JP2010237310A - Radiosensitive resin composition, partition for organic el display element, insulating film, and forming method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiosensitive resin composition which has sufficient resolution, high resistance to a resist stripper or the like, excellent radiation sensitivity, and high light-shielding performance during heating. <P>SOLUTION: The radiosensitive resin composition for forming partitions and insulating films includes: [A] an alkali-soluble resin of a copolymer obtained by copolymerization of (a1) an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride and (a2) a monomer containing a compound selected from a group of phenol skeleton-containing unsaturated compounds, bisphenol skeleton-containing compounds, and naphthalene skeleton-containing compounds; [B] a 1, 2-quinonediazide compound; and [C] a heat sensitive dye. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

  Organic EL display elements are self-luminous and have no viewing angle dependency, and since they are solid-state elements, they have excellent impact resistance, low voltage drive, low power consumption, and high operational stability in the low temperature range. There are various advantages compared to Since the organic EL display element has these advantages, it is particularly expected to be applied to mobile applications such as portable terminals and in-vehicle devices, and has been actively researched.

Such an organic EL display element is generally manufactured by the following method. First, a transparent electrode (hole injection electrode) such as tin-doped indium oxide (ITO) and a hole transport layer pattern are formed on a substrate. Next, in the passive organic EL display element, after forming an insulating film pattern and a cathode barrier rib pattern, the organic EL layer, the electron transport layer, and the cathode (electron injection electrode) are patterned by vapor deposition. In an active organic EL display element, an ITO pattern and an insulating film pattern that also serves as a partition of the organic EL layer are formed, and then the organic EL layer pattern is formed by a masking method, an inkjet method, or the like, and then an electron A transport layer and a cathode (electron injection electrode) are formed. Here, as the organic EL layer, a material obtained by doping quinacridone or coumarin into a base material base such as Alq ₃ or BeBq ₃ is used, and as a cathode material, a low work function metal such as Mg or Ag is mainly used. It is common to use materials.

  In recent years, in order to meet the demand for higher definition, organic EL display elements having a higher aperture ratio have been studied. However, there is a certain limit to improving the aperture ratio for the following reasons. That is, in order to increase the aperture ratio in the passive organic EL display element, it is necessary to reduce the pattern width of the insulating film and the cathode barrier rib. However, a certain strength is required for these portions, and in terms of resolution. Since there is a limit to the reduction in pattern width, a sufficiently high aperture ratio cannot be obtained. Further, in the active organic EL display element, it is necessary to provide a constant interval between the pixels in order to avoid a short circuit of the ITO pattern for each pixel, and thus there is a limit in improving the aperture ratio.

  Recently, an active organic EL display element having a structure capable of realizing a higher aperture ratio has been studied. Such an active organic EL display element is manufactured by the following method, for example. First, a driving terminal is formed on a substrate such as glass, and a first insulating film serving also as a planarizing film is formed thereon. Next, a transparent electrode (hole injection electrode) pattern such as ITO is formed thereon. The pattern formation at this time is usually performed by a wet etching method. Further, a hole transport layer pattern is formed thereon by a masking method. Subsequently, an ITO pattern and a pattern of the second insulating film that also serves as a partition of the organic EL layer, and a pattern of the organic EL layer are formed by a masking method, an ink jet method, etc., and then an electron transport layer and a cathode (electron injection electrode) Are sequentially formed. At this time, in order to establish conduction between the ITO electrode (hole injection electrode) and the driving terminal, it is necessary to form a through hole or a U-shaped depression of about 1 to 15 μm in the first insulating film.

  By the way, it is known that the organic EL light-emitting layer, whether it is a low-molecular light-emitting layer or a polymer light-emitting layer, rapidly deteriorates when it comes into contact with moisture, and its light-emitting state is inhibited. It is considered that such moisture enters from the environment, and a trace amount of moisture contained in the insulating film material in the form of adsorbed water may gradually enter the organic EL layer.

  Up to the present, it has sufficient resolution to form through holes or U-shaped depressions necessary to achieve higher aperture ratios, has excellent planarization performance, and resist stripping used when forming transparent electrodes A material that has a high resistance to a liquid and that can form an insulating film that prevents intrusion of impurities (mainly moisture) that inhibit light emission has not been proposed.

  On the other hand, attempts have been made to provide a light shielding property to the base of the insulating film and / or the element isolation structure for the purpose of increasing the contrast and improving the visibility in a display device using an organic EL display element (for example, special features). (See Kaihei 11-273870 and JP-A 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 properties of the light-shielding cured film and the black matrix. When such a large amount of colorant is used, since the exposed radiation is absorbed by the colorant, the effective intensity of the radiation in the coating film is reduced, and the radiation sensitivity (exposure sensitivity) for pattern formation is reduced. ) Is reduced.

  A method of adding a heat-sensitive material and a developer to a positive resist containing an alkali-soluble resin such as a novolak resin and diazoquinone as a specific method for imparting light-shielding properties to partition walls and insulating films without reducing radiation sensitivity (For example, refer to JP-A-10-170715 and JP-A-2008-122501). In this method, a positive-type radiation-sensitive resin composition in which a heat-sensitive material that develops a black color upon application of heat and a developer is added in advance is used. In such a radiation-sensitive resin composition, the heat-sensitive material is in an unreacted state and is not black before exposure, so that the resin composition itself does not have light-shielding properties and the radiation sensitivity deteriorates. There is nothing.

  However, the temperature required for forming patterns, partition walls, or insulating films in organic EL display elements is generally around 200 ° C. Therefore, the developers and color formers disclosed in JP-A-10-170715 and JP-A-2008-122501 have insufficient heat resistance with respect to this temperature, and satisfactory light shielding properties cannot be obtained. However, it has been pointed out that there is a risk of sublimation during pattern formation and contamination of the firing furnace.

JP-A-11-273870 JP 2002-116536 A JP-A-10-170715 JP 2008-122501 A

  The present invention has been made on the basis of the above circumstances, and its purpose is to have a sufficient resolution capable of forming a through hole or a U-shaped depression in an insulating film, and excellent in flattening performance. A radiation-sensitive resin composition for forming partition walls and insulating films of organic EL display elements that has high resistance to a resist stripping solution used when forming a transparent electrode and has both excellent radiation sensitivity and high light-shielding property during heating To provide things.

（式（Ｉ）中、Ｒ^１は水素原子又は炭素数１〜４のアルキル基であり、Ｒ^２〜Ｒ^６は同一もしくは異なり、水素原子、ヒドロキシル基又は炭素数１〜４のアルキル基であり、Ｂは単結合、−ＣＯＯ−、又は−ＣＯＮＨ−であり、ｍは０〜３の整数であるが、但し、Ｒ^２〜Ｒ^６の少なくとも１つはヒドロキシル基である。式（ＩＩ）中、Ｒ^１は水素原子又は炭素数１〜４のアルキル基であり、Ｙ^１及びＹ^２は同一もしくは異なり、水素原子又は炭素数１〜６のアルキル基であり、Ｘ^１〜Ｘ^４は同一もしくは異なり、水素原子、炭素数１〜４のアルキル基又はハロゲン原子であり、Ｚは単結合又は−Ｏ（ＣＨ_２）_ｗ−であり、ｗは１〜６の整数である。式（ＩＩＩ）中、Ｒ^１は水素原子又は炭素数１〜４のアルキル基であり、Ｚは単結合又は−Ｏ（ＣＨ_２）_ｗ−であり、ｗは１〜６の整数である。） The present invention made to solve the above problems
[A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, and (a2) a phenol skeleton-containing unsaturated compound represented by the following formula (I), a compound represented by the following formula (II), and 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 following formula (III):
[B] A radiation-sensitive resin composition for forming partition walls and insulating films containing a 1,2-quinonediazide compound, and [C] a thermal dye.

