KR102006751B1 - Radiation-sensitive resin composition, cured film for display device, method for forming the cured film for display device, and display device - Google Patents
Radiation-sensitive resin composition, cured film for display device, method for forming the cured film for display device, and display device Download PDFInfo
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- KR102006751B1 KR102006751B1 KR1020130136135A KR20130136135A KR102006751B1 KR 102006751 B1 KR102006751 B1 KR 102006751B1 KR 1020130136135 A KR1020130136135 A KR 1020130136135A KR 20130136135 A KR20130136135 A KR 20130136135A KR 102006751 B1 KR102006751 B1 KR 102006751B1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/12—Sulfonium compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
Abstract
(Problem) A radiation sensitive resin composition having sufficient resolution and sensitivity, and a cured film for a display element which are excellent in compression performance, transmittance, light resistance, voltage preservation rate and low dielectric constant.
[Means for Solving the Problems] In order to solve the above problems,
[A] Alkali-soluble resin,
[B] Polymerizable compound having an ethylenically unsaturated bond
[C] A radiation-sensitive resin composition containing at least one selected from the photopolymerization initiators represented by the following formula (1) or (2).
Description
The present invention relates to a radiation-sensitive resin composition, a cured film for a display element, a method for forming a cured film for a 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 formed in order to insulate between wirings arranged in a generally layered form, and the upper part of the semiconductor element is also flattened in the organic electroluminescence element, A flattening film is formed on the film to laminate the electrode and the light emitting layer.
For example, a thin film transistor liquid crystal display device 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. Therefore, the interlayer insulating film is exposed to the high temperature conditions in the process of forming the transparent electrode film, or exposed to the stripping solution of the resist used for forming the pattern of the electrode. Therefore, sufficient heat resistance and solvent resistance are required It becomes.
In the conventional interlayer insulating film for a liquid crystal display element, a positive-tone radiation-sensitive resin composition using an acid generator such as naphthoquinone diazide is used from the viewpoint of patterning performance (see JP-A-2001-354822) .
In recent years, attention has been paid to the performance of the negative-tone radiation-sensitive resin composition, such as high sensitivity and high light transmittance of the resultant cured film, and application of the negative-tone radiation-sensitive resin composition has been progressing (see Japanese Patent Laid-Open Publication No. 2000-162769) .
In recent years, TFT liquid crystal display devices are in the trend of large-screen, high-brightness, high-definition, high-speed response, thinning, and the composition for forming an interlayer insulating film used therefor has high sensitivity. Low dielectric constant, high transmittance, and the like.
On the other hand, most of the members used in the liquid crystal display element, the spacer, the protective film, the coloring pattern for the color filter, and the like are mostly formed using a negative-tone radiation-sensitive resin composition (see Japanese Patent Laid-Open Publication No. 6-43643). In recent years, liquid crystal display elements are required to have larger screen size, higher luminance, and thinner shape. From the viewpoints of shortening the processing time and reducing the cost, the sensitivity and the resolution of the negative radiation sensitive resin composition are required to be high.
As a countermeasure against the shortening of the process time, a technique of a radiation-sensitive resin composition containing an oxime ester-based photopolymerization initiator has been studied (JP-A-2005-227525, WO 2008/078686, See Publication No. WO 2009/081483). However, such a photopolymerization initiator has many compounds having the maximum absorption in the visible region, and the photopolymerization initiator itself often has a slight red color. When such a conventional photopolymerization initiator is used to form a cured film, the cured film also exhibits a slightly red color and the light transmittance is lowered, so that it may not be applicable to liquid crystal display elements or organic electroluminescence elements .
From such a situation, development of a radiation-sensitive resin composition having sufficient resolution and sensitivity, and a cured film for a display device excellent in compression performance, transmittance, light resistance, voltage conservation rate, low dielectric constant, developing resistance, heat resistance and solvent resistance have been desired.
The object of the present invention is to provide a radiation-sensitive resin composition having sufficient resolution and sensitivity, and a radiation-sensitive resin composition which is excellent in compression performance, transmittance, light resistance, voltage holding ratio, low dielectric constant, Thereby providing an excellent cured film for a display element.
According to an aspect of the present invention,
[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 the photopolymerization initiators represented by the following formula (1) or (2) (hereinafter also referred to as "[C] photopolymerization initiator"):
(In the formula (1), R 1 and R 2 each independently represent 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, an arylalkyl group having 7 to 30 carbon atoms R 1 and R 2 may combine with each other to form a fluorene group;
R 3 and R 4 each independently represent 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 heterocyclic group having 4 to 20 carbon atoms; X represents a direct bond or a carbonyl group;
In formula (2), R 1 , R 2 , R 3 or R 4 are the same as defined in formula (1);
R 5 is, 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, a hydroxyl group ;
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; and a is an integer of 0 to 4).
