JP2014134763A - Radiation-sensitive resin composition, cured film for display element, method for forming cured film for display element, and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition having sufficient resolution and sensitivity, and to provide a cured film for a display element excellent in compressive performance, transmittance, light resistance, voltage retaining ratio, and reduction in dielectric.SOLUTION: A radiation-sensitive resin composition includes: [A] an alkali-soluble resin; [B] a polymerizable compound having an ethylenically unsaturated bond; and [C] at least one selected from photopolymerization initiators represented by formula (1) and (2), respectively.

Description

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

In an electronic component such as a thin film transistor type liquid crystal display element, an interlayer insulating film is generally provided to insulate between wirings arranged in layers, and the upper part of a semiconductor element is flattened in an organic electroluminescence element. A flattening film is provided for stacking the electrode and the light emitting layer on the flattening film.
For example, a thin film transistor type liquid crystal display element is manufactured through a process of forming a transparent electrode film on an interlayer insulating film and further forming a liquid crystal alignment film thereon. For this reason, the interlayer insulating film is exposed to high temperature conditions in the transparent electrode film forming process or exposed to a resist stripping solution used for electrode pattern formation. Solvent properties are required.

As a conventional interlayer insulating film for liquid crystal display elements, a positive radiation sensitive resin composition using an acid generator such as naphthoquinonediazide is used from the viewpoint of patterning performance (see JP-A-2001-354822). ).
In recent years, attention has been paid to the high sensitivity of the negative radiation-sensitive resin composition and the performance such as the high light transmittance of the resulting cured film, and the application of the negative radiation-sensitive resin composition is progressing (Japanese Patent Laid-Open No. 2000-162769). No. publication).
In recent years, TFT-type liquid crystal display elements have been in the trend of larger screens, higher brightness, higher definition, faster response, thinner thickness, etc., and the composition for forming an interlayer insulating film used therefor has high sensitivity. In addition, the interlayer insulating film to be formed is required to have higher performance than ever in terms of low dielectric constant and high transmittance.

On the other hand, among members used for liquid crystal display elements, many spacers, protective films, coloring patterns for color filters, and the like are formed using a negative radiation-sensitive resin composition (Japanese Patent Laid-Open No. 6-43643). reference). In recent years, liquid crystal display devices have been required to have larger screens, higher brightness, thinner thickness, etc. From the viewpoint of shortening process time and cost, high sensitivity and high sensitivity of negative radiation sensitive resin compositions are required. Resolution is required.
As countermeasures for shortening the above process time, techniques of radiation-sensitive resin compositions containing an oxime ester photopolymerization initiator have been studied (Japanese Patent Application Laid-Open No. 2005-227525, WO2008 / 077866, WO2009 / 081483). See the official gazette). However, many of these photopolymerization initiators have a maximum absorption in the visible region, and the photopolymerization initiator itself is often slightly reddish. When a cured film is formed using such a conventional photopolymerization initiator, the cured film also exhibits a slightly red color, and the light transmittance decreases, so that it may not be applicable to some liquid crystal display elements and organic electroluminescence elements. is there.

  Under such circumstances, a radiation-sensitive resin composition having sufficient resolution and sensitivity, and a display excellent in compression performance, transmittance, light resistance, voltage holding ratio, low dielectric constant, development resistance, heat resistance and solvent resistance. Development of a cured film for an element is desired.

JP 2001-354822 A JP 2000-162769 A JP-A-6-43643 JP 2005-227525 A WO2008 / 078686 Publication WO2009 / 081483

  The present invention has been made based on the circumstances as described above, and its purpose is to provide a radiation-sensitive resin composition having sufficient resolution and sensitivity, as well as compression performance, transmittance, light resistance, voltage holding ratio, low It is to provide a cured film for a display element which is excellent in dielectric constant, development resistance, heat resistance and solvent resistance.

The invention made to solve the above problems is
[A] alkali-soluble resin,
[B] a polymerizable compound having an ethylenically unsaturated bond (hereinafter also referred to as “[B] polymerizable compound”),
[C] A radiation-sensitive resin composition containing at least one selected from photopolymerization initiators represented by the following formula (1) or formula (2) (hereinafter also referred to as “[C] photopolymerization initiator”). Achieved by things.

(In Formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, carbon, An arylalkyl group represented by Formula 7 to 30. R ¹ and R ² may be bonded to each other to form a fluorene group.
R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a complex having 4 to 20 carbon atoms. A ring group is shown. X represents a direct bond or a carbonyl group.

In formula (2), R ¹ , R ² , R ³ or R ⁴ has the same definition as in formula (1).
R ⁵ represents R ⁶ , OR ⁶ , SR ⁶ , COR ⁶ , CONR ⁶ R ⁶ , NR ⁶ COR ⁶ , OCOR ⁶ , COOR ⁶ , SCOR ⁶ , OCSR ⁶ , COSR ⁶ , CSOR ⁶ , CN, halogen, hydroxyl group Show.
R ⁶ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms. X represents a direct bond or a carbonyl group. a is an integer of 0-4. )
The radiation-sensitive resin composition contains [A] alkali-soluble resin, [B] polymerizable compound, the above-mentioned specific amount of [C] photopolymerization initiator, [D] compound, [E] compound, and the like. The radiation-sensitive resin composition can easily form a fine and elaborate pattern by exposure and development utilizing radiation sensitivity, and has sufficient resolution and sensitivity. In addition, the radiation-sensitive resin composition contains a specific amount of the [C] photopolymerization initiator having the above specific structure, so that it is excellent in compression performance, transmittance, light resistance, voltage holding ratio and the like. A film can be formed. Furthermore, the radiation sensitive resin composition contains a [D] compound (compound containing a hindered phenol structure), so that the radiation sensitive resin composition has improved light resistance and heat resistance. A cured film can be formed.

[A] The alkali-soluble resin is
(A1) a structural unit having a carboxyl group (hereinafter also referred to as “(a1) structural unit”),
It is preferable to include a copolymer containing a structural unit (a2) having a polymerizable group (hereinafter also referred to as “(a2) structural unit”).

  [A] When the alkali-soluble resin contains the (a1) structural unit, a radiation-sensitive resin composition that optimizes solubility in an aqueous alkali solution and is excellent in radiation sensitivity can be obtained. Moreover, [A] alkali-soluble resin can improve the heat resistance and light resistance of the cured film for display elements obtained by including (a2) structural unit with (a1) structural unit.

[A] The copolymer having a structural unit containing at least one group selected from an oxiranyl group, an oxetanyl group and a (meth) acryloyl group as the polymerizable group of the structural unit (a2) of the alkali-soluble resin. Is preferred. The curability and the like of the obtained cured film for display element can be further improved.
The radiation sensitive resin composition of the present invention is further selected from the group consisting of [D] a compound containing a hindered phenol structure, a compound containing a hindered amine structure, a compound containing an alkyl phosphite structure, and a compound containing a thioether structure. A seed | species or 2 or more types of compounds (henceforth a [D] compound) can be included.
By including the [D] compound, it is possible to achieve both high sensitivity and resolution at the time of pattern formation of the resulting pattern.

  [C] It is preferable that the usage-amount of a photoinitiator is the range of 0.1-10 mass parts with respect to 100 mass parts of [A] alkali-soluble resin. [C] By making the usage-amount of a photoinitiator into the said range, it becomes possible to make compatible the sensitivity at the time of pattern formation, and the transmittance | permeability of the film | membrane obtained at a high level.

[B] The polymerizable unsaturated compound is particularly preferably a polymerizable unsaturated compound having a hydroxyl group or a carboxyl group. By using a polymerizable unsaturated compound having a hydroxyl group or a carboxyl group, both the developability during pattern formation and the heat resistance and solvent resistance of the resulting cured film can be achieved at a high level.
Furthermore, the radiation sensitive resin composition of the present invention includes [E] thioxanthone compound, acetophenone compound, biimidazole compound, triazine compound, O-acyl oxime compound (other than [C] photopolymerization initiator), thiol. It can contain at least 1 type, or 2 or more types of compounds (henceforth a [E] compound) selected from the group which consists of a system type compound.
By including the [E] compound, it is possible to achieve both sensitivity and resolution at the time of pattern formation at a high level.