(In Formula (I), R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^{2 to} R ⁶ are the same or different and are 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, in formula (II) , 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 are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and X ^{1 to} X ⁴ are the same or Differently, it is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, Z is a single bond or —O (CH ₂ ) _w —, and w is an integer of 1 to 6. In the formula (III) , ^{R 1} is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Z is a single If or -O _{(CH 2) w} - a and, w is an integer from 1 to 6).

  The partition wall and the insulating film-forming radiation-sensitive resin composition include an unsaturated carboxylic acid that acts as both an alkali-soluble resin and a developer, a copolymer such as a phenol skeleton-containing unsaturated compound, a thermal dye, Therefore, it has heat resistance to high temperatures during the formation of the partition walls and insulating film, and can prevent sublimation of the developer. In addition to excellent radiation sensitivity and developability, it also has high light-shielding properties during heating. It is done.

  In addition to the components (a1) and (a2), the alkali-soluble resin [A] in the radiation-sensitive resin composition is obtained by copolymerizing a monomer containing (a3) an epoxy group-containing unsaturated compound. It is preferable that it is a copolymer. [A] By using such an epoxy group-containing unsaturated compound as a component of a copolymer that is an alkali-soluble resin as a component, the heat resistance of partition walls and insulating films formed from the radiation-sensitive resin composition and It becomes possible to further increase the surface hardness.

  The content of the thermal dye of the [C] component in the radiation sensitive resin composition is preferably 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin of the [A] component. . By setting the content of the thermosensitive dye as the component [C] within such a range, the absorption sensitivity to heat, radiation sensitivity, heat resistance, and solvent resistance can be maintained at appropriate levels.

Moreover, the formation method of the partition for organic EL display elements of this invention and the insulating film for organic EL display elements is as follows.
(1) The process of forming the coating film of the said radiation sensitive resin composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) It includes a step of developing the coating film irradiated with radiation in step (2), and a step of (4) heating the coating film developed in step (3).

  In the case where the partition and the insulating film of the organic EL display element are produced by the above process using the radiation sensitive resin composition, the light sensitive dye contained in the composition is in an unreacted state before the exposure. However, when it is heated after exposure, it exhibits high light shielding properties, and the contrast of the display device including the organic EL display element having the partition and the insulating film is improved.

  As described above, since the radiation-sensitive resin composition of the present invention uses an alkali-soluble resin, which is a predetermined copolymer, as a developer, it has heat resistance against high temperatures during the formation of partition walls and insulating films. Further, sublimation of the developer can be prevented, and in addition to excellent radiation sensitivity and developability, a high light shielding property during heating can be obtained.

  The radiation-sensitive resin composition for forming partition walls and insulating films of the present invention includes an [A] component alkali-soluble resin, a [B] component 1,2-quinonediazide compound, a [C] component heat-sensitive dye, and other optional components. Contains ingredients. Hereinafter, each component will be described.

[A] Component [A] The component includes (a1) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, and (a2) a phenol skeleton-containing unsaturated compound represented by the above formula (I), the above formula (II) And a monomer comprising a compound selected from the group consisting of compounds represented by the above formula (III). Hereinafter, this copolymer is referred to as “copolymer [A]”. In addition to the compound (a1) and the compound (a2), the copolymer [A] includes (a3) an epoxy group-containing unsaturated compound, and / or (a4) other than these compounds (a1) to (a3). It may be a copolymer obtained by copolymerizing a monomer containing an unsaturated compound having radical polymerizability. Copolymer [A] is an alkali-soluble resin, but also functions as a developer in the radiation-sensitive resin composition. According to the radiation-sensitive resin composition containing the copolymer [A], in addition to high heat resistance, high radiation sensitivity and high developability during the formation of the partition walls and the insulating film, excellent light shielding properties can be obtained during heating.

  The copolymer [A] can be produced by radical polymerization of the compounds (a1) and (a2) and the arbitrary compounds (a3) and (a4) in a solvent in the presence of a polymerization initiator. Copolymer [A] is preferably a structural unit derived from compound (a1) based on the total of structural units derived from compounds (a1), (a2), (a3) and (a4). 5-40 mass%, Especially preferably, it contains 10-30 mass%. By using the structural unit derived from the compound (a1) at such a ratio, the solubility of the copolymer [A] in the aqueous alkaline solution in the development step can be controlled within an appropriate range.

  The compound (a1) is an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride having radical polymerizability. Examples of the compound (a1) include monocarboxylic acids, dicarboxylic acids, anhydrides of dicarboxylic acids, mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids, and monopolymers having a carboxyl group and a hydroxyl group at both ends. Examples thereof include (meth) acrylates, polycyclic compounds 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;
Examples of dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like;
As anhydrides of dicarboxylic acids, for example, anhydrides of the compounds exemplified as the above dicarboxylic acids;
As mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids, for example, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] and the like;

Examples of the mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends, such as ω-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 and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene. Ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6- Methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] And hept-2-ene anhydride.

  Of these compounds (a1), monocarboxylic acid and dicarboxylic acid anhydrides are preferably used. Among these, acrylic acid, methacrylic acid, and maleic anhydride are particularly preferably used from the viewpoints of copolymerization reactivity with other compounds, solubility in an aqueous alkali solution, and availability. These compounds (a1) are used alone or in combination.

  Copolymer [A] is preferably a structural unit derived from compound (a2) based on the total of structural units derived from compounds (a1), (a2), (a3) and (a4). 1-50 mass%, Especially preferably, it contains 3-40 mass%. By using 1 mass% or more of the structural unit derived from the compound (a2), the radiation sensitivity of the radiation-sensitive resin composition can be improved. On the other hand, when the amount of the structural unit is 50% by mass or less, it is possible to prevent the solubility in the alkaline aqueous solution from being excessively increased in the development step in forming the partition walls and the insulating film.

  The compound (a2) is selected from the group consisting of a phenol skeleton-containing unsaturated compound represented by the above formula (I), a compound represented by the above formula (II), and a compound represented by the above formula (III). It is a compound.

  The phenol skeleton-containing unsaturated compound represented by the above formula (I) can be classified into compounds represented by the following formulas (IV) to (VIII) according to the definitions of B and m.

（式（ＩＶ）中、ｎは１から３の整数であり、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、及びＲ^６の定義は式（Ｉ）に同じである。）

(In formula (IV), 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 in formula (I).)

（式（Ｖ）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、及びＲ^６の定義は、上記式（Ｉ）に同じである。）

(In formula (V), the definitions of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are the same as those in formula (I) above.)

（式（ＶＩ）中、ｐは１から３の整数である。Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、及びＲ^６の定義は上記式（Ｉ）に同じである。）

(In formula (VI), p is an integer of 1 to 3. The definitions of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are the same as those in formula (I) above.)

（式（ＶＩＩ）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、及びＲ^６の定義は上記式（Ｉ）に同じである。）

(In formula (VII), the definitions of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are the same as those in formula (I) above.)

（式（ＶＩＩＩ）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、及びＲ^６の定義は上記式（Ｉ）に同じである。）

(In formula (VIII), the definitions of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are the same as those in formula (I) above.)

  Among these phenol skeleton-containing unsaturated compounds, N- (3,5-dimethyl-4-hydroxybenzyl) (meth) acrylamide, N- (4-hydroxyphenyl) (meth) acrylamide, 4-hydroxybenzyl (meth) Acrylate, 4-hydroxyphenyl (meth) acrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, α-methyl-o-hydroxystyrene, α-methyl-m-hydroxystyrene, α-methyl-p- Hydroxystyrene is preferably used from the viewpoint of enhancing the radiation sensitivity of the radiation-sensitive resin composition, increasing the development margin (allowable range of development time), and improving the heat resistance of the obtained partition wall and insulating film.