The radiation sensitive resin composition contains the [A] alkali-soluble resin, the [B] polymerizable compound, the specific amount of the [C] photopolymerization initiator, and the [D] compound and the [E] compound. The radiation-sensitive resin composition of the present invention can easily form fine and elaborate patterns by exposure and development using radiation-sensitive properties, and has sufficient resolution and sensitivity. In addition, the radiation sensitive resin composition can form a cured film for a display element excellent in compression performance, transmittance, light resistance, voltage preservation rate and the like by containing a specific amount of the [C] photopolymerization initiator having the above specific structure. Further, the radiation-sensitive resin composition contains the [D] compound (a compound containing a hindered phenol structure or the like), so that the radiation-sensitive resin composition can form a cured film for a display element having enhanced light resistance and heat resistance have.
The alkali-soluble resin [A]
(a1) a structural unit having a carboxyl group (hereinafter also referred to as "(a1) structural unit"),
(a2) a structural unit having a polymerizable group (hereinafter also referred to as a " structural unit (a2) ").
When the [A] alkali-soluble resin contains the structural unit (a1), a radiation-sensitive resin composition having excellent radiation sensitivity and excellent solubility in an alkali aqueous solution can be obtained. Further, the heat resistance and light resistance of the resulting cured film for a display element can be improved by containing the structural unit (a2) in addition to the structural unit (a1) of the alkali-soluble resin [A].
The polymerizable group in the structural unit (a2) of the [A] alkali-soluble resin is preferably a copolymer having a structural unit containing at least one kind of group selected from an oxiranyl group, an oxetanyl group and a (meth) acryloyl group . The curability and the like of the resulting cured film for a display element can be further improved.
The radiation sensitive resin composition of the present invention may further contain a compound containing a hindered phenol structure [D], a compound containing a hindered amine structure, a compound containing an alkyl phosphite structure, and a compound containing a thioether structure (Hereinafter, also referred to as [D] compound).
By including the [D] compound, it becomes possible to achieve a high level of sensitivity and resolution at the time of pattern formation of the obtained pattern.
The amount of the [C] photopolymerization initiator used is preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the [A] alkali-soluble resin. By setting the amount of the [C] photopolymerization initiator to be in the above range, it becomes possible to achieve a high level of both the sensitivity at the time of pattern formation and the transmittance of the obtained film.
The polymerizable compound [B] 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 at the time of pattern formation and the heat resistance and solvent resistance of the resulting cured film can be made compatible at a high level.
Further, the radiation-sensitive resin composition of the present invention may further contain at least one selected from the group consisting of [E] thioxanthone compounds, acetophenone compounds, nonimidazole compounds, triazine compounds, O-acyloxime compounds (other than the [C] , And a thiol-based compound (hereinafter also referred to as [E] compound).
By including the [E] compound, it becomes possible to achieve compatibility between sensitivity and resolution at the time of pattern formation at a high level.
The radiation sensitive resin composition is preferably used for forming a cured film for a display element. The present invention suitably includes a cured film for a display element formed of the radiation sensitive resin composition and a display element having the cured film for a display element.
The method for forming a cured film for a display element of the present invention is characterized in that,
(1) a step of forming a coating film on a substrate using the 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) 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 excellent in compression performance, transmittance, light resistance, low dielectric constant, voltage holding ratio and the like.
The term " radiation " of the " radiation-sensitive resin composition " in the present specification is a concept including visible light, ultraviolet light, far ultraviolet light, X-ray,
INDUSTRIAL APPLICABILITY As described above, the radiation sensitive resin composition of the present invention has a sufficient resolution and sensitivity because it can easily form fine and precise patterns. In addition, the radiation sensitive resin composition can form a cured film for a display element excellent in compression performance, transmittance, light resistance, voltage holding ratio, and the like. Therefore, the radiation sensitive resin composition can be used as a protective film for a display element color filter, a spacer, an interlayer insulating film for an array, a color filter for color separation of a solid-state image pickup element, a color filter for an organic electroluminescence display element, A color filter for a flexible display, a protective film for a touch panel, a photoresist for forming a metal wiring or a metal bump, a substrate, or the like.
(Mode for carrying out the invention)
<Radiation-Resistant Resin Composition>
The radiation sensitive resin composition of the present invention contains the [A] alkali-soluble resin, the [B] polymerizable compound, and the [C] photopolymerization initiator. Further, the radiation sensitive resin composition may contain the [D] compound and the [E] compound as suitable components. Furthermore, the radiation sensitive resin composition may contain other optional components as long as the effect of the present invention is not impaired. Hereinafter, each component will be described in detail.