  The radiation-sensitive resin composition is preferable for forming a cured film for a display element. Moreover, the display element provided with the cured film for display elements formed from the said radiation sensitive resin composition and this cured film for display elements is suitably contained in this invention.

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

  According to the forming method of the present invention, it is possible to form a cured film for a display element that is excellent in compression performance, transmittance, light resistance, low dielectric constant, voltage holding ratio, and the like.

  The “radiation” of the “radiation-sensitive resin composition” in the present specification is a concept including visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like.

  As described above, the radiation-sensitive resin composition of the present invention can easily form a fine and elaborate pattern, and has sufficient resolution and sensitivity. Moreover, the said radiation sensitive resin composition can form the cured film for display elements which is excellent in compression performance, the transmittance | permeability, light resistance, a voltage holding rate, etc. Therefore, the radiation-sensitive resin composition includes a protective film for color filters for display elements, spacers, interlayer insulating films for arrays, color filters for color separation of solid-state imaging elements, color filters for organic electroluminescence display elements, electronic paper, etc. It is suitable for a color filter for flexible display, a protective film for touch panel, a resist for photofabrication used for forming metal wiring and metal bumps, processing a substrate, and the like.

<Radiation sensitive resin composition>
The radiation sensitive resin composition of the present invention contains [A] an alkali-soluble resin, [B] a polymerizable compound, and [C] a photopolymerization initiator. Moreover, the said radiation sensitive resin composition can contain a [D] compound and a [E] compound as a suitable component. Furthermore, the said radiation sensitive resin composition may contain another arbitrary component, unless the effect of this invention is impaired. Hereinafter, each component will be described in detail.
<[A] alkali-soluble resin>
[A] The alkali-soluble resin is not particularly limited as long as it is an alkali-dissociating resin, but is preferably a resin containing (a1) structural unit and (a2) structural unit. In addition, [A] alkali-soluble resin may contain other structural units other than (a1) structural unit and (a2) structural unit, unless the effect of this invention is impaired.

[A] The alkali-soluble resin can be synthesized by radical polymerization of a compound giving each structural unit in the presence of a polymerization initiator in a solvent. Hereinafter, the compound which gives each structural unit is explained in full detail. In addition, these compounds may use 2 or more types together.
[(A1) Structural unit]
(A1) The structural unit is at least one structural unit selected from the group consisting of a structural unit derived from an unsaturated carboxylic acid and a structural unit derived from an unsaturated carboxylic acid anhydride. (A1) Examples of compounds that give structural units include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids, both terminals Examples thereof include mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group, unsaturated polycyclic compounds having a carboxy group, and anhydrides thereof.

  Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like. As an anhydride of unsaturated dicarboxylic acid, the anhydride of the compound illustrated as said dicarboxylic acid etc. are mentioned, for example. Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], and the like. It is done. Examples of the mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends include ω-carboxypolycaprolactone mono (meth) acrylate. Examples of unsaturated polycyclic compounds 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, 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] hept-2-ene anhydride and the like.

  Of these, monocarboxylic acid and dicarboxylic acid anhydrides are preferred, and (meth) acrylic acid and maleic anhydride are more preferred from the viewpoints of copolymerization reactivity, solubility in alkaline aqueous solutions, and availability.

[A] The content ratio of the (a1) structural unit in the alkali-soluble resin is preferably 5 mol% to 30 mol%, more preferably 10 mol% to 25 mol%, based on all structural units. (A1) A radiation-sensitive resin composition that optimizes the solubility of the alkali-soluble resin in an alkaline aqueous solution and has excellent radiation sensitivity by adjusting the content ratio of the structural unit to 5 mol% to 30 mol%. can get.
[(A2) Structural unit]
(A2) The structural unit is a structural unit having a polymerizable group. Examples of the polymerizable group include an oxiranyl group (1,2-epoxy structure), an oxetanyl group (1,3-epoxy structure), a (meth) acryloyl group, and a vinyl group. Of these, oxiranyl group, oxetanyl group, and (meth) acryloyl group are preferable from the viewpoint of improving heat resistance and light resistance.

The structural unit having an oxiranyl group (hereinafter also referred to as (a2-1) structural unit) represents a structural unit obtained by polymerizing an unsaturated compound having an oxiranyl group.
Specific examples of the unsaturated compound having an oxiranyl group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid. -3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl O-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, and the like.

The structural unit having an oxetanyl group (hereinafter also referred to as (a2-2) structural unit) represents a structural unit obtained by polymerizing an unsaturated compound having an oxetanyl group. Examples of the unsaturated compound having an oxetanyl group include 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- ( (Acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2, 2-difluorooxetane, 3- (acryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-acryloyloxy) Ethyl) oxetane, 3- 2-acryloyloxyethyl) -2-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (2-acryloyl) Oxyethyl) -2-pentafluoroethyloxetane, 3- (2-acryloyloxyethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) -2,2-difluorooxetane, 3- (2-acryloyloxy) Ethyl) -2,2,4-trifluorooxetane, 3- (2-acryloyloxyethyl) -2,2,4,4-tetrafluorooxetane and other acrylic acid esters;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) 2-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (2-methacryloyloxyethyl) -2- Pentafluoroethyloxetane, 3- (2-methacryloyloxyethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) -2,2-difluorooxetane, 3- (2-methacryloyloxyethyl) -2,2 , 4-trifluorooxetane, methacrylic acid esters such as 3- (2-methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane, and the like.

  Among these unsaturated compounds having an oxiranyl group and unsaturated compounds having an oxetanyl group, glycidyl methacrylate, 2-methylglycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzylglycidyl ether, m- Vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, 3- (methacryloyloxymethyl) -3-ethyloxetane are copolymerization reactivity, compression performance of cured film for display element, light resistance It is preferable from the viewpoint of improvement.

[A] The content ratio of the (a2-1) structural unit or the (a2-2) structural unit in the alkali-soluble resin is preferably 5 mol% to 60 mol%, more preferably 10 mol, based on all structural units. % To 50 mol%. By setting the content ratio of (a2-1) structural unit or (a2-2) structural unit to 5 mol% to 60 mol%, a cured film for display element having excellent curability and the like can be formed.
The structural unit having a (meth) acryloyl group (hereinafter also referred to as (a2-3) structural unit) is a structural unit represented by the following formula (3). In the following formula (3), R ⁷ and R ⁸ are a hydrogen atom or a methyl group. R ⁹ is a group represented by the above formula (4-1) or formula (4-2). n is an integer of 1 to 6. In formula (4-1), R ¹⁰ represents a hydrogen atom or a methyl group. In formula (4-1) and formula (4-2), * represents a site bonded to the oxygen atom in formula (3).

(In formula (3), R ⁷ and R ⁸ are a hydrogen atom or a methyl group. R ⁹ is a group represented by the above formula (4-1) or formula (4-2). It is an integer from 1 to 6.

In formula (4-1), R ¹⁰ represents a hydrogen atom or a methyl group. In formula (4-1) and formula (4-2), * represents a site bonded to the oxygen atom in formula (3). )
(A2-3) The structural unit is such that the carboxy group in the structural unit (a1) reacts with the unsaturated compound having the oxiranyl group forming the structural unit (a2-1) to form an ester bond. Is obtained. For example, when a copolymer having (a1) a structural unit is reacted with a compound such as glycidyl methacrylate or 2-methylglycidyl methacrylate that gives the structural unit (a2-1) R ⁹ in the above formula (3) is a group represented by the above formula (4-1). On the other hand, when a compound such as (a4) structural unit is reacted with a compound such as 3,4-epoxycyclohexylmethyl methacrylate, R ⁹ in the above formula (3) is represented by the above formula (4-2). It becomes the basis.

The (a2-3) structural unit can be obtained by reacting a hydroxyl group-containing polymer with an unsaturated isocyanate compound.

  Examples of the unsaturated isocyanate compound include (meth) acrylic acid derivatives. Specific examples thereof include 2- (meth) acryloyloxyethyl isocyanate, 4- (meth) acryloyloxybutyl isocyanate, (meth ) 2- (2-isocyanatoethoxy) ethyl acrylate and the like. As these commercial products, Karenz AOI (manufactured by Showa Denko KK) as a commercial product of 2-acryloyloxyethyl isocyanate, Karenz MOI (manufactured by Showa Denko KK), methacryl As a commercial product of the acid 2- (2-isocyanatoethoxy) ethyl, Karenz MOI-EG (manufactured by Showa Denko KK) can be mentioned.