  The compound represented by the above formula (II) is a compound in which a polymerizable unsaturated group is introduced into one hydroxyl group of a bisphenol type compound. Examples of the compound represented by the formula (II) include 4,4′-isopropylidenediphenol, 4,4′-isopropylidenebis (2-chlorophenol), 4,4′-isopropylidenebis (2 , 6-dibromophenol), 4,4′-isopropylidenebis (2,6-dichlorophenol), 4,4′-isopropylidenebis (2-methylphenol), 4,4′-isopropylidenebis (2, 6-dimethylphenol), 4,4′-isopropylidenebis (2-t-butylphenol), 4,4′-s-butylidenediphenol, 4,4′-s-butylidenebis (2-methylphenol), and other bisphenols Examples include compounds in which a (meth) acryloyl group is introduced into one hydroxyl group of a type compound. Among these, a compound in which a (meth) acryloyl group is introduced into one hydroxyl group of 4,4′-isopropylidenediphenol is particularly preferable from the viewpoint of improving the color development performance of the formed compound of the component [A].

  The compound represented by the above formula (III) is a compound in which a polymerizable unsaturated group is introduced into one hydroxyl group of naphthalenediol. Naphthalenediol may be any isomer of 1,2-isomer, 1,3-isomer, 1,4-isomer, 1,5-isomer, 2,3-isomer, and 2,6-isomer, A mixture of these may also be used. Specific examples of the compound represented by the formula (III) include 1-acryloyloxy-4-naphthol, 1-acryloyloxy-5-naphthol, 2-acryloyloxy-6-naphthol, 1-methacryloyloxy-4- Examples include naphthol, 1-methacryloyloxy-5-naphthol, 2-methacryloyloxy-6-naphthol, and the like. Among these compounds, 1-methacryloyloxy-4-naphthol is particularly preferable from the viewpoint of improving the color development performance and copolymerizability of the compound [A] formed.

  Copolymer [A] is a structural unit derived from compound (a3), which is an epoxy group-containing unsaturated compound having radical polymerizability, from compounds (a1), (a2), (a3) and (a4). The content is preferably 10 to 80% by mass, particularly preferably 20 to 70% by mass, based on the total of derived structural units. By setting the amount of the structural unit derived from this compound (a3) to 10% by mass or more, the heat resistance and surface hardness of the obtained partition wall and insulating film are improved. On the other hand, the storage stability of a radiation sensitive resin composition can be kept high by making the quantity of this structural unit 80 mass% or less.

  Examples of the compound (a3) include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and 3,4-epoxybutyl acrylate. , Methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzylglycidyl ether M-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, and the like. Among these compounds (a3), glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclo Hexyl methacrylate or the like is preferably used from the viewpoint of increasing the copolymerization reactivity with other compounds and the heat resistance and surface hardness of the resulting partition walls and insulating film. These compounds (a3) are used alone or in combination.

  The copolymer [A] comprises a structural unit derived from the compound (a4) which is an unsaturated compound having radical polymerizability other than the above compounds (a1), (a2) and (a3). Based on the total of structural units derived from (a2), (a3) and (a4), the content is preferably 5 to 70% by mass, particularly preferably 5 to 50% by mass. By making the structural unit derived from this compound (a4) 5 mass% or more, the storage stability of the radiation-sensitive resin composition can be improved. On the other hand, when the amount of the structural unit is 70% by mass or less, the solubility of the composition in an alkaline aqueous solution can be promoted in the development step in forming the partition walls and the insulating film.

  Examples of the compound (a4) include methacrylic acid chain alkyl ester, acrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, methacrylic acid ester having a hydroxyl group, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, and acrylic acid aryl ester. Unsaturated dicarboxylic acid diester, bicyclo unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, unsaturated compound having tetrahydrofuran skeleton, unsaturated compound having furan skeleton, unsaturated compound having tetrahydropyran skeleton, pyran Examples thereof include unsaturated compounds having a skeleton, unsaturated compounds having a skeleton represented by the following formula (IX), and other unsaturated compounds.

（式（ＩＸ）中、Ｒ^７は水素原子又はメチル基である。ｑは１以上の整数である。）

(In Formula (IX), R ⁷ is a hydrogen atom or a methyl group. 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-ethylhexyl methacrylate, isodecyl methacrylate, and n-lauryl methacrylate. , Tridecyl methacrylate, n-stearyl methacrylate, etc .;
Examples of acrylic acid chain alkyl esters such as methyl acrylate and isopropyl acrylate;
Examples of cyclic alkyl esters of methacrylic acid include 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, etc .;
Examples of the methacrylic acid ester having a hydroxyl group include hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, and 2-methacryloxyethylglycoside. Such;

Examples of acrylic acid cyclic alkyl esters include 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;
Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate;
Examples of acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate;
Unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate and the like;

  Examples of the bicyclo unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2.1] hept. 2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2. 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5- Cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [2. 2.1] Hept-2 Ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5 , 6-Dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′- Hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2 .1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene and the like;

Examples of maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate, N -Succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like;
Examples of unsaturated aromatic compounds include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and the like;
Examples of conjugated dienes include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like;

Examples of unsaturated compounds containing a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, and 3- (meth) acryloyloxytetrahydrofuran-2-one;
Examples of unsaturated compounds containing a furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-ene-2. -One, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2-yl -Hex-1-en-3-one, acrylic acid-2-furan-2-yl-1-methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-hepten-3-one, and the like;
Examples of unsaturated compounds containing a tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one, 2-methacrylic acid tetrahydropyran-2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, etc .;

Examples of unsaturated compounds containing a pyran skeleton include 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyran, 4- (1,5-dioxa-6-oxo- 7-octenyl) -6-methyl-2-pyran and the like;
Examples of unsaturated compounds containing a skeleton represented by the above formula (IX) include polyethylene glycol (n = 2 to 10) mono (meth) acrylate, polypropylene glycol (n = 2 to 10) mono (meth) acrylate, and the like;
Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Among these compounds (a4), methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid cyclic alkyl ester, unsaturated dicarboxylic acid diester, bicyclounsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene An unsaturated compound containing a tetrahydrofuran skeleton, an unsaturated compound containing a tetrahydropyran skeleton, and an unsaturated compound containing a skeleton represented by the above formula (IX) are preferably used. Among these, styrene, t-butyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, 1,3-butadiene, bicyclo [2.2.1] hept-2-ene, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, 3- (meth) acryloyloxytetrahydrofuran-2-one, 1 -(Tetrahydropyran-2-oxy) -butyl-3-en-2-one, furfuryl (meth) acrylate, N-cyclohexylmaleimide has copolymerization reactivity with other compounds, and solubility in an aqueous alkali solution To preferred. 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 compounds is a monomer, a methacrylic acid / tricyclo [5.2.1.0 ^2,6] decan-8-yl Methacrylate / glycidyl methacrylate / 2-methylcyclohexyl acrylate / N- (3,5-dimethyl-4-hydroxybenzyl) methacrylamide copolymer, methacrylic acid / glycidyl methacrylate / 1- (tetrahydropyran-2-oxy)- Butyl-3-en-2-one / N-cyclohexylmaleimide / p-methoxystyrene / 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- off Cycloalkenyl maleimide / N-(4-hydroxyphenyl) methacrylamide copolymers, methacrylic acid / glycidyl methacrylate / tricyclo [5.2.1.0 ^2,6] decan-8-yl methacrylate / n-lauryl methacrylate / 3 -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-8-yl methacrylate / glycidyl methacrylate / styrene / p-vinylbenzyl glycidyl ether / Tetrahydrofurfuryl methacrylate / 4-hydroxyphenyl methacrylate copolymer, methacrylic acid / glycidyl methacrylate / N-cyclohexylmaleimide / 3-methacryloyloxytetrahydrofuran-2-one / tetrahydrofurfuryl methacrylate / 4-hydroxyphenyl methacrylate copolymer, methacrylic acid / Glycidyl methacrylate / tetrahydrofurfuryl methacrylate / N-phenylmaleimide / 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 / α-methyl-p-hydroxystyrene copolymer, methacrylic acid / glycidyl methacrylate / tetrahydrofurfuryl Methacrylate / N- cyclohexyl maleimide / n-lauryl methacrylate / alpha-methyl -p- hydroxystyrene copolymer, methacrylic acid / tricyclo [5.2.1.0 ^2,6] decan-8-yl methacrylate / glycidyl methacrylate A copolymer of a compound in which a methacryloyl group is introduced into one hydroxyl group of 2,2-methylcyclohexyl acrylate / 4,4′-isopropylidene-diphenol, methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] Examples include decan-8-yl methacrylate / glycidyl methacrylate / 2-methylcyclohexyl acrylate / 1-methacryloyloxy-4-naphthol copolymer.

