spiro [isobenzofuran- , 9 '- (9H) xanthene] -3-one (C-1) were mixed and dissolved in diethylene glycol ethyl methyl ether to have a solid content concentration of 30 mass% To prepare a solution (S-1) of a radiation-sensitive resin composition.

[Examples 2 to 5, 7 to 10, Comparative Examples 1 to 4]

(S-2) to ((C-2)) of the radiation-sensitive resin composition were prepared in the same manner as in Example 1, except that the kind and amount as shown in Table 1 were used as the components [A], [ S-5), (S-7) to (S-10) and (s-1) to (s-4) were prepared.

[Example 6]

(S) solution of the radiation-sensitive resin composition was obtained in the same manner as in Example 1, except that the solution was dissolved in diethylene glycol ethyl methyl ether / propylene glycol monomethyl ether acetate = 6/4 (molar ratio) so that the solid content concentration became 20 mass% -6).

In Table 1, the abbreviations of the components represent the following compounds.

(1.0 mol) and 1,2-naphthoic acid (B-1): 4,4'- [1- [4- [1- [4- hydroxyphenyl] 5-sulfonic acid chloride (2.0 mol) in acetonitrile

(B-2): A condensation product of 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride

(3H), 9 '- (9H) xanthene (C-1): 2'-anilino-6' ] -3-one (trade name S205, manufactured by Yamada Kakugo Kogyo Co., Ltd.)

(3H), 9 '-( 9H (9H) -quinolinone &lt; / RTI &gt; ) Xanthene-3-one (trade name: ETAC, manufactured by Yamada Kagaku Kogyo Co., Ltd.)

(C-3): 3'-N, N-dibenzylamino-6'-N, N-diethylaminospiro [isobenzofuran- (Trade name GREEN DCF, manufactured by Hodogaya Chemical Co., Ltd.)

(3H), 9 '-( N-ethyl-N- (4-methylphenyl)) aminospiro [ - (9H) xanthene] -3-one (trade name ATP, manufactured by Yamada Kakugo Kogyo Co., Ltd.)

(G) Surfactant: SH28PA (manufactured by Dow Corning Toray Silicone Co., Ltd.)

(H) Adhesion Adjuster:? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane

(X-1) low molecular weight color developing agent: BONJET BLACK0052 (manufactured by Orient Kagakuko Kogyo Co., Ltd.)

(X-2) Low molecular weight developer: 4-phenylphenol

&Lt; Evaluation of performance as barrier rib and insulating film &

[Examples 11 to 20, Comparative Examples 5 to 8]

Various properties of the barrier rib and the insulating film were evaluated using the thus-prepared radiation-sensitive resin composition as follows.

[Evaluation of radiation sensitivity]

A composition shown in Table 2 was coated on a silicon substrate using a spinner for Examples 11 to 15, 17 to 20 and Comparative Examples 5 to 8 and a slit die coater for Example 16, Lt; 0 &gt; C for 2 minutes on a hot plate to form a coating film having a film thickness of 3.0 mu m. The resulting coating film was subjected to exposure by changing the exposure time through a pattern mask having a predetermined pattern using a PLA-501F exposure apparatus (ultra-high pressure mercury lamp) manufactured by Canon Kabushiki Kaisha, Methyl-ammonium hydroxide aqueous solution at 25 占 폚 for 80 seconds by a puddle method. Subsequently, the substrate was subjected to water washing with ultra-pure water for 1 minute and dried to form a pattern on the wafer. The amount of exposure required to completely dissolve the space pattern of 3.0 μm line-and-space (10: 1) was measured. This value is shown in Table 2 as radiation sensitivity (exposure sensitivity). When the value is 1000 J / m &lt; 2 &gt; or less, the sensitivity is good.