  Of these unsaturated isocyanate compounds, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 4-methacryloyloxybutyl isocyanate or 2- (2-methacrylic acid) is selected from the viewpoint of reactivity with a polymer having a hydroxyl group. Isocyanatoethoxy) ethyl is preferred. An unsaturated isocyanate compound can be used individually or in mixture of 2 or more types.

The reaction between the hydroxyl group-containing polymer and the unsaturated isocyanate compound is carried out in the presence of a suitable catalyst as necessary, preferably in a polymer solution containing a polymerization inhibitor, while stirring at room temperature or under heating. This can be carried out by introducing an unsaturated isocyanate compound. Examples of the catalyst include di-n-butyltin (IV) dilaurate; and examples of the polymerization inhibitor include p-methoxyphenol.
(A2-3) The proportion of the unsaturated isocyanate compound used in producing the polymer having a structural unit is preferably 0.1 to 95 mol%, more preferably 1 with respect to the hydroxyl group in the polymer. It is 0.0-80 mol%, Most preferably, it is 5.0-75 mol%. When the use ratio of the unsaturated isocyanate compound is 0.1 to 95 mol%, the reactivity with the polymer, the heat resistance and the elastic properties of the resulting cured film are further improved, which is preferable.

  In addition, as [A] alkali-soluble resin, (a1) structural unit and (a2-1) structural unit or (a2-2) structural unit resin, (a1) structural unit and (a2-3) structural unit You may mix with resin containing.

[Other structural units]
[A] Examples of the compound that gives other structural units other than (a1) structural unit and (a2) structural unit, which may be included as long as the effect of the present invention is not impaired by the alkali-soluble resin, include, for example, a hydroxyl group (meta ) Acrylic acid ester, (meth) acrylic acid chain alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated aromatic compound, conjugated diene, unsaturated compound having tetrahydrofuran skeleton, etc. Can be mentioned.

  Examples of the (meth) acrylic acid ester having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate, and methacrylate. Examples include 2-hydroxyethyl acid, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate, and the like.

  Examples of the (meth) acrylic acid chain alkyl ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, N-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, acrylic acid Examples include isodecyl, n-lauryl acrylate, tridecyl acrylate, and n-stearyl acrylate.

  Examples of the (meth) acrylic acid cyclic alkyl ester include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.02,6] decan-8-yl methacrylate, and tricyclomethacrylate [5. 2.1.02,6] decan-8-yloxyethyl, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.02,6] decan-8-yl acrylate, tricyclo [ 5.2.1.02,6] decan-8-yloxyethyl acrylate, isobornyl acrylate and the like.

  Examples of the (meth) acrylic acid aryl ester include phenyl methacrylate, benzyl methacrylate, phenyl acrylate, and benzyl acrylate.

  Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, N-phenylmaleimide, N-cyclohexylmaleimide, and N-tolyl. Maleimide, N-naphthylmaleimide, N-ethylmaleimide, N-hexylmaleimide, N-benzylmaleimide and the like can be mentioned. Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

  Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like.

  [A] Examples of the solvent used in the polymerization reaction for synthesizing the alkali-soluble resin include alcohol, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, and propylene glycol. Examples thereof include monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, ketone and ester.

  [A] As the polymerization initiator used in the polymerization reaction for synthesizing the alkali-soluble resin, those generally known as radical polymerization initiators can be used. Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-). 2,4-dimethylvaleronitrile) and the like.

  [A] In the polymerization reaction for producing the alkali-soluble resin, a molecular weight modifier can be used to adjust the molecular weight. Examples of the molecular weight modifier 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; Examples thereof include xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide; terpinolene and α-methylstyrene dimer.

[A] As a weight average molecular weight (Mw) of alkali-soluble resin, 1,000-30,000 are preferable and 5,000-20,000 are more preferable. [A] By making Mw of alkali-soluble resin into the said specific range, the sensitivity and developability of the said radiation sensitive resin composition can be improved. In addition, Mw and number average molecular weight (Mn) of the polymer in this specification were measured by gel permeation chromatography (GPC) under the following conditions.
Apparatus: GPC-101 (Showa Denko)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 combined with mobile phase: tetrahydrofuran Column temperature: 40 ° C.
Flow rate: 1.0 mL / min Sample concentration: 1.0 mass%
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene <[B] polymerizable compound>
[B] The polymerizable compound contained in the radiation-sensitive resin composition is not particularly limited as long as it is a polymerizable compound having an ethylenically unsaturated bond. For example, ω-carboxypolycaprolactone mono (meth) acrylate , Ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene Glycol di (meth) acrylate, bisphenoxyethanol full orange (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, 2- (2′-vinyl) Xyloxy) ethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate In addition to tri (2- (meth) acryloyloxyethyl) phosphate, ethylene oxide-modified dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, etc., it has a linear alkylene group and an alicyclic structure, and Ureta obtained by reacting a compound having two or more isocyanate groups with a compound having one or more hydroxyl groups in the molecule and having 3 to 5 (meth) acryloyloxy groups (Meth) acrylate compounds, and the like.

[B] The polymerizable compound is preferably a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate.
Furthermore, as the polymerizable unsaturated compound having a hydroxyl group or a carboxyl group, dipentaerythritol penta (meth) acrylate or succinic acid-modified pentaerythritol triacrylate is preferable. By including these polymerizable unsaturated compounds having a hydroxyl group or a carboxyl group, the developability at the time of pattern formation and the heat resistance and solvent resistance of the resulting cured film can be achieved at a high level.

[B] Examples of commercially available polymerizable compounds include:
Aronix M-400, M-402, M-405, M-450, M-1310, M-1600, M-1960, M-7100, M-8030, M-8060, M-8100, M-8530, M-8560, M-9560, M-9050, Aronix TO-756, TO-1450, TO-1382 (above, Toagosei Co., Ltd.);
KAYARAD DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, MAX-3510 (above, Nippon Kayaku Co., Ltd.);
Viscoat 295, 300, 360, GPT, 3PA, 400, 802 (Osaka Organic Chemical Industries, Ltd.);
As a urethane acrylate compound, New Frontier R-1150 (Daiichi Kogyo Seiyaku Co., Ltd.);
KAYARAD DPHA-40H, UX-5000 (Nippon Kayaku Co., Ltd.);
UN-9000H (Negami Kogyo Co.);
Aronix M-5300, M-5600, M-5700, M-210, M-220, M-240, M-270, M-6200, M-305, M-309, M M-310, M-315 (above, Toagosei Co., Ltd.);
KAYARAD HDDA, KAYARAD HX-220, HX-620, R-526, R-167, R-604, R-684, R-551, R-712, UX-2201, UX-2301 UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (above, Nippon Kayaku Co., Ltd.);
Art Resin UN-9000PEP, UN-9200A, UN-7600, UN-333, UN-1003, UN-1255, UN-6060PTM, UN-6060P (Negami Industrial Co., Ltd.);
SH-500B biscoat 260, 312 and 335HP (above, Osaka Organic Chemical Industry Co., Ltd.).

[B] A polymeric compound can be used individually or in mixture of 2 or more types. As content of the [B] polymeric compound in the said radiation sensitive resin composition, 10 mass parts-700 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 20 mass parts-600 mass parts. Is more preferable. [B] By setting the content of the polymerizable compound in the above specific range, the radiation-sensitive resin composition is a cured film for a display element having sufficient light resistance, heat resistance, and voltage holding ratio even at a low exposure amount. Can be formed.
<[C] Photopolymerization initiator>
[C] The photopolymerization initiator is a photopolymerization initiator represented by the above formula (1) or formula (2), and the content of the [C] photopolymerization initiator in the radiation-sensitive resin composition is: [A] It is 0.1 mass part or more and 10 mass parts or less with respect to 100 mass parts of alkali-soluble resin. The radiation-sensitive resin composition contains a specific amount of the [C] photopolymerization initiator having the above specific structure, so that it is excellent in compression performance, transmittance, light resistance, low dielectric constant, voltage holding ratio, etc. A cured film for an element can be formed.