The polystyrene-converted 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 copolymer Mw of [A] and 2 × 10 ³ or more, with obtaining a sufficient development margin radiation-sensitive resin composition, residual film ratio of the coating film formed (patterned thin film is properly remained Ratio) can be prevented, and the pattern shape and heat resistance of the resulting partition and insulating film can be kept good. On the other hand, when the Mw of the copolymer [A] is 1 × 10 ⁵ or less, high radiation sensitivity can be maintained and a good pattern shape can be obtained. The molecular weight distribution (hereinafter referred to as “Mw / Mn”) of the copolymer [A] is preferably 5.0 or less, more preferably 3.0 or less. By making Mw / Mn of the copolymer [A] 5.0 or less, the pattern shape of the obtained partition wall and insulating film can be kept good. In addition, since the radiation-sensitive resin composition containing the copolymer [A] having Mw and Mw / Mn in the preferable range as described above has high developability, no development residue is generated in the development step. A predetermined pattern shape can be easily 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, and propylene glycol monoalkyls. Examples include ether acetate, propylene glycol monoalkyl ether propionate, aromatic hydrocarbons, ketones, and other esters.

Examples of these solvents include alcohols such as methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, and 3-phenyl-1-propanol;
Ethers such as tetrahydrofuran;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Examples of ethylene glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of the diethylene glycol alkyl ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and the like;
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;

As 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;
As propylene glycol monoalkyl ether propionate, for example, propylene monoglycol methyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate, etc .;
Examples of aromatic hydrocarbons include toluene and xylene;
Examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, etc .;

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

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

  As the polymerization initiator used in the polymerization reaction for producing the copolymer [A], those generally known as radical polymerization initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile) Azo compounds such as; benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, organic peroxides such as 1,1′-bis- (t-butylperoxy) cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.

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

[B] Component [B] component used for the radiation sensitive resin composition of this invention is a 1, 2- quinonediazide compound which generate | occur | produces carboxylic acid by irradiation of a radiation. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used.

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

As these mother nuclei, as trihydroxybenzophenone, for example, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone and the like;
Examples of tetrahydroxybenzophenone include 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, etc .;
Examples of pentahydroxybenzophenone include 2,3,4,2 ′, 6′-pentahydroxybenzophenone and the like;
Examples of hexahydroxybenzophenone include 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone and the like;

  Examples of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, and 1,1,1-tri (p-hydroxyphenyl). ) Ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-4) -Hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl- 4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene 5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl -7,2 ', 4'-trihydroxy flavan like;

  As other mother nucleus, for example, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 2- [bis {(5-isopropyl-4-hydroxy- 2-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) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene.

  Among these mother nuclei, 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 preferred.

  The 1,2-naphthoquinone diazide sulfonic acid halide is preferably 1,2-naphthoquinone diazide sulfonic acid chloride. Specific examples of 1,2-naphthoquinone diazide sulfonic acid chloride include 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1,2-naphthoquinone diazide-5-sulfonic acid chloride. Among these, it is particularly preferable to use 1,2-naphthoquinonediazide-5-sulfonic acid chloride.

  In the condensation reaction of the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazidesulfonic acid halide, preferably 30 to 85 moles relative to the number of OH groups in the phenolic compound or alcoholic compound. %, More preferably 1,2-naphthoquinonediazidesulfonic acid halide corresponding to 50 to 70 mol% can be used. The condensation reaction can be carried out by a known method.

  Further, as the 1,2-quinonediazide compound, 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, for example, 2,3,4-trihydroxybenzophenone-1,2 -Naphthoquinonediazide-4-sulfonic acid amide etc. are also used suitably.

  These [B] components can be used individually or in combination of 2 or more types. The ratio of the component [B] used in the radiation sensitive resin composition is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the copolymer [A]. By setting the ratio of the component [B] in the radiation-sensitive resin composition to 5 parts by mass or more, the difference in solubility between the irradiated portion and the unirradiated portion with respect to the alkaline aqueous solution that is the developer increases, and patterning is easy. At the same time, the heat resistance and solvent resistance of the partition and the insulating film obtained are kept good. On the other hand, when the ratio of the component [B] is 100 parts by mass or less, the solubility in the alkaline aqueous solution in the radiation irradiated portion is maintained at a sufficiently high level, and development can be easily performed.

[C] Component [C] component is a thermal dye. The term “thermosensitive dye” as used herein means a compound having a property of developing color when heated in a state of receiving an electron-accepting compound (for example, proton such as acid). As thermal dyes, in particular, colorless compounds that have partial skeletons such as lactones, lactams, sultones, spiropyrans, esters, amides, etc., and these partial skeletons rapidly open or cleave when contacted with electron-accepting compounds Is preferred.

  Examples of such thermal dyes include 3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide (referred to as “crystal violet lactone”), 3,3-bis (4-dimethyl). Aminophenyl) phthalide, 3- (4-dimethylaminophenyl) -3- (4-diethylamino-2-methylphenyl) -6-dimethylaminophthalide, 3- (4-dimethylaminophenyl) -3- (1, 2-dimethylindol-3-yl) phthalide, 3- (4-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3,3-bis (1,2-dimethylindole-3- Yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3-bis 9-ethylcarbazol-3-yl) -6-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -6-dimethylaminophthalide, 3- (4-dimethylaminophenyl)- 3- (1-methylpyrrol-3-yl) -6-dimethylaminophthalide,

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

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

  3,6-dimethoxyfluorane, 3-dimethylamino-7-methoxyfluorane, 3-diethylamino-6-methoxyfluorane, 3-diethylamino-7-methoxyfluorane, 3-diethylamino-7-chlorofluorane, 3 -Diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-6,7-dimethylfluorane, 3-N-cyclohexyl-Nn-butylamino-7-methylfluorane, 3-diethylamino-7- Dibenzylaminofluorane, 3-diethylamino-7-octylaminofluorane, 3-diethylamino-7-di-n-hexylaminofluorane, 3-diethylamino-7-anilinofluorane, 3-diethylamino-7- ( 2'-fluorophenylamino) fluorane, 3-diethylamino- -(2'-chlorophenylamino) fluorane, 3-diethylamino-7- (3'-chlorophenylamino) fluorane, 3-diethylamino-7- (2 ', 3'-dichlorophenylamino) fluorane, 3-diethylamino-7- ( 3'-trifluoromethylphenylamino) fluorane, 3-di-n-butylamino-7- (2'-fluorophenylamino) fluorane, 3-di-n-butylamino-7- (2'-chlorophenylamino) Fluorane, 3-N-isopentyl-N-ethylamino-7- (2′-chlorophenylamino) fluorane,