<[A] alkali-soluble resin>
The alkali-soluble resin [A] is not particularly limited as long as it is a resin having alkali dissociation property, but it is preferably a resin containing the structural unit (a1) and the structural unit (a2). Here, the alkali-soluble resin [A] may contain other structural units than the structural units (a1) and (a2) structural units, so long as the effect of the present invention is not impaired.
[A] The alkali-soluble resin can be synthesized by radical polymerization of a compound which gives each structural unit in the presence of a polymerization initiator in a solvent. Hereinafter, the compounds giving each structural unit are described in detail. Two or more of these compounds may be used in combination.
[(a1) Structural unit]
The structural unit (a1) 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 carbonic anhydride. Examples of the compound giving the structural unit (a1) include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids, Mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at the terminal, an unsaturated polycyclic compound having a carboxyl group, and an anhydride 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. The anhydrides of the unsaturated dicarboxylic acids include, for example, anhydrides of the compounds exemplified as the dicarboxylic acids. Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl ] And the like. Examples of the mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals include ω-carboxypolycaprolactone mono (meth) acrylate and the like. Examples of the unsaturated polycyclic compound having a carboxyl group and anhydrides thereof include 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- 5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto- [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] And the like.
Of these, monocarboxylic acids and anhydrides of dicarboxylic acids are preferable, and (meth) acrylic acid and maleic anhydride are more preferable in view of solubility and availability of an aqueous alkaline solution, copolymerization reactivity, and alkaline aqueous solution.
The proportion of the structural unit (a1) in the alkali-soluble resin [A] is preferably 5% by mole to 30% by mole, and more preferably 10% by mole to 25% by mole based on the total structural units. When the content of the structural unit (a1) is from 5 mol% to 30 mol%, the radiation-sensitive resin composition having an excellent radiation sensitivity while optimizing the solubility of the alkali-soluble resin [A] in an alkali aqueous solution is obtained.
[(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, an oxiranyl group, an oxetanyl group and a (meth) acryloyl group are preferable from the viewpoint of improvement of heat resistance and light resistance.
The structural unit having an oxiranyl group (hereinafter also referred to as a structural unit (a2-1)) 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 glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α-n-butyl acrylate Glycidyl acrylate, 3,4-epoxybutyl acrylate, methacrylic acid-3,4-epoxybutyl acrylate, 6,7-epoxyhexyl acrylate, methacrylic acid-6,7-epoxyheptyl acrylate, , 7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and 3,4-epoxycyclohexyl methacrylate.
The structural unit having an oxetanyl group (hereinafter also referred to as a structural unit (a2-2)) 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- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (Acryloyloxymethyl) -2,2,4-trifluoroacetate, 3- (acryloyloxymethyl) -2,2-difluorooxetane, 3- Oxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-acryloyloxyethyl) oxetane, 3- Ethyl oxetane, 3- (2-acryloyloxyethyl) -3-ethyl oxetane, 3- (2-acryloyloxyethyl) -2-trifluoromethyl oxetane, 3- (2-acryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (2-acryloyloxyethyl) -2-phenyloxetane, 3- , 2-diflu (2-acryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (2-acryloyloxyethyl) -2,2,4,4-tetrafluoro Acrylic acid esters such as oxetane;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) (Methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2- (Methacryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (Methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) 3- (2-methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (2-methacryloyloxyethyl) (2-methacryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (2-methacryloyloxyethyl) -2-phenyloxetane, 3- ) -2,2-difluorooxetane, 3- (2- Methacrylic acid, such as kryloyloxyethyl) -2,2,4-trifluorooxetane and 3- (2-methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane Ester etc. are mentioned.
Among these unsaturated compounds having an oxiranyl group and unsaturated compounds having an oxetanyl group, glycidyl methacrylate, 2-methylglycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl Vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, methacrylic acid 3,4-epoxycyclohexyl, 3- (methacryloyloxymethyl) -3-ethyloxetane, From the viewpoints of copolymerization reactivity, compression performance of the cured film for a display element, and light resistance.
The content ratio of the (a2-1) structural unit or (a2-2) structural unit in the alkali-soluble resin [A] is preferably 5 mol% to 60 mol% based on the total structural units, 10 mol% to 50 mol%. By setting the content ratio of the (a2-1) structural unit or (a2-2) structural unit to 5 mol% to 60 mol%, a cured film for a display element having excellent curability can be formed.
(Hereinafter also referred to as (a2-3) structural unit) having a (meth) acryloyl group is a structural unit represented by the following formula (3). In the following formula (3), R 7 and R 8 are each a hydrogen atom or a methyl group. R 9 is a group represented by the following formula (4-1) or (4-2). n is an integer of 1 to 6; In the formula (4-1), R 10 is a hydrogen atom or a methyl group. In the formulas (4-1) and (4-2), * represents a bonding site to an oxygen atom in the following formula (3)
(3), R 7 and R 8 are each a hydrogen atom or a methyl group, R 9 is a group represented by the formula (4-1) or (4-2) Is an integer;
In the formula (4-1), R 10 is a hydrogen atom or a methyl group; In the formulas (4-1) and (4-2), * represents a moiety bonded to the oxygen atom in the formula (3).