In the above formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, carbon An arylalkyl group of formula 7 to 30 is shown. R ¹ and R ² may be bonded to each other to form a fluorene group.
R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a complex having 4 to 20 carbon atoms. A ring group is shown. X represents a direct bond or a carbonyl group.

In said formula (2), R < ¹ >, R < ² >, R < ³ > or R < ⁴ > is the same as the definition in Formula (1).
R ⁵ represents R ⁶ , OR ⁶ , SR ⁶ , COR ⁶ , CONR ⁶ R ⁶ , NR ⁶ COR ⁶ , OCOR ⁶ , COOR ⁶ , SCOR ⁶ , OCSR ⁶ , COSR ⁶ , CSOR ⁶ , CN, halogen, hydroxyl group Show.
R ⁶ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms. X represents a direct bond or a carbonyl group. a is an integer of 0-4.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t -Butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-dodecyl group and the like can be mentioned.

Examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R ¹ and R ² include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a bornyl group, a norbornyl group, an adamantyl group, and the like. Is mentioned.
As an aryl group having 6 to 30 carbon atoms. A phenyl group, a naphthyl group, a tolyl group, a xylyl group, etc. are mentioned. In the case of phenyl groups, they may be bonded to each other to form a fluorene group.
Examples of the arylalkyl group having 7 to 30 carbon atoms include a benzyl group and a phenethyl group.

C 1-20 alkyl group represented by R ³ , R ⁴ and R ⁶ , C 4-20 alicyclic hydrocarbon group, C 6-30 aryl group, C 7-30 carbon group The arylalkyl group is the same as in R ¹ and R ² .
Examples of the heterocyclic group having 4 to 20 carbon atoms include a 2-furyl group, a furfuryl group, a 2-thienyl group, a 2-thenyl group, a 2-thenoyl group, a 2-pyrrolyl group, a 2-pyridyl group, a piperidino group, A tetrahydrofuryl group, a tetrahydrofurfuryl group, a tetrahydrofuranyl group, etc. are mentioned.

In the above formula (1) or formula (2), R ¹ and R ² are methyl group, ethyl group, n-propyl group, i-propyl, n-hexyl, n-octyl, n-dodecyl group, cyclohexyl, respectively. Group, phenyl group, fluorene group, R ³ is a methyl group, ethyl group, phenyl group, tolyl group, xylyl group, R ⁴ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ⁴ is methyl group. It is preferably a group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.
[C] By making a photoinitiator into the said specific compound, the sensitivity and solubility of the [C] photoinitiator to a radiation sensitive resin composition can be improved.

  [C] Examples of the photopolymerization initiator include compounds represented by the following formulas (C-1) to (C-12).

[C] The content of the photopolymerization initiator is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the [A] alkali-soluble resin. . [C] By setting the content of the photopolymerization initiator in the above specific range, the sensitivity of the radiation-sensitive composition and the light resistance, compression performance, sensitivity, and low dielectric constant of the resulting cured film for display element are further reduced. Can be improved.
<[D] Compound>
[D] The compound is at least one compound selected from the group consisting of a compound containing a hindered phenol structure, a compound containing a hindered amine structure, a compound containing a phosphite structure, and a compound containing a thioether structure. When the radiation sensitive resin composition contains the [D] compound, a cured film for a display element with improved light resistance and heat resistance can be formed. This is because the [D] compound can suppress molecular cleavage of the [A] alkali-soluble resin by capturing radicals generated during exposure, heating, etc., or by decomposing a peroxide generated by oxidation. This is presumed to be due to this. In addition, since the [D] compound is a compound containing the said structure, even if the said radiation sensitive resin composition contains this [D] compound, the high sensitivity with respect to a radiation is maintained, and the hardening for display elements obtained There is little decrease in transmittance and voltage holding ratio of membranes and the like.

  Examples of the compound containing a hindered phenol structure include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-). tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) ) Isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide), 3,3 ′ 3 ", 5,5 ', 5" -hexa-tert-butyl-a, a', a "-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthio) Methyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], Hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) Methyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1 , 3, -Triazin-2-ylamine) phenol, 2,5-di-tert-butylhydroquinone, etc. Among these, as a compound containing a hindered phenol structure, pentaerythritol tetrakis [3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate] 2,5-di-tert-butylhydroquinone, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene is preferred.

  As a commercial item of the compound containing a hindered phenol structure, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330 (above, ADEKA), Sumizer GM, Sumizer GS, Sumizer MDP-S, Sumizer BBM-S, Sumizer WX-R, Sumizer Z-80, IR13 NOX, NOGA, IRNOX IRGANOX1726, IRGANOX1425WL, IRG NOX1520L, IRGANOX245, IRGANOX259, IRGANOX3114, IRGANOX565, IRGAMOD295 (above, Ciba Japan), Yoshinox BHT, Yoshinox BB, Yoshinox 2246G, Yoshinox 425, Yoshinox T17, Yoshinox T17, Yoshinox T17, Yoshinox T17, Yoshinox T17 , API Corporation) and the like.

Examples of the compound containing a hindered amine structure include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6) -Pentamethyl-4-piperidyl) 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acryloyl- , 2,6,6-tetramethyl-4-piperidyl) 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1,2,2, 6,6-pentamethyl-4-piperidyl) decandioate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionyloxy] -1- [2- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl -2- (2,2,6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6 6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetra Compounds such as carboxylates;
N, N ′, N ″, N ′ ″-tetrakis- [4,6-bis- [butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino]- Triazin-2-yl] -4,7-diazadecane-1,10-diamine, dibutylamine and 1,3,5-triazine.N, N′-bis (2,2,6,6-tetramethyl-4- Piperidyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, dibutylamine, 1,3,5-triazine and N, N Polycondensate with '-bis (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{(1,1,3,3-tetramethylbutyl) amino-1,3,5- Triazine-2,4-diyl} {(2,2,6,6-tetramethyl- -Piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] and 1,6-hexanediamine-N, N′-bis (2,2,6,6- Polycondensation product of tetramethyl-4-piperidyl) and morpholine-2,4,6-trichloro-1,3,5-triazine, poly [(6-morpholino-s-triazine-2,4-diyl) [ Piperidine rings such as (2,2,6,6-tetramethyl-4-piperidyl) imino] -hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] have a triazine skeleton. A plurality of high molecular weight HALS bonded to each other through a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 1,2,3,4-butanetetracarboxylic acid and , 2,2,6,6-Pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane And a polymer such as a compound in which a piperidine ring is bonded via an ester bond. Of these, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate is preferred as the compound containing a hindered amine structure.

  Examples of commercially available compounds containing a hindered amine structure include ADK STAB LA-52, ADK STAB LA57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63P, ADK STAB LA-68LD, ADK STAB LA-77 and ADK STAB LA-82. ADEKA STAB LA-87 (above, ADEKA), sumizer 9A (Sumitomo Chemical), CHIMASSORB119FL, CHIMASSORB2020FDL, CHIMASSORB944FDL, TINUVIN622LD, TINUVIN144, TINUVIN765, TINUVIN770DF, etc.

  Examples of the compound containing a phosphite structure include tris (nonylphenyl) phosphite, tris (p-tert-octylphenyl) phosphite, tris [2,4,6-tris (α-phenylethyl)] phosphite, Tris (p-2-butenylphenyl) phosphite, bis (p-nonylphenyl) cyclohexyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, di (2,4-di-tert- Butylphenyl) pentaerythritol diphosphite, 2,2′-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus, distearyl pentaerythritol diphosphite, 4, 4'-isopropylide-diphenol alkyl phosphite, teto Tridecyl-4,4′-butylidene-bis (3-methyl-6-tert-butylphenol) diphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenephosphite, 2,6- Di-tert-butyl-4-methylphenyl phenyl pentaerythritol diphosphite, 2,6-tert-butyl-4-methylphenyl phenyl pentaerythritol diphosphite, 2,6-di-tert-butyl- 4-ethylphenyl stearyl pentaerythritol diphosphite, di (2,6-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,6-di-tert-amyl-4-methylphenyl phenyl・ Pentaerythritol diphosphite The Among these, compounds containing a phosphite structure include 2,2′-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus, distearyl pentaerythritol diphos. Fight is preferred.