3-Nn-hexyl-N-ethylamino-7- (2'-chlorophenylamino) fluorane, 3-diethylamino-6-chloro-7-anilinofluorane, 3-di-n-butylamino-6- Chloro-7-anilinofluorane, 3-diethylamino-6-methoxy-7-anilinofluorane, 3-di-n-butylamino-6-ethoxy-7-anilinofluorane, 3-pyrrolidino-6 Methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-morpholino-6-methyl-7-anilinofluorane, 3-dimethylamino-6-methyl-7- Anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-di-n-butylamino-6-methyl-7-anilinofluorane, 3-di-n Pentylamino-6-methyl-7-anilinofluorane, 3-N-ethyl-N-methylamino-6-methyl-7-anilinofluorane, 3-Nn-propyl-N-methylamino-6 -Methyl-7-anilinofluorane, 3-Nn-propyl-N-ethylamino-6-methyl-7-anilinofluorane, 3-Nn-butyl-N-methylamino-6-methyl -7-anilinofluorane, 3-Nn-butyl-N-ethylamino-6-methyl-7-anilinofluorane, 3-N-isobutyl-N-methylamino-6-methyl-7-ani Linofluorane, 3-N-isobutyl-N-ethylamino-6-methyl-7-anilinofluorane, 3-N-isopentyl-N-ethylamino-6-methyl-7-anilinofluorane, 3- Nn-hexy -N-methylamino-6-methyl-7-anilinofluorane, 3-N-cyclohexyl-N-ethylamino-6-methyl-7-anilinofluorane, 3-N-cyclohexyl-Nn-propyl Amino-6-methyl-7-anilinofluorane, 3-N-cyclohexyl-Nn-butylamino-6-methyl-7-anilinofluorane, 3-N-cyclohexyl-Nn-hexylamino- 6-methyl-7-anilinofluorane, 3-N-cyclohexyl-Nn-octylamino-6-methyl-7-anilinofluorane,

3-N- (2′-methoxyethyl) -N-methylamino-6-methyl-7-anilinofluorane, 3-N- (2′-methoxyethyl) -N-ethylamino-6-methyl-7 -Anilinofluorane, 3-N- (2'-methoxyethyl) -N-isobutylamino-6-methyl-7-anilinofluorane, 3-N- (2'-ethoxyethyl) -N-methylamino -6-methyl-7-anilinofluorane, 3-N- (2'-ethoxyethyl) -N-ethylamino-6-methyl-7-anilinofluorane, 3-N- (3'-methoxypropyl) ) -N-methylamino-6-methyl-7-anilinofluorane, 3-N- (3'-methoxypropyl) -N-ethylamino-6-methyl-7-anilinofluorane, 3-N- (3′-Ethoxypropyl) -N-me Ruamino-6-methyl-7-anilinofluorane, 3-N- (3′-ethoxypropyl) -N-ethylamino-6-methyl-7-anilinofluorane, 3-N- (2′-tetrahydro Furfuryl) -N-ethylamino-6-methyl-7-anilinofluorane, 3-N- (4′-methylphenyl) -N-ethylamino-6-methyl-7-anilinofluorane, 3- Diethylamino-6-ethyl-7-anilinofluorane, 3-diethylamino-6-methyl-7- (3′-methylphenylamino) fluorane, 3-diethylamino-6-methyl-7- (2 ′, 6′- Dimethylphenylamino) fluorane, 3-di-n-butylamino-6-methyl-7- (2 ′, 6′-dimethylphenylamino) fluorane, 3-di-n-butylamino-7- ( ', 6'-dimethylphenylamino) fluorane, 2,2-bis [4'-(3-N-cyclohexyl-N-methylamino-6-methylfluorane) -7-ylaminophenyl] propane, 3- [ Fluoranes such as 4 ′-(4-phenylaminophenyl) aminophenyl] amino-6-methyl-7-chlorofluorane, 3- [4 ′-(dimethylaminophenyl)] amino-5,7-dimethylfluorane ,

  3- (2-Methyl-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (2-n-propoxycarbonylamino-4-di-n) -Propylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (2-methylamino-4-di-n-propylaminophenyl) -3- (1 -Ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (2-methyl-4-di-n-hexylaminophenyl) -3- (1-n-octyl-2-methylindole-3- Yl) -4,7-diazaphthalide, 3,3-bis (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3,3-bis (1-n-octyl-2-methylindole- -Yl) -4-azaphthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (2-ethoxy-4) -Diethylaminophenyl) -3- (1-octyl-2-methylindol-3-yl) -4 or 7-azaphthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2- Methylindol-3-yl) -4 or 7-azaphthalide, 3- (2-hexyloxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4 or 7-azaphthalide 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-phenylindol-3-yl) -4 or 7-azaphthalide, 3 (2-butoxy-4-diethylaminophenyl) -3- (1-ethyl-2-phenylindol-3-yl) -4 or 7-azaphthalide 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3 -Phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho- (3-methoxybenzo) spiropyran, 3-propyl-spiro-dibenzopyran-3,6-bis (dimethylamino) fluorene-9 Phthalides such as -spiro-3 '-(6'-dimethylamino) phthalide, 3,6-bis (diethylamino) fluorene-9-spiro-3'-(6'-dimethylamino) phthalide,

  Others 2'-anilino-6 '-(N-ethyl-N-isopentyl) amino-3'-methylspiro [isobenzofuran-1 (3H), 9'-(9H) xanthen-3-one, 2'-anilino -6 '-(N-ethyl-N- (4-methylphenyl)) amino-3'-methylspiro [isobenzofuran-1 (3H), 9'-(9H) xanthen] -3-one, 3'-N , N-dibenzylamino-6′-N, N-diethylaminospiro [isobenzofuran-1 (3H), 9 ′-(9H) xanthen] -3-one, 2 ′-(N-methyl-N-phenyl) And amino-6 ′-(N-ethyl-N- (4-methylphenyl)) aminospiro [isobenzofuran-1 (3H), 9 ′-(9H) xanthen] -3-one.

  Commercial products of these thermal dyes include ETAC, RED500, RED520, CVL, S-205, BLACK305, BLACK400, BLACK100, BLACK500, H-7001, GREEN300, NIR BLACK78, BLUE220, H-3035, BLUE203, ATP, H -1046, H-2114 (manufactured by Yamada Chemical Co., Ltd.), ORANGE-DCF, Vermilion-DCF, PINK-DCF, RED-DCF, BLMB, CVL, GREEN-DCF, TH-107 (Hodogaya Chemical Co., Ltd.) ) And the like. Among these commercial products, ETAC, S-205, BLACK305, BLACK400, BLACK100, BLACK500, H-7001, GREEN300, NIR BLACK78, H-3035, ATP, H-1046, H-2114, GREEN-DCF are formed. The visible light absorption rate of the film to be formed is preferable.

  These thermal dyes can also be used in combination of two or more components depending on the visible light spectrum required for the partition walls and the insulating film. The proportion of the [C] component used in the radiation-sensitive resin composition is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the copolymer [A]. . By setting the ratio of the component [C] to 0.1 part by mass or more, it is possible to efficiently absorb a desired light beam and develop light shielding properties. On the other hand, by setting the ratio 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 kept good.

Other optional components The radiation-sensitive resin composition of the present invention contains the above-mentioned components [A], [B] and [C] as essential components, and [D] a thermosensitive acid-generating compound as required. , [E] a polymerizable compound having at least one ethylenically unsaturated double bond, an epoxy resin other than [F] copolymer [A], [G] a surfactant, and [H] an adhesion assistant can do.