The structural unit (a2-3) is obtained by reacting (a1) a carboxy group in the structural unit with an unsaturated compound having an oxiranyl group forming the aforementioned structural unit (a2-1) to form an ester bond. Specifically, for example, there may be mentioned, for example, (meth) acrylic acid esters such as (meth) acrylic esters of (meth) acrylic esters such as glycidyl methacrylate, When a compound is reacted, R 9 in the formula (3) becomes a group represented by the formula (4-1). On the other hand, when (a4) a compound giving a structural unit is reacted with a compound such as 3,4-epoxycyclohexylmethyl methacrylate, R 9 in the formula (3) The
The structural unit (a2-3) can be obtained by reacting a polymer having a hydroxyl group with an unsaturated isocyanate compound.
Examples of the unsaturated isocyanate compound include (meth) acrylic acid derivatives, and specific examples thereof include 2- (meth) acryloyloxyethyl isocyanate, 4- (meth) acryloyloxybutyl Isocyanate, and 2- (2-isocyanatoethoxy) ethyl (meth) acrylate. As commercial products of these, commercial products of 2-acryloyloxyethyl isocyanate include Karenz AOI (manufactured by Showa Denko K.K.) and 2-methacryloyloxyethyl isocyanate commercially available as Car lens MOI (Manufactured by Showa Denko K.K.) as a commercially available product of 2- (2-isocyanatoethoxy) ethyl methacrylate.
Among these unsaturated isocyanate compounds, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 4-methacryloyloxybutyl isocyanate or methacrylic acid 2 is preferable from the viewpoint of reactivity with a polymer having a hydroxyl group. - (2-isocyanatoethoxy) ethyl is preferred. The unsaturated isocyanate compounds may be used alone or in combination of two or more.
The reaction of the polymer having a hydroxyl group with the unsaturated isocyanate compound is carried out by adding an unsaturated isocyanate compound to a solution of a polymer containing a polymerization inhibitor, preferably in the presence of a suitable catalyst, at room temperature or under heating, . Examples of the catalyst include di-n-butyl tin dilaurate (IV) and the like; Examples of the polymerization inhibitor include p-methoxyphenol and the like.
The ratio of the unsaturated isocyanate compound used in the production of the polymer having a structural unit (a2-3) is preferably from 0.1 to 95 mol%, more preferably from 1.0 to 80 mol%, based on the hydroxyl group in the polymer, And particularly preferably 5.0 to 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 property of the obtained cured film are further improved, which is preferable.
Examples of the alkali-soluble resin (A) include a resin containing a structural unit (a1) and a structural unit (a2-1) or a structural unit (a2-2) May be mixed with the resin.
[Other structural units]
Examples of the compound which imparts the structural unit other than the structural unit (a2) and the structural unit (a1) which may contain the alkali-soluble resin (A) as long as the effect of the present invention is not impaired include, for example, (Meth) 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, tetrahydrofuran skeleton and the like.
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, 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate and the like.
Examples of the alkyl (meth) acrylate chain alkyl esters include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, Hexyl acrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, sec- , 2-ethylhexyl acrylate, isodecyl acrylate, n-lauryl acrylate, tridecyl acrylate, and n-stearyl acrylate.
Examples of the (meth) acrylic acid cyclic alkyl esters include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 2,6 ] decane-8-methacrylic acid, Tricyclo [5.2.1.0 2,6 ] decane-8-yloxyethyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 2,6 ] decane- 8-yl acrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yloxyethyl acrylate, and isobornyl acrylate.
Examples of the (meth) acrylic acid aryl esters include phenyl methacrylate, benzyl methacrylate, phenyl acrylate, and benzyl acrylate.
Examples of the unsaturated aromatic compound include styrene,? -Methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-tolyl maleimide, N-naphthyl maleimide, N-ethyl maleimide, N-hexyl maleimide and N-benzyl maleimide. Examples of the conjugated dienes 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) acryloyloxy Tetrahydrofuran-2-one, and the like.
Examples of the solvent used in the polymerization reaction for synthesizing the [A] alkali-soluble resin include alcohols, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol Dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates, propylene glycol monoalkyl ether propionates, ketones, and esters.
As the polymerization initiator used in the polymerization reaction for synthesizing the [A] 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.
In the polymerization reaction for producing the [A] alkali-soluble resin, a molecular weight regulator may be used to adjust the molecular weight. Examples of the molecular weight regulator 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; Azetidine derivatives such as dimethylzantogen sulfide and diisopropylzantogen disulfide; Terpinolene, alpha -methylstyrene dimer, and the like.