  Examples of commercially available compounds containing a phosphite structure include, for example, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, Examples include ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010, ADK STAB TPP (hereinafter referred to as ADEKA), and IRGAFOS 168 (BASF).

  Examples of the compound containing a thioether structure include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (3-lauryl thiopropionate) Pentaerythritol tetrakis (3-octadecyl thiopropionate), pentaerythritol tetrakis (3-myristyl thiopropionate), pentaerythritol tetrakis (3-stearyl thiopropionate), and the like. Among these, pentaerythritol tetrakis (3-lauryl thiopropionate) is preferable as the compound containing a thioether structure.

  Examples of commercially available compounds containing a thioether structure include, for example, ADK STAB AO-412S, ADK STAB AO-503 (above, ADEKA), SUMIZER TPL-R, SUMIZER TPM, SUMIZER TPS, SUMIZER TP-D, SUMIZER CHEMICAL, and SUMITOMO CHEMICAL IRGANOXPS800FD, IRGANOXPS802FD (BASF), DLTP, DSTP, DMTP, DTTP (above, API Corporation) and the like.

  [D] A compound can be used individually or in mixture of 2 or more types. As content of the [D] compound in the said radiation sensitive resin composition, 0.01 mass part or more and 10 mass parts or less are preferable with respect to 100 mass parts of [A] polymers, and 0.1 mass part or more and 5 or less. Less than the mass part is more preferable. [D] By making content of a compound into the said range, the light resistance and heat resistance of the cured film for display elements formed from the said radiation sensitive resin composition can be improved effectively.

[D] A compound is a compound containing the said hindered phenol structure, and content of this [D] compound is 0.01 mass part or more and 10 mass parts or less with respect to 100 mass parts of [A] alkali-soluble resin. It is preferable that In the radiation-sensitive resin composition, the [D] compound is the above compound, and the light resistance and heat resistance of the cured film for a display element to be formed can be further increased by containing the compound in the specific amount. .
<[E] compound>
The said radiation sensitive resin composition may contain a [E] compound individually or in 2 types or more. The [E] compound can be used in combination with the [C] photopolymerization initiator to form a more preferable pattern, for example, as a spacer shape, and [C] exhibits a sensitizing action depending on the type of the photopolymerization initiator. You can also. In the case of an interlayer insulating film, the adhesion between the substrate and the interlayer insulating film can be improved.

  Examples of the compound [E] include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds. Examples thereof include compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds and the like. Among these, the [E] compound preferably contains at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds. .

  Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone. 2,4-diisopropylthioxanthone and the like.

  Examples of acetophenone compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl). ) Butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 , 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole and the like. In addition, when using a biimidazole-type compound as a photoinitiator, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. The hydrogen donor means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In the present invention, hydrogen donors can be used alone or in combination of two or more, but one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable in that the sensitivity can be further improved.

  Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5- Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s -Triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyrene) Le) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n- butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine.

  Examples of the O-acyloxime compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), and ethanone-1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H- Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like.

[E] As content of a compound, 0.01 mass part-60 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 1 mass part-55 mass parts are more preferable. [E] By making content of a compound into the said specific range, hardening by exposure is fully obtained and adhesiveness with a board | substrate can be ensured appropriately.
<Other optional components>
In addition to [A] alkali-soluble resin, [B] polymerizable compound, [C] photopolymerization initiator, [D] compound, and [E] compound, the radiation-sensitive resin composition impairs the effects of the present invention. If necessary, other optional components such as [F] adhesion assistant, [G] surfactant, [H] epoxy compound, [I] storage stabilizer may be contained. These other optional components may be used alone or in combination of two or more. Hereinafter, each component will be described in detail.
[[F] Adhesion aid]
[F] The adhesion assistant can be used to improve the adhesion between the obtained cured film and the substrate. [F] As the adhesion assistant, a functional silane coupling agent having a reactive functional group such as a carboxy group, a methacryloyl group, a vinyl group, an isocyanate group, or an oxiranyl group is preferable. For example, trimethoxysilylbenzoic acid, γ- Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Etc.

[F] The content of the adhesion assistant is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less with respect to 100 parts by mass of [A] alkali-soluble resin. [F] When the content of the adhesion assistant exceeds 20 parts by mass, there is a tendency that development residue is likely to occur.
[[G] Surfactant]
[G] Surfactant can be used in order to further improve the film-forming property of the radiation sensitive resin composition. [G] Examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant.

  As the fluorosurfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of the terminal, main chain and side chain is preferable. Commercially available fluorosurfactants include, for example, Footent FT-100, -110, -140A, -150, -250, -251, -300, -310, -400S. , Fantient FTX-218, and -251 (above, Neos).

  Commercially available silicone surfactants include, for example, Tore Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (above, Toray Dow Corning Silicone).

[G] As content of surfactant, [A] 1.0 mass part or less is preferred to 100 mass parts of alkali-soluble resin, and 0.7 mass part or less is more preferred. [G] When the content of the surfactant exceeds 1.0 part by mass, film unevenness is likely to occur.
[[H] epoxy compound]
The said radiation sensitive resin composition can contain a [H] epoxy compound. Examples of the [H] epoxy compound include compounds having two or more 3,4-epoxycyclohexyl groups in one molecule.

  Examples of the compound having two or more 3,4-epoxycyclohexyl groups in one molecule include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate and bis (3,4-epoxycyclohexylmethyl). ) Adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, methylenebis (3 4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), lactone-modified 3,4-epoxycyclohexyl Methyl-3 ', 4'-epoxycyclohexane carboxylate and the like.

As other [H] epoxy compounds, for example,
Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, Diglycidyl ethers of bisphenol compounds such as brominated bisphenol F diglycidyl ether and brominated bisphenol S diglycidyl ether;
Polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether Glycidyl ether;
Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;
Phenol novolac type epoxy resin;
Cresol novolac type epoxy resin;
Polyphenol type epoxy resin;
Cycloaliphatic epoxy resin;
Diglycidyl esters of aliphatic long-chain dibasic acids;
Glycidyl esters of higher fatty acids;
Examples include epoxidized soybean oil and epoxidized linseed oil.

[H] Examples of commercially available epoxy compounds include:
As a bisphenol A type epoxy resin, Epicoat 604, 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (above, Japan Epoxy Resin Co., Ltd.) and the like;
As bisphenol F type epoxy resin, Epicoat 807 (Japan Epoxy Resin Co., Ltd.) and the like;
As a phenol novolak type epoxy resin, Epicoat 152, 154, 157S65 (above, Japan Epoxy Resin Co., Ltd.), EPPN 201, 202 (above, Nippon Kayaku Co., Ltd.), etc .;
As cresol novolac type epoxy resin, EOCN102, 103S, 104S, 1020, 1025, 1027 (Nippon Kayaku Co., Ltd.), Epicoat 180S75 (Japan Epoxy Resin Co., Ltd.) and the like;
As polyphenol type epoxy resin, Epicoat 1032H60, XY-4000 (above, Japan Epoxy Resin Co., Ltd.) and the like;
Cyclic aliphatic epoxy resins include CY-175, 177, 179, Araldite CY-182, 192, 184 (above, manufactured by BASF), ERL-4234, 4299, 4221, 4206 (above, UC. C), Shodyne 509 (Showa Denko), Epicron 200, 400 (above, Dainippon Ink), Epicoat 871, 872 (above Japan Epoxy Resin), ED-5661, 5661 (above, Celanese coating)
Examples of the aliphatic polyglycidyl ether include Epolite 100MF (Kyoeisha Chemical Co., Ltd.) and Epiol TMP (Nippon Yushi Co., Ltd.).

  Of these, bisphenol A type epoxy resins and phenol novolac type epoxy resins are preferred.

[H] The content of the epoxy compound is preferably 50 parts by mass or less and more preferably 30 parts by mass or less with respect to 100 parts by mass of the [A] alkali-soluble resin. [H] When the usage-amount of an epoxy compound exceeds 50 mass parts, there exists a tendency for the storage stability of the said radiation sensitive resin composition to fall.
[[I] Storage stabilizer]
Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitronitroso compounds, and more specifically, 4-methoxyphenol, N-nitroso-N-phenylhydroxylamine aluminum. Etc.