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

As these sulfonium salts,
Examples of the alkylsulfonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- ( Benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate, etc .;

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

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

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

Examples of the benzothiazonium salt include
3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-methoxybenzyl) benzothiazonium hexafluoroantimonate , 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, in particular, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate Nate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, and 3-benzylbenzothiazonium hexafluoroantimonate are preferably used.

  Examples of commercially available products of these thermosensitive acid-generating compounds include Sun-Aid SI-L85, SI-L110, SI-L145, SI-L150, SI-L160 (manufactured by Sanshin Chemical Industry Co., Ltd.). It is done.

  The proportion of the component [D] used in the radiation sensitive resin composition is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the copolymer [A]. By setting the blending amount of the component [D] to 0.1 to 20 parts by mass, a cured film having sufficient strength can be formed, and generation of precipitates can be prevented in the coating film forming process. It becomes.

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

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

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

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

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

  The proportion of the [E] component used in the radiation-sensitive resin composition is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass with respect to 100 parts by mass of the copolymer [A]. [E] By making the compounding amount of the component 1 to 50 parts by mass, the heat resistance and surface hardness of the obtained partition wall and insulating film can be improved, and the film roughness in the coating film forming process on the substrate Can be suppressed.

  The epoxy resin other than the copolymer [A] as the component [F] 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 novolac type epoxy resins, cycloaliphatic epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, heterocyclic rings. Examples thereof include a resin obtained by (co) polymerizing a formula epoxy resin and glycidyl methacrylate. Of these, bisphenol A type epoxy resins, cresol novolac type epoxy resins, glycidyl ester type epoxy resins and the like are particularly preferable.

  The proportion of the [F] component used in the radiation-sensitive resin composition is preferably 30 parts by mass or less with respect to 100 parts by mass of the copolymer [A]. By using the [F] component at such a ratio, the heat resistance and surface hardness of the partition and the insulating film obtained from the radiation-sensitive resin composition can be further improved, and the radiation-sensitive resin on the substrate. When forming the coating film of the composition, a high degree of film thickness uniformity can be obtained. The copolymer [A] can also be referred to as an “epoxy resin”, but differs from the [F] component in that it has alkali solubility. [F] component is alkali-insoluble.

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

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

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

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

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

  In the radiation sensitive resin composition, the surfactant of the component [G] is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the copolymer [A]. It is. By setting the blending amount of the surfactant to 0.01 to 5 parts by mass, it is possible to suppress the occurrence of film roughness when a coating film is formed on the substrate.

  In the radiation sensitive resin composition of this invention, in order to improve adhesiveness with a board | substrate, the adhesion adjuvant which is [H] component can be used. As such an adhesion assistant, a functional silane coupling agent is preferably used. Examples of functional silane coupling agents include silane coupling agents having reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, and epoxy groups. Specific examples of functional silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxy Examples thereof include propyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. In the radiation-sensitive resin composition, such an adhesion assistant is preferably 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass with respect to 100 parts by mass of the copolymer [A]. By setting the blending amount of the adhesion assistant of [H] component to 0.1 to 20 parts by mass, sufficient adhesion to the substrate is expressed without causing development residue in the development process, and a pattern can be easily formed. Can be formed.

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

  As the solvent used for the preparation of the radiation sensitive resin composition, the above [A], [B] and [C] components and optional components ([D] to [H] components) are uniformly dissolved. And as long as it does not react with each component, it is not particularly limited. As such a solvent, the thing similar to the solvent illustrated as a solvent which can be used in order to manufacture copolymer [A] can be mentioned.

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

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

  When a high boiling point solvent is used in combination as a solvent for the radiation sensitive resin composition, the amount used is preferably 1 to 40% by mass, more preferably 3 to 30% by mass or more based on the total amount of the solvent. By setting it as 1-40 mass%, the applicability | paintability at the time of coating-film formation can be made further favorable, and also the fall of a radiation sensitivity and a residual film rate can be suppressed.

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

Formation of Partition Wall and Insulating Film Next, a method for forming the partition wall and the insulating film of the present invention using the above-mentioned radiation sensitive resin composition will be described. The method includes the following steps in the order described below.
(1) The process of forming the coating film of the radiation sensitive resin composition of this invention on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) a step of developing the coating film irradiated with radiation in step (2), and (4) a step of heating the coating film developed in step (3).

(1) Step of forming a coating film of a radiation sensitive resin composition on a substrate In the step (1), a solution of the radiation sensitive resin composition of the present invention is applied to the substrate surface, and preferably prebaked. To remove the solvent and 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 method for applying the composition solution is not particularly limited. For example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an ink jet method is adopted. can do. Among these coating methods, the spin coating method and the slit die coating method are particularly preferable. The pre-baking conditions vary depending on the type of each component, the use ratio, and the like, but can be, for example, 60 to 110 ° C. for 30 seconds to 15 minutes. As a film thickness of the coating film formed, it can be set as 3-6 micrometers as a value after a prebaking.

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

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

(3) Development step (3) In the development step, the coating film irradiated with radiation in the step (2) is developed to remove the irradiated portion and form a desired pattern. it can. Examples of the developer used for the development processing include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine. , Triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5- An aqueous solution of an alkali (basic compound) such as diazabicyclo [4,3,0] -5-nonane can be used. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution described above, or an alkaline aqueous solution containing a small amount of various organic solvents that dissolve the radiation-sensitive resin composition is used as a developer. Can be used. Furthermore, as a developing method, for example, an appropriate method such as a liquid filling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time varies depending on the composition of the radiation-sensitive resin composition, but can be, for example, 30 to 120 seconds.

  It is necessary to strictly control the development time of conventionally known radiation-sensitive resin compositions because the formed pattern peels when the development time exceeds about 20 to 25 seconds from the optimum value. On the other hand, since the radiation sensitive resin composition of the present invention has a high development margin, it is possible to form a good pattern even when the excess time from the optimum development time is 30 seconds or more, which is an advantage in product yield. Is big.

(4) Heating step (4) In the heating step, after the developing step (3) above, the patterned thin film is preferably rinsed with running water, and then preferably irradiated with radiation from a high-pressure mercury lamp or the like. By irradiating the entire surface (post-exposure), the 1,2-quinonediazide compound remaining in the thin film is decomposed. Next, the thin film is subjected to a heat treatment (post-bake treatment) by using a heating device such as a hot plate or an oven to perform a thin film curing treatment. The exposure amount in the post-exposure is preferably about 2,000 to 5,000 J / m ² . Moreover, the baking temperature in this hardening process is 120-250 degreeC, for example. Although heating time changes with kinds of heating apparatus, for example, when performing heat processing on a hotplate, it can be set to 30 to 90 minutes when performing heat processing in oven, for 30 to 90 minutes. At this time, a step baking method or the like in which a heating process is performed twice or more can also be used. In this manner, a patterned thin film corresponding to the target partition wall or insulating film can be formed on the surface of the substrate.

  The partition wall or the insulating film formed as described above has radiation sensitivity, development margin (development scale), solvent resistance, heat resistance, total light transmittance (as will be clarified from Examples described later). Excellent characteristics are exhibited in all points of light-shielding property) and relative permittivity (dielectric property measure).

  The present invention will be described more specifically with reference to synthesis examples and examples. However, the present invention is not limited to the following examples.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the copolymers obtained from the following synthesis examples and comparative synthesis examples were measured by gel permeation chromatography (GPC) according to the following specifications.
Apparatus: GPC-101 (made by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 (manufactured by Showa Denko KK) Mobile phase: Tetrahydrofuran containing 0.5% by mass of phosphoric acid

Example of copolymer synthesis [Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 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, N- (3 , 5-dimethyl-4-hydroxybenzyl) methacrylamide and 3 parts by weight of α-methylstyrene dimer were charged and purged with nitrogen, and then gently stirred. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-1]. This copolymer [A-1] had a polystyrene-reduced weight average molecular weight (Mw) of 8,000 and a molecular weight distribution (Mw / Mn) of 2.3. Moreover, the solid content concentration of the polymer solution obtained here was 34.4 mass%.