The weight average molecular weight (Mw) of the alkali-soluble resin [A] is preferably 1,000 to 30,000, more preferably 5,000 to 20,000. By setting the Mw of the alkali-soluble resin [A] within the above-specified range, the sensitivity and developability of the radiation-sensitive resin composition can be enhanced. The Mw and the number average molecular weight (Mn) of the polymer in the present specification were measured by gel permeation chromatography (GPC) under the following conditions.
Device: GPC-101 (Showa Denko)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804
Mobile Phase: Tetrohydrofuran
Column temperature: 40 DEG C
Flow rate: 1.0 mL / min
Sample density: 1.0 mass%
Sample injection amount: 100 μL
Detector: differential refractometer
Standard material: monodisperse polystyrene
≪ [B] Polymerizable compound >
The [B] 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. Examples thereof include ω-carboxypolycaprolactone mono (meth) acrylate, ethylene (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (Meth) acrylate, 2-hydroxy-3- (meth) acryloyl (meth) acrylate, (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloyloxyethyl) phosphate, ethylene oxide-modified dipentaerythritol (Meth) acrylate, succinic acid-modified pentaerythritol tri (meth) acrylate and the like, a compound having a straight chain alkylene group and an alicyclic structure and having at least two isocyanate groups, and a compound having at least one hydroxyl group , And urethane (meth) acrylate compounds obtained by reacting a compound having three to five (meth) acryloyloxy groups.
[B] The polymerizable compound is preferably a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate.
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 the hydroxyl group or the polymerizable unsaturated compound having 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 made compatible at a high level.
Examples of commercially available products of the [B] polymerizable compound include, for example,
ARONIX M-400, M-402, M-405, M-450, M-1310, M-1600, M-1960, M- 8030, M-8060, M-8100, M-8530, M-8560, M-9050, Aronix TO-756, TO-1450 and TO-1382.
KAYARAD DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, and MAX-3510 (above, Nippon Kayakusa);
Viscoat 295, Dong 300, Dong 360, Dong GPT, Dong 3PA, Dong 400, Dong 802 (above, Yukiko Kakuko Osaka);
As the urethane acrylate compound, New Prontier R-1150 (Daiichi Kyoei Co., Ltd.);
KAYARAD DPHA-40H, UX-5000 (above, Nippon Kayaku);
ARTRESIN UN-9000H (Nagamiko);
ARONIX M-5300, M-5600, M-5700, M-210, M-220, M-240, M-270, M-6200, M-305, M-309 , Dong M-310, Dong M-315 (above, Toagose);
KAYARAD HDDA, KAYARAD HX-220, HX-620, R-526, R-167, R-604, R-684, R-551, R-712, (Or later), the UX-3201, the UX-3301, the UX-4101, the UX-6101, the UX-7101, the UX-8101, the UX- 0937, the MU- Nippon Kayakusa);
Art Resin UN-9000PEP, UN-9200A, UN-7600, UN-333, UN-1003, UN-1255, UN-6060PTM, UN-6060P and SH-500B teacher);
Biscott 260, 312, 335 HP (above, Yukiko Osaka Kakuko), and the like.
[B] The polymerizable compounds may be used alone or in combination of two or more. The content of the [B] polymerizable compound in the radiation sensitive resin composition is preferably 10 parts by mass to 700 parts by mass, more preferably 20 parts by mass to 600 parts by mass, per 100 parts by mass of the [A] alkali-soluble resin Do. By setting the content of the [B] polymerizable compound within the above-specified range, the radiation sensitive resin composition can form a cured film for a display element having sufficient light resistance, heat resistance and voltage holding ratio even at a low exposure dose.
≪ [C] Photopolymerization initiator >
[C] The photopolymerization initiator is a photopolymerization initiator represented by the above formula (1) or (2), and the content of the [C] photopolymerization initiator in the radiation sensitive resin composition is from 100 parts by mass of the [A] 0.1 parts by mass or more and 10 parts by mass or less, The radiation sensitive resin composition contains a specific amount of the [C] photopolymerization initiator having the specific structure described above to form a cured film for a display element excellent in compression performance, transmittance, light resistance, low dielectric constant, voltage preservation rate and the like.
In the formula (1), R 1 and R 2 each independently represent 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, an arylalkyl group having 7 to 30 carbon atoms . R 1 and R 2 may be bonded to each other to form a fluorene group.
R 3 and R 4 each independently represent 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 heterocyclic group having 4 to 20 carbon atoms. X represents a direct bond or a carbonyl group.
In the formula (2), R 1 , R 2 , R 3 or R 4 are the same as defined in the formula (1).
R 5 is, 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, a hydroxyl group .
Each R 6 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 to 4;
Examples of the alkyl group having 1 to 20 carbon atoms represented by R 1 and R 2 include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- - pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-dodecyl group and the like.