[Evaluation of Developing Margin]

A coating film was formed on the silicon substrate in the same manner as the above [evaluation of radiation sensitivity]. Using a PLA-501F exposure apparatus (ultrahigh-pressure mercury lamp) manufactured by Canon Inc., a mask having a pattern of 3.0 占 퐉 line-and-space (10: 1) was interposed, Evaluation was carried out at an exposure amount corresponding to the value of the radiation sensitivity measured in the following manner. The development was carried out in the aqueous solution of tetramethylammonium hydroxide having the concentration shown in Table 2 at 25 캜 with the development time being changed by the puddle method. Subsequently, the substrate was subjected to water washing with ultra-pure water for 1 minute and dried to form a pattern on the wafer. At this time, the developing time necessary for the line line width to become 3.0 mu m is shown in Table 2 as the optimum developing time. In addition, when further development was continued from the optimum developing time, the time until the line pattern of 3.0 mu m was peeled off was measured and shown in Table 2 as the developing margin (allowable range of developing time). When this value is 30 seconds or more, the developing margin is good.

[Evaluation of solvent resistance]

A coating film was formed on the silicon substrate in the same manner as the above [evaluation of radiation sensitivity]. The obtained coating film was heated in a clean oven at 220 占 폚 for 1 hour to obtain a cured film. The film thickness (T1) of the obtained cured film was measured. Then, the silicon substrate on which the cured film was formed was immersed in dimethylsulfoxide controlled at a temperature of 70 占 폚 for 20 minutes, and then the film thickness t1 of the cured film was measured to determine the rate of film thickness change {| t1-T1 | / T1} x 100 [%]. The results of the film thickness change ratio are shown in Table 2. When this value is 4% or less, the solvent resistance is good. In the evaluation of the solvent resistance, patterning of the film to be formed is not necessary, so that the irradiation step and the developing step are omitted, and only the film forming step and the heating step are performed for evaluation.

[Evaluation of Heat Resistance]

A cured film was formed in the same manner as in the evaluation of the solvent resistance, and the film thickness (T2) of the obtained cured film was measured. Subsequently, the silicon substrate on which the cured film was formed was further baked at 240 DEG C for 1 hour in a clean oven, and then the film thickness t2 of the cured film was measured, and the film thickness change rate {| t2-T2 | / T2} x 100 [%]. The results of the heat resistance are shown in Table 2. When this value is 1% or less, it can be said that the heat resistance is good.

[Evaluation of total light transmittance (light shielding property)]

A cured film was formed on a glass substrate in the same manner as in [evaluation of solvent resistance] except that a glass substrate "Corning 7059 (manufactured by Corning) was used instead of the silicon substrate. Using a spectrophotometer &quot; 150-20 type double beam &quot; (manufactured by Hitachi Seisakusho), the total light transmittance of the glass substrate having the cured film was measured at a wavelength in the range of 380 to 780 nm. The values of total light transmittance are shown in Table 2. When this value is less than 50%, the light shielding property can be said to be good.

[Evaluation of relative dielectric constant]

The compositions shown in Table 2 were applied using a spinner for Examples 11 to 15, 17 to 20 and Comparative Examples 5 to 8 and a slit die coater for Example 16 on polished SUS304 substrates And then prebaked on a hot plate at 90 DEG C for 2 minutes to form a coating film having a film thickness of 3.0 mu m. The resulting coating film was fired in a clean oven at 220 占 폚 for 1 hour to obtain a cured film. A Pt / Pd electrode pattern was formed on the cured film by a vapor deposition method to prepare a sample for measuring the relative dielectric constant. The relative dielectric constant of the sample was measured by the CV method at a frequency of 10 kHz using an HP16451B electrode manufactured by Yokogawa, Hewlett-Packard Co., Ltd. and an HP4284A fresh-field LCR meter. The results of the relative dielectric constant are shown in Table 2. When this value is 3.7 or less, the dielectric constant is good. Further, in the evaluation of the dielectric constant, patterning of the film to be formed is not necessary, so that the irradiation step and the development step are omitted, and only the coating film forming step and the heating step are performed for evaluation.

From the results shown in Table 2, it can be seen that in Examples 11 to 20 using the radiation sensitive resin compositions prepared in Examples 1 to 10, the radiation sensitivity (exposure sensitivity), developing margin, solvent resistance, heat resistance, total light transmittance, All of the points were well balanced. Particularly, in all the embodiments, a total light transmittance of 45% or less can be obtained without using a separate color developer, and remarkably good light shielding performance is achieved. On the other hand, in Comparative Example 5 using a composition not containing a phenol skeleton-containing unsaturated compound as a constituent compound of the copolymer and Comparative Example 6 using a composition containing no thermosensitive dye and a developer, a total light transmittance of less than 50% The total light transmittance of the latter was 70%, which was very high. In Comparative Example 7 using a composition containing a low molecular weight color developing agent but not containing a heat dye, a total light transmittance of less than 50% was obtained, but the radiation sensitivity became extremely poor. Also in Comparative Example 8 (corresponding to Patent Documents 3 and 4) in which a composition containing no phenol skeleton-containing unsaturated compound as a constituent compound of the copolymer and also containing a thermosensitive dye and containing a low molecular weight color developing agent was used , And a total light transmittance of less than 50% could not be obtained.