[Synthesis Example 2]
A flask equipped with a condenser and a stirrer was charged with 9 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 12 parts by weight of methacrylic acid, 12 parts by weight of p-methoxystyrene, 15 parts by weight of 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, 40 parts by weight of glycidyl methacrylate, N-cyclohexylmaleimide After 10 parts by mass, 10 parts by mass of N- (3,5-dimethyl-4-hydroxybenzyl) methacrylamide and 3 parts by mass of α-methylstyrene dimer were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-2]. The copolymer [A-2] had a polystyrene equivalent weight average molecular weight (Mw) of 8,100 and a molecular weight distribution (Mw / Mn) of 2.4. Moreover, the solid content concentration of the polymer solution obtained here was 32.7 mass%.

[Synthesis Example 3]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 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, 4-hydroxybenzyl methacrylate After 20 parts by mass and 3 parts by mass of α-methylstyrene dimer were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-3]. The polystyrene equivalent weight average molecular weight (Mw) of the copolymer [A-3] was 8,500, and the molecular weight distribution (Mw / Mn) was 2.3. Moreover, the solid content concentration of the polymer solution obtained here was 34.1% by mass.

[Synthesis Example 4]
A flask equipped with a condenser and a stirrer was charged with 8 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 11 parts by weight of methacrylic acid, 12 parts by weight of tetrahydrofurfuryl methacrylate, 40 parts by weight of glycidyl methacrylate, 15 parts by weight of N-cyclohexylmaleimide, 10 parts by weight of n-lauryl methacrylate, 10 parts by weight of α-methyl-p-hydroxystyrene, And 3 parts by mass of α-methylstyrene dimer were charged and purged with nitrogen, and then gently stirred. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer [A-4]. The copolymer [A-4] had a polystyrene equivalent weight average molecular weight (Mw) of 8,000 and a molecular weight distribution (Mw / Mn) of 2.3. Moreover, the solid content concentration of the polymer solution obtained here was 31.9 mass%.

[Synthesis Example 5]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 14 parts by weight of methacrylic acid, 16 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 20 parts by weight of 2-methylcyclohexyl acrylate, 40 parts by weight of glycidyl methacrylate, 4,4 ′ -10 parts by mass of a compound in which a methacryloyl group was introduced into one hydroxyl group of isopropylidenediphenol and 3 parts by mass of α-methylstyrene dimer were charged and purged with nitrogen, followed by gentle stirring. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-5]. This copolymer [A-5] had a polystyrene-reduced weight average molecular weight (Mw) of 7,000 and a molecular weight distribution (Mw / Mn) of 2.5. Moreover, the solid content concentration of the polymer solution obtained here was 34.8 mass%.

[Synthesis Example 6]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 14 parts by weight of methacrylic acid, 16 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 20 parts by weight of 2-methylcyclohexyl acrylate, 40 parts by weight of glycidyl methacrylate, 1-methacryloyloxy After 10 parts by weight of -4-naphthol and 3 parts by weight of α-methylstyrene dimer were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-6]. The copolymer [A-6] had a polystyrene equivalent weight average molecular weight (Mw) of 8,000 and a molecular weight distribution (Mw / Mn) of 2.5. Moreover, the solid content concentration of the polymer solution obtained here was 34.6% by mass.

[Comparative Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 8 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 12 parts by weight of methacrylic acid, 12 parts by weight of p-methoxystyrene, 15 parts by weight of 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, 40 parts by weight of glycidyl methacrylate, N-cyclohexylmaleimide 10 parts by mass, 10 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, and 3 parts by mass of α-methylstyrene dimer were charged and purged with nitrogen, and then gently stirred. . The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [a-1]. The copolymer [a-1] had a polystyrene equivalent weight average molecular weight (Mw) of 8,900 and a molecular weight distribution (Mw / Mn) of 2.5. Moreover, the solid content concentration of the polymer solution obtained here was 32.9 mass%.

<Preparation of radiation-sensitive resin composition>
[Example 1]
The amount of the solution containing the copolymer [A-1] of Synthesis Example 1 as the component [A] is equivalent to 100 parts by mass (solid content) of the copolymer, and 4,4 ′-[ 1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) 30 parts by mass of the condensate (B-1), and 2′-anilino-6 ′-(N-ethyl-N-isopentyl) amino-3′-methylspiro [isobenzofuran-1 (3H), 9 ′-(9H) xanthen] -3-one (C-1) 5 parts by mass were mixed and dissolved in diethylene glycol ethyl methyl ether so that the solid content concentration was 30% by mass. Filtration with membrane filter And the solution (S-1) of the radiation sensitive resin composition was prepared.

[Examples 2-5, 7-10, Comparative Examples 1-4]
As the components [A], [B] and [C], except that the types and amounts shown in Table 1 were used, the solution (S-2) of the radiation sensitive resin composition as in Example 1 was used. (S-5), (S-7) to (S-10), and (s-1) to (s-4) were prepared.

[Example 6]
A solution of the radiation sensitive resin composition (as in Example 1) except that it was dissolved in diethylene glycol ethyl methyl ether / propylene glycol monomethyl ether acetate = 6/4 (molar ratio) so that the solid content concentration was 20% by mass. S-6) was prepared.

In Table 1, the abbreviations of the components indicate the following compounds.
(B-1): 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide Condensation product (B-2) of -5-sulfonic acid chloride (2.0 mol): 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensate (C-1) of sulfonic acid chloride (2.0 mol): 2'-anilino-6 '-(N-ethyl-N-isopentyl) amino-3'-methylspiro [isobenzofuran-1 (3H) , 9 ′-(9H) xanthene] -3-one (manufactured by Yamada Chemical Co., Ltd., trade name S205)
(C-2) 2'-anilino-6 '-(N-ethyl-N- (4-methylphenyl)) amino-3'-methylspiro [isobenzofuran-1 (3H), 9'-(9H) xanthene] -3-On (Yamada Chemical Industry Co., Ltd., trade name ETAC)
(C-3) 3′-N, N-dibenzylamino-6′-N, N-diethylaminospiro [isobenzofuran-1 (3H), 9 ′-(9H) xanthen] -3-one (Hodogaya Chemical ( Product name GREEN DCF)
(C-4) 2 ′-(N-methyl-N-phenyl) amino-6 ′-(N-ethyl-N- (4-methylphenyl)) aminospiro [isobenzofuran-1 (3H), 9 ′-( 9H) Xanthene] -3-one (manufactured by Yamada Chemical Co., Ltd., trade name ATP)
(G) Surfactant: SH28PA (Toray Dow Corning Silicone Co., Ltd.)
(H) Adhesion aid: β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (X-1) low molecular developer: BONJET BLACK0052 (manufactured by Orient Chemical Co., Ltd.)
(X-2) Low molecular developer: 4-phenylphenol

<Performance evaluation as partition walls and insulating films>
[Examples 11 to 20, Comparative Examples 5 to 8]
Using the radiation-sensitive resin composition prepared as described above, various characteristics as a partition and an insulating film were evaluated as follows.

[Evaluation of radiation sensitivity]
For Examples 11-15, 17-20, and Comparative Examples 5-8, a spinner was used, and for Example 16, a slit die coater was used to apply the composition described in Table 2 on the silicon substrate. The film was prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was exposed by changing the exposure time through a pattern mask having a predetermined pattern using a PLA-501F exposure machine (extra high pressure mercury lamp) manufactured by Canon Inc. The film was developed with an aqueous solution of tetramethylammonium hydroxide having the concentration described in No. 2 by a puddle method at 25 ° C. for 80 seconds. Next, running water was washed with ultrapure water for 1 minute and dried to form a pattern on the wafer. The amount of exposure required to completely dissolve the 3.0 μm line-and-space (10 to 1) space pattern was measured. This value is shown in Table 2 as radiation sensitivity (exposure sensitivity). It can be said that the sensitivity is good when this value is 1000 J / m ² or less.