As content of a preservation | save stabilizer, 3.0 mass parts or less are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 1.0 mass part or less is more preferable. When content of a storage stabilizer exceeds 3.0 mass parts, the sensitivity of the said radiation sensitive resin composition may fall and a pattern shape may deteriorate.
<Method for preparing radiation-sensitive resin composition>
In addition to [A] alkali-soluble resin, [B] polymerizable compound, [C] photopolymerization initiator and [D] compound, the radiation-sensitive resin composition includes [E] compound and other compounds as necessary. It is prepared by mixing arbitrary components at a predetermined ratio. The radiation sensitive resin composition is preferably used in a solution state after being dissolved in an appropriate solvent.

  Solvents used for the preparation of the radiation sensitive resin composition include [A] alkali-soluble resin, [B] polymerizable compound, [C] photopolymerization initiator, [D] compound, [E] compound, and other Any component that dissolves or disperses uniformly and does not react with each component is used.

As the solvent, for example, from the viewpoints of solubility of each component, reactivity with each component, ease of film formation, etc.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;
Acetic acid ethylene glycol monomethyl ether, acetic acid ethylene glycol monoethyl ether, acetic acid ethylene glycol mono-n-propyl ether, acetic acid ethylene glycol mono-n-butyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid diethylene glycol mono-n-propyl Acetic acid (poly) alkylene glycol monoalkyl ethers such as ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate ;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexane-2-one;
Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, N-butyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Ethyl 2-hydroxy-2-methylpropionate, 2 Hydroxy-3-methyl-butyric acid methyl, other esters such as ethyl 2-oxo acid;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like.

  Among these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (propylene glycol monoethyl ether acetate (PGMEA)), 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol Methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Ethyl ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, i-butyl acetate , Formic acid n- amyl acetate, i- amyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl ethyl pyruvate are preferred, propylene glycol monomethyl ether acetate is more preferable. The solvent can be used alone or in combination of two or more.

  Furthermore, in order to improve the in-plane uniformity of the film thickness together with the solvent, a high boiling point solvent can be used in combination. Examples of the high boiling point solvent include benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, Examples include diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate. The high boiling point solvent can be used alone or in combination of two or more.

The content of the solvent is not limited, but the total concentration of each component excluding the solvent of the radiation-sensitive resin composition is 5% by mass from the viewpoint of applicability and stability of the obtained radiation-sensitive resin composition. The amount of ˜50% by mass is preferable, and the amount of 10% by mass to 40% by mass is more preferable. When the radiation-sensitive resin composition is prepared in a solution state, the solid content concentration (components other than the solvent in the composition solution) may be any concentration (for example, depending on the purpose of use, desired film thickness, etc. 5 mass% to 50 mass%). The more preferable solid content concentration varies depending on the method of forming the coating film on the substrate, which will be described later. The composition solution thus prepared can be used after being filtered using a Millipore filter or the like having a pore diameter of about 0.5 μm.
<Method for forming cured film for display element>
The radiation-sensitive resin composition is preferable for forming a cured film for a display element. Moreover, the cured film for display elements formed from the said radiation sensitive resin composition is suitably contained in this invention.

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

According to the forming method of the present invention, it is possible to form a cured film for a display element that is excellent in compression performance, transmittance, light resistance, voltage holding ratio, development resistance, heat resistance and solvent resistance. Hereinafter, each process is explained in full detail.
[Step (1)]
In this step, a transparent conductive film is formed on one surface of the transparent substrate, and a coating film of the radiation-sensitive resin composition is formed on the transparent conductive film. Examples of the transparent substrate include glass substrates such as soda lime glass and alkali-free glass, and resin substrates made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide.

  Examples of the transparent conductive film provided on one surface of the transparent substrate include a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO2), an ITO film made of indium oxide-tin oxide (In2O3-SnO2), and the like.

  When a coating film is formed by a coating method, the coating film is preferably formed by heating (pre-baking) the coated surface after coating the solution of the radiation sensitive resin composition on the transparent conductive film. Can do. As solid content concentration of the composition solution used for a coating method, 5 mass%-50 mass% are preferable, 10 mass%-40 mass% are more preferable, 15 mass%-35 mass% are especially preferable. Examples of the application method of the radiation sensitive resin composition include spraying, roll coating, spin coating (spin coating), slit coating (slit die coating), bar coating, and ink jet coating. An appropriate method can be adopted. Of these, spin coating or slit coating is preferred.

The prebaking conditions vary depending on the type of each component, the blending ratio, and the like, but are preferably 70 ° C. to 120 ° C. and about 1 to 15 minutes. The film thickness after pre-baking of the coating film is preferably 0.5 μm to 10 μm, and more preferably about 1.0 μm to 7.0 μm.
[Step (2)]
In this step, radiation is applied to at least a part of the formed coating film. At this time, when irradiating only a part of the coating film, for example, a method of irradiating through a photomask having a predetermined pattern can be used. Examples of radiation used for irradiation include visible light, ultraviolet light, and far ultraviolet light. Of these, radiation having a wavelength in the range of 250 nm to 550 nm is preferable, and radiation including ultraviolet light of 365 nm is more preferable.

Radiation dose (exposure dose), as a value measured by a luminometer intensity at a wavelength 365nm of the radiation emitted (OAI model 356, Optical Associates Ltd. ^{Inc.), 100J / m 2 ~5,000J} / m 2 is Preferably, 200 J / m ^{2 to} 3,000 J / m ² is more preferable.

The radiation-sensitive resin composition has a higher sensitivity than conventionally known compositions, and a desired film thickness even when the radiation dose is 700 J / m ² or less, and even 600 J / m ² or less. A cured film for a display element having a good shape, excellent adhesion and high hardness can be obtained.
[Step (3)]
In this step, the coated film after irradiation is developed to remove unnecessary portions and form a predetermined pattern. Examples of the developer used for the development include aqueous solutions of alkaline compounds such as inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate, and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Can be mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant may be added to the aqueous solution of the alkaline compound.

The developing method may be any of a liquid filling method, a dipping method, a shower method, and the like, and the developing time is preferably about 10 seconds to 180 seconds at room temperature. Subsequent to the development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then a desired pattern is obtained by air drying with compressed air or compressed nitrogen.
[Step (4)]
In this step, a cured film for display element is obtained by heating the obtained patterned coating film with a suitable heating device such as a hot plate or oven. The heating temperature is about 100 ° C to 250 ° C. The heating time is, for example, about 5 to 30 minutes on a hot plate and about 30 to 180 minutes for an oven.
<Method for manufacturing display element>
A display element provided with the said cured film for display elements is also suitably contained in this invention. As a method for manufacturing a display element, first, a pair (two) of transparent substrates having a transparent conductive film (electrode) on one side is prepared, and the radiation-sensitive resin composition is formed on the transparent conductive film of one of the substrates. Is used to form a spacer or a protective film or both in accordance with the method described above. Subsequently, an alignment film having liquid crystal alignment ability is formed on the transparent conductive film and the spacer or protective film of these substrates. These substrates are arranged facing each other with a certain gap (cell gap) so that the liquid crystal alignment direction of each alignment film is orthogonal or antiparallel, with the surface on which the alignment film is formed inside. A liquid crystal is filled in the cell gap defined by the surface of the substrate (alignment film) and the spacer, and the filling hole is sealed to constitute a liquid crystal cell. Then, the display element of the present invention is bonded to both outer surfaces of the liquid crystal cell such that the polarizing direction is aligned or orthogonal to the liquid crystal alignment direction of the alignment film formed on one surface of the substrate. can get.

  As another method, a pair of transparent substrates on which a transparent conductive film, an interlayer insulating film, a protective film, a spacer, or both, and an alignment film are formed are prepared in the same manner as described above. After that, along the edge of one substrate, an ultraviolet curable sealant is applied using a dispenser, and then the liquid crystal is dropped in the form of fine droplets using a liquid crystal dispenser, and the two substrates are bonded together under vacuum. . Then, both the substrates are sealed by irradiating the sealing agent part with ultraviolet rays using a high-pressure mercury lamp. Finally, the display element of the present invention is obtained by attaching polarizing plates to both outer surfaces of the liquid crystal cell.