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 boronyl group, a norbornyl group, an adamantyl group, etc. .
Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a naphthyl group, a tolyl group and a xylyl group. In the case of a phenyl group, 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.
The alkyl group having 1 to 20 carbon atoms, the alicyclic hydrocarbon group having 4 to 20 carbon atoms, the aryl group having 6 to 30 carbon atoms, and the arylalkyl group having 7 to 30 carbon atoms represented by R 3 , R 4 and R 6 are represented by 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-thienyl group, a 2-pyrrolyl group, a 2-pyridyl group, , A tetrahydrofuryl group, a tetrahydrofurfuryl group, and a tetrahydrofuranyl group.
In the above formula (1) or (2), R 1 and R 2 are each a methyl group, ethyl group, n-propyl group, i-propyl group, n-hexyl group, n-octyl group, n-dodecyl group, , a phenyl group, a fluorenyl group, and R 3 is a methyl group, an ethyl group, a phenyl group, a tolyl group, a xylylene group, R 4 is an alkyl group or a phenyl group having 1 to 6 carbon atoms, R 4 is a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl Lt; / RTI > X is preferably a direct bond.
When the [C] photopolymerization initiator is used as the specific compound, the sensitivity and solubility of the [C] photopolymerization initiator in the 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).
The content of the [C] photopolymerization initiator is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 5 parts by mass or less, based on 100 parts by mass of the [A] alkali- By setting the content of the photopolymerization initiator [C] to the above-specified range, the sensitivity of the radiation sensitive composition and the resulting light resistance, compression performance, sensitivity and low dielectric constant of the cured film for a display device can be further improved.
≪ [D] Compound >
The [D] 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 to be. By containing the [D] compound in the radiation-sensitive resin composition, a cured film for a display element having enhanced light resistance and heat resistance can be formed. This is presumably because the [D] compound can inhibit the cleavage of the molecule of the alkali-soluble resin [A] by capturing radicals generated during exposure, heating, etc., or by decomposing the peroxide generated by the oxidation. In addition, since the [D] compound is a compound containing the above structure, even when the radiation-sensitive resin composition contains the [D] compound, it is possible to maintain high sensitivity to radiation and to obtain a cured film for a display element The lowering of the transmittance and the voltage holding ratio is small.
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-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6- Hydroxybenzyl) benzene, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert- 5,5 ', 5 "-hexa-tert-butyl-a, a', a" - (mesitylene-2,4,6-triyl) tri- ) -cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylene bis (oxyethylene) bis [3- (5- Nate], hexamethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) (4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine-2,4,6- , 3H, 5H) -thione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin- Di-tert-butylhydroquinone, etc. Among them, as the compound having a hindered phenol structure, pentaerythritol tetrakis [3- (3,5-di-tert-butyl- Butylphenyl) propionate], 2,5-di-tert-butylhydroquinone, tris (3,5-di-tert- -2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene.
Examples of commercial products of the compound containing a hindered phenol structure include adekastab AO-20, adecastab AO-30, adecastab AO-40, adecastab AO-50, Sumilizer GM, sumilizer GS, sumilizer MDP-S, sumilizer BBM-S, sumilizer WX (to be referred to as " sumilizer WX " -R, Sumilizer GA-80 (Sumitomo Chemical Co., Ltd., IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1098, IRGANOX 1135, IRGANOX 1330, IRGANOX 1726, IRGANOX 1425WL, IRGANOX 1520L, IRGANOX 259, IRGANOX 259, , IRGANOX 565, IRGAMOD 295 (or above), Yoshinox BHT, Yoshinox BB, Yoshinox 2246G, Yoshinox 425, Yoshinox 250, Yoshinox 930, Yoshinox SS, Yoshinox TT, Yoshin Knox 917, Yoshinox 314 (available from 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- -Perpyridyl) succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octyloxy-2,2,6,6- 4-piperidyl) sebacate, bis (N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy- , 6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) 2- (3,5- Bis (3,5-di-tert-butylphenyl) malonate, bis (1-acryloyl-2,2,6,6-tetramethyl- Butyl-4-hydroxybenzyl) -2-butyl maleate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) decanedioate, 2,2,6,6-tetra Methyl-4-piperidyl methacrylate, 4- [3- (3,5-di-tert-butyl- Di-tert- Propyloxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2- (2,2,6,6-tetramethyl- (2,2,6,6-tetramethyl-4-piperidyl) -1, 2, 6-tetramethyl- 2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate and the like;
N, N ', N' ', N'''-tetrakis- [4,6-bis- [butyl- (N-methyl-2,2,6,6-tetramethylpiperidin- ] - triazin-2-yl] -4,7-diazadecane-1,10-diamine with dibutylamine and 1,3,5-triazine N, N'-bis (2,2,6, Condensation product of 6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine with N- (2,2,6,6-tetramethyl-4-piperidyl) , Polycondensates of dibutylamine with 1,3,5-triazine and N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{ 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} Methylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] and 1,6-hexanediamine-N, N'-bis (2,2,6,6- 4-piperidyl) and morpholine-2,4,6-trichloro-1,3,5-triazine, poly [(6-morpholino-s-triazine- ) [(2,2,6,6-tetramethyl-4-piperidyl) imino] -hexamethylene [(2,2,6,6-tetramethyl-4- Ridyl) imino]], a high molecular weight HALS in which a plurality of piperidine rings are bonded via a triazine skeleton, dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidine and 3,9-bis (2-hydroxy- Dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, and other polymers such as compounds in which a piperidine ring is bonded via an ester bond. Among them, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate is preferable as a compound containing a hindered amine structure.