[Evaluation of development margin]
Similarly to the above [Evaluation of Radiation Sensitivity], a coating film was formed on a silicon substrate. Using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc., a mask having a 3.0 μm line and space (10 to 1) pattern was applied to the obtained coating film. Exposure is carried out with an exposure amount corresponding to the value of radiation sensitivity measured in the above [Evaluation of radiation sensitivity], and the solution is obtained by changing the development time with an aqueous tetramethylammonium hydroxide solution having the concentration shown in Table 2 at 25 ° C. Developed by prime method. Next, running water was washed with ultrapure water for 1 minute and dried to form a pattern on the wafer. At this time, the development time necessary for the line width to be 3.0 μm is shown in Table 2 as the optimum development time. Further, when the development was further continued from the optimum development time, the time until the 3.0 μm line pattern was peeled off was measured and shown in Table 2 as a development margin (allowable development time range). When this value is 30 seconds or more, it can be said that the development margin is good.

[Evaluation of solvent resistance]
Similarly to the above [Evaluation of Radiation Sensitivity], a coating film was formed on a silicon substrate. The obtained coating film was heated at 220 ° C. for 1 hour in a clean oven to obtain a cured film. The film thickness (T1) of the obtained cured film was measured. And after immersing the silicon substrate in which this cured film was formed in dimethyl sulfoxide temperature-controlled at 70 degreeC for 20 minutes, the film thickness (t1) of the said cured film was measured, and the film thickness change rate by immersion {| T1-T1 | / T1} × 100 [%] was calculated. The results of the film thickness change rate are shown in Table 2. When this value is 4% or less, it can be said that the solvent resistance is good. In the evaluation of the solvent resistance, the patterning of the film to be formed is unnecessary, so the radiation irradiation step and the development step were omitted, and only the coating film formation step and the heating step were performed for evaluation.

[Evaluation of heat resistance]
A cured film was formed in the same manner as the evaluation of the solvent resistance, and the film thickness (T2) of the obtained cured film was measured. Next, the silicon substrate on which this cured film is formed is additionally baked in a clean oven at 240 ° C. for 1 hour, and then the thickness (t2) of the cured film is measured, and the rate of change in film thickness by additional baking {| t2−T2 | / T2} × 100 [%] was calculated. The results of 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 the glass substrate in the same manner as in the above [Evaluation of solvent resistance] except that a glass substrate “Corning 7059 (manufactured by Corning)” was used instead of the silicon substrate. Using a spectrophotometer "150-20 type double beam (manufactured by Hitachi, Ltd.)", the total light transmittance of the glass substrate having this cured film was measured at a wavelength in the range of 380 to 780 nm. The total light transmittance values are shown in Table 2. When this value is less than 50%, it can be said that the light shielding property is good.

[Evaluation of relative permittivity]
Compositions listed in Table 2 on a polished SUS304 substrate using Examples 11-15, 17-20, and Comparative Examples 5-8 using a spinner, and Example 16 using a slit die coater. Then, it was pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was baked at 220 ° C. for 1 hour in a clean oven to obtain a cured film. About this cured film, the Pt / Pd electrode pattern was formed by the vapor deposition method, and the sample for relative dielectric constant measurement was created. The relative dielectric constant of the sample was measured by the CV method at a frequency of 10 kHz, using an HP16451B electrode and an HP4284A precision LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd. The results of the relative dielectric constant are shown in Table 2. When this value is 3.7 or less, it can be said that the dielectric constant is good. In the evaluation of the dielectric constant, patterning of the film to be formed is unnecessary, so the radiation irradiation step and the development step were omitted, and only the coating film forming step and the heating step were performed for evaluation.

  From the results shown in Table 2, in Examples 11 to 20 using the radiation-sensitive resin compositions prepared in Examples 1 to 10, radiation sensitivity (exposure sensitivity), development margin, solvent resistance, heat resistance It was found that all points of the total light transmittance and the relative dielectric constant were excellent with good balance. In particular, in all of the Examples, a total light transmittance of 45% or less was obtained without using a separate developer, and a remarkably good light shielding property was 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 thermal dye and a developer, less than 50% The total light transmittance of the latter was not obtained, and in particular, the latter total light transmittance was a very high value of 70%. In Comparative Example 7 using a composition containing no low-molecular color developer and containing no thermal dye, a total light transmittance of less than 50% was obtained, but the radiation sensitivity was extremely poor. Furthermore, Comparative Example 8 (in the case of Patent Documents 3 and 4) using a composition that does not contain a phenol skeleton-containing unsaturated compound as a constituent compound of the copolymer, does not contain a thermal dye, and contains a low-molecular developer. However, a total light transmittance of less than 50% was not obtained.

  From the results of these examples and comparative examples, the radiation-sensitive resin composition of the present invention has sufficient developability to form a through-hole or a U-shaped depression in the insulating film, and at the same time with respect to the solvent. It has been found that since it has high resistance and has excellent radiation sensitivity and high light shielding properties, it can be suitably used as a partition wall and an insulating film.

  Since the radiation-sensitive resin composition of the present invention uses a predetermined alkali-soluble resin as a developer, it has heat resistance to high temperatures during the formation of the partition walls and the insulating film, and the sublimation of the developer can be prevented. In addition to excellent radiation sensitivity and developability, high light shielding properties during heating can be obtained. Therefore, the organic EL element provided with the partition and the insulating film formed from such a radiation sensitive resin composition is suitably used as an electronic component of a display device exhibiting good contrast.

Claims (7)

[A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, and (a2) a phenol skeleton-containing unsaturated compound represented by the following formula (I), a compound represented by the following formula (II), and 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 following formula (III):
[B] A partition and a radiation-sensitive resin composition for forming an insulating film containing a 1,2-quinonediazide compound and [C] a thermosensitive dye.

(In Formula (I), R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^{2 to} R ⁶ are the same or different and are 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, in formula (II) , 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 are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and X ^{1 to} X ⁴ are the same or Differently, it is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, Z is a single bond or —O (CH ₂ ) _w —, and w is an integer of 1 to 6. In the formula (III) , ^{R 1} is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Z is a single If or -O _{(CH 2) w} - a and, w is an integer from 1 to 6).   The alkali-soluble resin [A] is a copolymer obtained by copolymerizing a monomer containing an epoxy group-containing unsaturated compound in addition to the components (a1) and (a2). 1. The radiation sensitive resin composition according to 1.   3. The sensation according to claim 1, wherein the content of the thermosensitive dye of the component [C] is 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin of the component [A]. Radiation resin composition.   The partition for organic EL display elements formed from the radiation sensitive resin composition of Claim 1, Claim 2 or Claim 3.   The insulating film for organic EL display elements formed from the radiation sensitive resin composition of Claim 1, Claim 2 or Claim 3. (1) The process of forming the coating film of the radiation sensitive resin composition of Claim 1, Claim 2 or Claim 3 on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A method for forming a partition for an organic EL display element, comprising: a step of developing the coating film irradiated with radiation in step (2); and (4) a step of heating the coating film developed in step (3). (1) The process of forming the coating film of the radiation sensitive resin composition of Claim 1, Claim 2 or Claim 3 on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) The process of developing the coating film irradiated with the radiation in the step (2), and (4) The method of forming the insulating film for organic EL display elements, comprising the step of heating the coating film developed in the step (3) .