  Examples of the liquid crystal used in each of the above methods include nematic liquid crystal and smectic liquid crystal. In addition, as a polarizing plate used outside the liquid crystal cell, a polarizing film in which a polarizing film called an “H film” that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films, or an H film Examples thereof include a polarizing plate made of itself.

EXAMPLES Hereinafter, although this invention is explained in full detail based on an Example, this invention is not interpreted limitedly to this Example.
<[A] Synthesis of alkali-soluble resin>
Synthesis example 1
A 500 ml scoop equipped with a condenser and a stirrer is charged with 5 parts by mass of 2,2-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate, and 18 parts by mass of methacrylic acid, tricyclomethacrylate [5.2. 1.0 ^2.6 ] 25 parts by weight of decan-8-yl, 5 parts of styrene, 30 parts by weight of hydroxyethyl methacrylate and 22 parts by weight of benzyl methacrylate were substituted with nitrogen, and then the solution was stirred gently. The temperature of was increased to 80 ° C. A copolymer solution having a solid content concentration of 28.8% was obtained by polymerization at this temperature for 5 hours.
It was Mw = 10000 when the weight average molecular weight (Mw) of the obtained copolymer solution was measured using GPC-101 (brand name: Showa Denko Co., Ltd. product).
Next, 14 parts by mass of 2-methacryloyloxyethyl isocyanate (trade name: Karenz MOI, manufactured by Showa Denko KK) and 0.1 part by mass of 4-methoxyphenol were added and stirred at 40 ° C. for 1 hour, and then further at 60 ° C. For 2 hours. The end point of the reaction was defined as the disappearance of a peak near 2270 cm ⁻¹ derived from the isocyanate group of 2-methacryloyloxyethyl isocyanate. The solid content concentration of the obtained resin solution was 30.0%, and Mw = 12000. This copolymer solution was designated as (A-1).
Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 4 parts by weight of 2,2′-azobisisobutyronitrile and 300 parts by weight of diethylene glycol methyl ethyl ether, and subsequently (a1) 23 parts by weight of methacrylic acid to give a structural unit, While charging 10 parts by weight of styrene to give other structural units, 32 parts by weight of benzyl methacrylate and 35 parts by weight of methyl methacrylate, and 2.7 parts by weight of α-methylstyrene dimer as a molecular weight regulator, The temperature of the solution was raised to 80 ° C., and this temperature was kept for 4 hours, and then raised to 100 ° C., and this temperature was kept for 1 hour for polymerization to obtain a solution containing a copolymer (solid content). Concentration = 24.9%). Mw of the obtained copolymer was 12,500.
Next, 1.1 parts by mass of tetrabutylammonium bromide and 0.05 parts by mass of 4-methoxyphenol as a polymerization inhibitor were added to the solution containing the copolymer, and after stirring at 90 ° C. for 30 minutes in an air atmosphere, methacrylic acid was added. A solution containing the copolymer (A-2) was obtained by adding 16 parts by mass of glycidyl and reacting at 90 ° C. for 10 hours (solid content concentration = 29.0%). Mw of the copolymer (A-2) was 14,200. The solution containing the copolymer (A-2) is added dropwise to hexane for reprecipitation purification, and the reprecipitated resin solid content is analyzed by ¹ H-NMR analysis for the reaction rate of glycidyl methacrylate ((a3) structure) Unit production rate) was calculated. Integration between the peak derived from the methacrylic group of glycidyl methacrylate at around 6.1 ppm and 5.6 ppm and the proton of the aromatic ring around 6.8 ppm to 7.4 ppm derived from the structural unit of benzyl methacrylate in the copolymer From the comparison of the ratio, the reaction rate between glycidyl methacrylate and the carboxy group in the copolymer was calculated. As a result, it was found that 96 mol% of the reacted glycidyl methacrylate reacted with the carboxy group in the copolymer.
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 250 parts by mass of diethylene glycol methyl ethyl ether, followed by 6 .. Parts, tricyclomethacrylic acid [5.2.1.02 ..] decane-8yl 32 parts by mass, styrene 5 parts by mass, butadiene 5 parts by mass and glycidyl methacrylate 40 parts by mass While stirring the solution, the temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a copolymer solution having a solid concentration of 31.0%. About the obtained copolymer solution, when Mw was measured using GPC, it was Mw = 11,000. This copolymer solution was designated as (A-3).
Synthesis example 4
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 propylene glycol monomethyl ether acetate. Subsequently, 20 parts by mass of styrene, 18 parts by mass of methacrylic acid, 20 parts by mass of tricyclo [5.2.02.] Decane-8-yl methacrylate, and 42 parts by mass of 3-ethyl-3-methacryloyloxymethyloxetane were charged. After the replacement, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a copolymer solution. The obtained polymer solution had a solid content concentration of 33.0%, and Mw was measured by GPC. As a result, Mw = 24,000. This copolymer solution was designated as (A-4).
<Preparation of radiation-sensitive resin composition>
The detail of each component used by the Example and the comparative example is shown below.
<[B] Polymerizable compound>
B-1: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Kayaku Co., Ltd.)
B-2: Succinic acid-modified pentaerythritol triacrylate (Aronix TO-756, Toagosei Co., Ltd.)
B-3: Trimethylolpropane triacrylate B-4: Biscoat 802 (mixture of tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate, Osaka Organic Chemical Co., Ltd.)
<[C] Photopolymerization initiator>
Compound represented by the above formula (C-2) Compound represented by the above formula (C-3)
Compound represented by the above formula (C-6) Compound represented by the above formula (C-8)
<[D] Compound>
D-1: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (IRGANOX 1010 BASF)
D-2: 2,5-di-tert-butylhydroquinone D-3: Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (ADK STAB AO-20, Adeka)
D-4: 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (Adekastab AO-330, Adeka)
D-5: Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (TINUVIN 770 BASF)
D-6: Distearyl pentaerythritol diphosphite (Adeka Stub PEP-8, Adeka)
D-7: Pentaerythritol tetrakis (3-laurylthiopropionate) (Adeka Stub AO-412S, Adeka)
<[E] compound>
E-1: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure 907, Ciba Specialty Chemicals)
E-2: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02, Ciba Specialty Chemicals) )
E-3: 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (Irgacure OXE01, Ciba Specialty Chemicals)
E-4: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one E-5: 4,4′-bis (diethylamino) benzophenone <[F] adhesion aid>
F-1: γ-Glycidoxypropyltrimethoxysilane <[G] surfactant>
G-1: FTX-218 (Neos)
[Example 1]
[A] 100 parts by mass of the copolymer solution (A-1) as an alkali-soluble resin in terms of solid content, [B] 100 parts by mass of (B-1) as a polymerizable compound, [C] a photopolymerization initiator (C-3) 5 parts by mass, (F-1) 5 parts by mass as an adhesion assistant, and (G-1) 0.5 parts by mass as a surfactant are mixed, and the solid content concentration is 30. After adding propylene glycol monomethyl ether acetate (PGMEA) so that it might become mass%, the radiation sensitive resin composition was prepared by filtering with a Millipore filter with a hole diameter of 0.5 micrometer.
[Examples 2-9 and Comparative Examples 1-2]
Each radiation sensitive resin composition was prepared in the same manner as in Example 1 except that the components of the types and contents shown in Table 1 were mixed. In Table 1, “-” indicates that the corresponding component was not used. In addition, although (F-1) as an adhesion assistant and (G-1) as a surfactant are not described in Table 1, they are added to the composition solution in the same manner as in Example 1.