Examples of commercial products of the compound containing a hindered amine structure include adecastab LA-52, adecastab LA-57, adecastab LA-62, adecastab LA-67, adecastab LA-63P (ADEKA), sumilizer 9A (Sumitomo Chemical), CHIMASSORB 119FL, CHIMASSORB 2020FDL, CHIMASSORB LA-87, Adekastab LA-82, Adecastab LA- 944FDL, TINUVIN 622LD, TINUVIN 144, TINUVIN 765, and TINUVIN 770DF (BASF).
Examples of the compound containing a phosphite structure include tris (nonylphenyl) phosphite, tris (p-tert-octylphenyl) phosphite, tris [2,4,6-tris (2,4-di-tert-butylphenyl) phosphite, di (2,4-di (tert-butylphenyl) phosphite, bis (p- butylphenyl) pentaerythritol diphosphite, 2,2'-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus, distearylpenta (3-methyl-6-tert-butylphenol) diphosphite, tetrakis (triphenylphosphine) diphosphite, 4,4'-isopropylidene-diphenol alkyl phosphite, Di (tert-butylphenyl) -4,4'-biphenylene phosphite, 2,6-di-tert-butyl-4-methylphenyl phenylpentaerythritol diphosphite, 2,6 tert-butyl-4-methylphenyl-phenyl-pentaerythritol diphosphite, 2, Di (tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,6-di-tert- Amyl-4-methylphenyl-phenyl-pentaerythritol diphosphite, and the like. Among them, compounds containing a phosphite structure include 2,2'-methylenebis (4,6-di-tert-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus, distearylpenta Erythritol diphosphite is preferred.
Examples of commercial products of compounds containing a phosphite structure include adecastab PEP-4C, adecastab PEP-8, adecastab PEP-8W, adecastab PEP-24G, adecastab PEP-36, Adecastabs HP-10, Adecastab 2112, Adecastab 260, Adecastab 522A, Adecastab 1178, Adecastab 1500, Adecastab C, Adecastab 135A, Adecastab 3010, Adecastab TPP (manufactured by ADEKA), IRGAFOS 168 (BASF), and the like.
Examples of the compound containing a thioether structure include, for example, dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol (3-laurylthiopropionate), pentaerythritol tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), pentaerythritol tetrakis (3-stearylthiopropionate), and the like. Among them, pentaerythritol tetrakis (3-laurylthiopropionate) is preferable as a compound containing a thioether structure.
(Commercially available from ADEKA), sumilizer TPL-R, sumilizer TPM, sumilizer TPS, sumilizer TP-D (commercially available from Sumitomo Chemical Co., Ltd.), commercial products of thioether structure-containing compounds such as adecastab AO-412S, adecastab AO- IRGANOXPS 800FD, IRGANOXPS 802FD (BASF), DLTP, DSTP, DMTP, DTTP (manufactured by API Corporation), and the like.
The [D] compounds may be used alone or in combination of two or more. The content of the [D] compound in the radiation-sensitive resin composition is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass or more and 5 parts by mass or less based on 100 parts by mass of the [A] alkali- More preferable. When the content of the [D] compound is within the above range, the light resistance and heat resistance of the cured film for a display element formed of the radiation sensitive resin composition can be effectively increased.
The [D] compound is a compound containing the hindered phenol structure, and the content of the [D] compound is preferably 0.01 part by mass to 10 parts by mass with respect to 100 parts by mass of the [A] alkali-soluble resin. The radiation-sensitive resin composition of the present invention can further improve the light resistance and heat resistance of the cured film for a display element to be formed by containing the above-mentioned compound in the specific amount.
≪ [E] Compound >
The radiation-sensitive resin composition may contain the [E] compound alone or in combination of two or more. The [E] compound can be used in combination with the [C] photopolymerization initiator, for example, in the form of a spacer to obtain a more preferable pattern, and depending on the kind of the [C] photopolymerization initiator, Further, in the case of the interlayer insulating film, the adhesion between the substrate and the interlayer insulating film can be improved.