The results of these Examples and Comparative Examples show that the radiation sensitive resin composition of the present invention has sufficient developability to such an extent that a through hole or a C-shaped groove of an insulating film can be formed, a high resistance to a solvent, And has excellent radiation sensitivity and high light shielding properties, it can be preferably used as a barrier rib and an insulating film.

&Lt; Industrial applicability >

The radiation sensitive resin composition of the present invention has heat resistance against high temperature at the time of forming the barrier ribs and the insulating film and can prevent the sublimation of the color developing agent, In addition to the sensitivity and developability, a high light shielding property at the time of heating can be obtained. Therefore, the organic EL element having the partition wall and the insulating film formed of such a radiation sensitive resin composition is preferably used as an electronic part of a display device showing a good contrast.

Claims (8)

(A2) a phenol skeleton-containing unsaturated compound represented by the following general formula (1), a bisphenol-type compound represented by the following general formula (2) A copolymer obtained by copolymerizing a compound having a polymerizable unsaturated group introduced therein and a monomer containing a compound selected from the group consisting of a compound in which a polymerizable unsaturated group is introduced into one of the hydroxyl groups of a naphthalenediol represented by the following formula ,
[B] a 1,2-quinonediazide compound,
[C] a heat-sensitive dye having a property of coloring by heating in a state containing an electron-accepting compound
Wherein the radiation-sensitive resin composition comprises:
&Lt; Formula 1 >

(2)

(3)

(Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² to R ⁶ are the same or different and each is a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, B is a single bond, COO-, or -CONH-, and m is an integer of 0 to 3, with the proviso that at least one of R ² to R ⁶ is a hydroxyl group;
Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y ¹ and Y ² are the same or different and each is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X ^{1 to} X ⁴ are the same or different, An alkyl group having 1 to 4 carbon atoms or a halogen atom; Z is a single bond or -O (CH ₂ ) _w -; w is an integer of 1 to 6;
In the formula (3), R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Z is a single bond or -O (CH ₂ ) _w -, and w is an integer of 1 to 6. The method according to claim 1,
Wherein the alkali-soluble resin of the component (A) is a copolymer obtained by copolymerizing (a3) a monomer containing an epoxy group-containing unsaturated compound in addition to the component (a1) and the component (a2). The method according to claim 1,
Wherein the content of the thermosensitive coloring matter of the [C] component is 0.1 part by mass or more and 30 parts by mass or less based on 100 parts by mass of the alkali-soluble resin of the component [A]. A barrier rib for an organic EL display device formed from the radiation sensitive resin composition according to any one of claims 1 to 3. An insulating film for an organic EL display device formed from the radiation sensitive resin composition according to any one of claims 1 to 3. (1) a step of forming a coating film of the radiation sensitive resin composition according to any one of claims 1 to 3 on a substrate,
(2) a step of irradiating at least a part of the coating film formed in the step (1)
(3) a step of developing the coated film irradiated with the radiation in the step (2)
(4) a step of heating the developed coating film in the step (3)
And forming a barrier rib for the organic EL display device. (1) a step of forming a coating film of the radiation sensitive resin composition according to any one of claims 1 to 3 on a substrate,
(2) a step of irradiating at least a part of the coating film formed in the step (1)
(3) a step of developing the coated film irradiated with the radiation in the step (2)
(4) a step of heating the developed coating film in the step (3)
Wherein the organic EL display element is formed on the substrate. 3. The method of claim 2,
The alkali-soluble resin of the component (A) is preferably a copolymer of a monomer containing an unsaturated compound having a radically polymerizable property, in addition to the component (a1), the component (a2) and the component (a3) Resin composition.