<Evaluation>
The following evaluation was implemented using each prepared radiation sensitive resin composition. In detail, about Examples 1-4 and Comparative Example 1, the cured film for display elements was formed using each radiation sensitive resin composition, and the resolution, sensitivity, and compression performance as a spacer were evaluated. About Examples 5-9 and the comparative example 2, the cured film for display elements was formed using each radiation sensitive resin composition, and the transmittance | permeability, light resistance, and voltage holding rate as an interlayer insulation film were evaluated. The results are shown in Table 2.
[Resolution (μm)]
Each radiation-sensitive resin composition solution was applied onto an alkali-free glass substrate with a spinner and then pre-baked on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 4.0 μm. Subsequently, the exposure amount is set to 200 J / m ^{2 to} 1,000 J / M using a high-pressure mercury lamp through a photomask having a plurality of circular residual patterns with different sizes in the diameter range of ⁸ μm to ²⁰ μm. Irradiation was performed with variable amount in the range of m ² . Then, shower development was performed by discharging a 0.40 mass% potassium hydroxide aqueous solution at 23 ° C. with a developing pressure of 1 kgf / cm ² and a nozzle diameter of 1 mm, and pure water washing was performed for 1 minute. Further, a patterned coating film was formed by post-baking in an oven at 230 ° C. for 30 minutes. At this time, the minimum pattern size to be formed was defined as the resolution (μm). If a pattern having a size of 12 μm or less is formed in a photomask of 12 μm or less, it can be determined that the resolution is good.
[Sensitivity (J / m ² )]
Except for using a photomask having a plurality of round residue patterns having a diameter of 15 μm, a round residue pattern was formed on the substrate in the same manner as in the resolution evaluation. The height of the circular residual pattern before and after development was measured using a laser microscope (VK-8500, Keyence Corporation). The residual film ratio (%) was determined from this value and the following formula.

Residual film ratio (%) = (height after development / height before development) × 100
The minimum exposure amount at which the remaining film ratio was 90% or more was defined as sensitivity (J / m ² ). When the exposure amount is 700 J / m ² or less, it can be determined that the sensitivity is good.
[Compression performance]
By operating in the same manner as in the sensitivity evaluation described above, a circular residual pattern was formed on the substrate with an exposure amount at which the residual film ratio was 90% or more. This pattern was subjected to a compression test with a load of 40 mN using a 50 μm square planar indenter with a micro compression tester (Fischer Scope H100C, Fisher Instruments), and the amount of compressive displacement (μm) relative to the load was measured. Further, the recovery rate (%) was calculated from the amount of displacement when a load of 40 mN and the amount of displacement when a load of 40 mN was removed. When the recovery rate is 90% or more and the amount of compressive displacement at a load of 40 mN is 0.15 μm or more, it can be determined that the compression performance is good.
[Transmissivity (%)]
With respect to the cured film for a display element obtained by operating in the same manner as the evaluation of the resolution except that the exposure was performed at an exposure amount of 800 J / m ² without using a photomask, the transmittance (%) at a wavelength of 400 nm was measured by spectroscopic analysis. Measured using a photometer (150-20 type double beam, Hitachi, Ltd.). When the transmittance is 90% or more, it can be determined that the transparency is good.
[Light resistance (%)]
A cured film for a display element was formed by operating in the same manner as the evaluation of the transmittance. About the obtained cured film for display elements, UV irradiation apparatus (UVX-02516S1JS01, USHIO, lamp; UVL-4001M3-N1) was irradiated with 500 kJ / m ² of UV light, and the remaining film ratio before and after irradiation was determined. Evaluated by seeking. When the remaining film ratio is 95% or more, it can be judged that the light resistance (%) is good.
[Voltage holding ratio (%)]
After spin-coating each radiation-sensitive resin composition on a soda glass substrate on which a SiO2 film for preventing elution of sodium ions is formed on the surface, and an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape The film was pre-baked for 10 minutes in a clean oven at 90 ° C. to form a coating film having a thickness of 2.0 μm. Next, the coating film was exposed at an exposure amount of 500 J / m 2 without using a photomask. Thereafter, the substrate is immersed in a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and further post-treated at 230 ° C. for 30 minutes. Baking was performed and the coating film was cured to form a permanent cured film. Next, the substrate on which this pixel is formed and the substrate on which the ITO electrode is simply deposited in a predetermined shape are bonded together with a sealant mixed with 0.8 mm glass beads, and then Merck liquid crystal (MLC6608) is injected. A liquid crystal cell was produced. Next, the liquid crystal cell was placed in a constant temperature layer at 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system (VHR-1A type, Toyo Technica Co., Ltd.). The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz. Here, the voltage holding ratio is a value of (liquid crystal cell potential difference after 16.7 milliseconds / voltage applied at 0 milliseconds). If the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot hold the applied voltage at a predetermined level for a time of 16.7 milliseconds, and the liquid crystal cannot be sufficiently aligned. There is a high risk of causing “burn-in”.
[Evaluation of dielectric constant]
Each of the compositions shown in Table 1 was applied onto a polished SUS substrate using a spinner and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. did. The obtained coating film was exposed with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Co., Ltd. so that the integrated irradiation amount was 3,000 J / m <2>, and then in a clean oven at 220 [deg.] C. for 1 hour. A cured film was formed on the substrate by heating. A dielectric constant measurement sample was prepared by forming a Pt / Pd electrode pattern on each of the cured films by vapor deposition. For each substrate, the relative dielectric constant was measured by the CV method at a frequency of 10 kHz using an HP16451B electrode and HP4284A precision LCR meter manufactured by Yokogawa Hewlett-Packard Co., Ltd. The results are shown in Table 1. When this value is 3.5 or less, it can be said that the relative dielectric constant is good.
In the evaluation of the relative dielectric constant, patterning of the film to be formed is unnecessary, so that only the coating film forming process, the post-exposure process and the heating process were performed.

  As is clear from the results in Table 2, the radiation-sensitive resin composition has good resolution, sensitivity, and compression performance in the case of spacer evaluation. When evaluated as an interlayer insulating film, the transmittance, light resistance, It was found to have a voltage holding ratio and a low dielectric constant.

Claims (10)

[A] alkali-soluble resin,
[B] a polymerizable compound having an ethylenically unsaturated bond,
[C] A radiation-sensitive resin composition containing at least one selected from photopolymerization initiators represented by the following formula (1) or formula (2).


(In Formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, carbon, An arylalkyl group represented by Formula 7 to 30. R ¹ and R ² may be bonded to each other to form a fluorene group.
R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a complex having 4 to 20 carbon atoms. A ring group is shown. X represents a direct bond or a carbonyl group.
In formula (2), R ¹ , R ² , R ³ or R ⁴ has the same definition as in formula (1).
R ⁵ represents R ⁶ , OR ⁶ , SR ⁶ , COR ⁶ , CONR ⁶ R ⁶ , NR ⁶ COR ⁶ , OCOR ⁶ , COOR ⁶ , SCOR ⁶ , OCSR ⁶ , COSR ⁶ , CSOR ⁶ , CN, halogen, hydroxyl group Show.
R ⁶ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms. X represents a direct bond or a carbonyl group. a is an integer of 0-4. ) [A] an alkali-soluble resin
(A1) a structural unit having a carboxyl group,
(A2) The radiation-sensitive resin composition according to claim 1, which is a copolymer containing a structural unit having a polymerizable group. 3. The copolymer (a2) according to claim 2, wherein the polymerizable group is a copolymer having a structural unit containing at least one group selected from an oxiranyl group, an oxetanyl group and a (meth) acryloyl group. The radiation sensitive resin composition as described.   Furthermore, it includes one or more compounds selected from the group consisting of [D] a compound containing a hindered phenol structure, a compound containing a hindered amine structure, a compound containing an alkyl phosphite structure, and a compound containing a thioether structure. The radiation sensitive resin composition as described in any one of Claim 1 to 3.   [C] The usage-amount of a photoinitiator is the range of 0.1-10 mass parts with respect to 100 mass parts of [A] alkali-soluble resin, It is any one of Claims 1-4. Radiation sensitive resin composition. [B] The radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the polymerizable compound having an ethylenically unsaturated bond is a polymerizable unsaturated compound having a hydroxyl group or a carboxyl group. . Further, one or more selected from the group consisting of [E] thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds (other than [C] component), and thiol compounds. The radiation sensitive resin composition as described in any one of Claims 1-6 containing the compound of these. The cured film for display elements formed from the radiation sensitive resin composition of any one of Claims 1-7. (1) The process of forming the coating film of the radiation sensitive resin composition of any one of Claims 1-7 on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) A step of developing the coating film irradiated with the radiation, and (4) A method for forming a cured film for a display element, comprising a step of baking the developed coating film. A display element provided with the cured film for display elements of Claim 8.