Examples of the [E] compound include a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, an O-acyloxime compound, an onium salt compound, a benzoin compound, an? -diketone compound, a polynuclear quinone compound, a diazo compound, and an imidosulfonate compound. Among them, the [E] compound preferably contains at least one member selected from the group consisting of a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, and an O-acyloxime compound .
Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- Oxalone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone.
Examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- -Morpholinophenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.
Examples of the imidazole 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. When a non-imidazole-based compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor in combination because it can improve the sensitivity. The hydrogen donor means a compound capable of donating a hydrogen atom to a radical generated from a nonimidazole compound by exposure. Examples of the hydrogen donor include mercapane-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; And amine hydrogen donors such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone. In the present invention, the hydrogen donors may be used singly or in combination of two or more, but it is preferable to use at least one kind of mercaptan hydrogen donor and at least one amine hydrogen donor in combination to improve the sensitivity .
Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) 2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan- Bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] 2- (4-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (Trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4 , 6-bis (trichloromethyl) -s-triazine, and the like.
Examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), ethanone- 1- [ 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuran-2-ylmethoxy) Ethyl-6- (2-methyl-4- (2, 2-dimethyl-thiazol- 1,3-dioxoranyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime).
The content of the [E] compound is preferably 0.01 part by mass to 60 parts by mass, more preferably 1 part by mass to 55 parts by mass, per 100 parts by mass of the [A] alkali-soluble resin. By setting the content of the [E] compound within the above-specified range, it is possible to sufficiently obtain the curing by exposure, and the adhesion with the substrate can be suitably ensured.
≪ Other optional components >
The radiation sensitive resin composition of the present invention may further contain, in addition to the [A] alkali-soluble resin, the [B] polymerizable compound, the [C] photopolymerization initiator, the [D] compound and the [ May optionally contain other optional components such as [F] adhesive auxiliary, [G] surfactant, [H] epoxy compound, [I] storage stabilizer and the like. 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] Adhesion aid can be used to improve the adhesion between the resulting cured film and the substrate. [F] As the adhesion aid, a functional silane coupling agent having a reactive functional group such as a carboxy group, a methacryloyl group, a vinyl group, an isocyanate group, and an oxiranyl group is preferable, and for example, trimethoxysilylbenzoic acid, -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? - (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, and the like.
[F] The content of the adhesion promoter is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, based on 100 parts by mass of the [A] alkali-soluble resin. [F] When the content of the adhesion promoting agent exceeds 20 parts by mass, development residue easily tends to be generated.
[[G] Surfactant]
The [G] surfactant can be used for further improving the film formability of the radiation-sensitive resin composition. [G] As the surfactant, for example, a fluorine-based surfactant, a silicone-based surfactant, and the like can be mentioned.
As the fluorine-based surfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least any of the terminal, main chain and side chain is preferable. Examples of commercial products of the fluorinated surfactants include ftergent FT-100, 110, -140A, -150, -250, -251, -300, -310, 400S, Fotogen FTX-218, and Dong-251 (manufactured by NEOS).
Examples of commercial products of silicone surfactants include toric silicone DC3PA, copper DC7PA, copper SH11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH-190, copper SH-193, copper SZ- 6032, SF-8428, DC-57, DC-190 (trade name, Toray, Dow Corning, Silicone).
The content of the [G] surfactant is preferably 1.0 part by mass or less, and more preferably 0.7 part by mass or less, based on 100 parts by mass of the [A] alkali-soluble resin. If the content of the [G] surfactant exceeds 1.0 part by mass, film unevenness easily occurs.
[[H] epoxy compound]
The radiation sensitive resin composition may contain an [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, bis (3,4-epoxy Cyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'- Hexane carboxylate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis (3,4-epoxycyclohexane Carboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 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 diglyme Diglycidyl ethers of bisphenol compounds such as cy- idyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol S diglycidyl ether;
1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Polyglycidyl ethers of polyhydric alcohols such as cidyl 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 novolak type epoxy resins;
Cresol novolak type epoxy resin;
Polyphenol type epoxy resins;
Cyclic aliphatic epoxy resins;
Diglycidyl esters of aliphatic long chain dibasic acids;
Glycidyl esters of higher fatty acids;
Epoxidized soybean oil, and epoxidized linseed oil.
As a commercially available product of the [H] epoxy compound, for example,
Epikote 604, Copper 1001, Copper 1002, Copper 1003, Copper 1004, Copper 1007, Copper 1009, Copper 1010, Copper 828 (above, Japan Epoxy Resins Co., Ltd.) as the bisphenol A type epoxy resin;
As bisphenol F type epoxy resin, Epikote 807 (Japan Epoxy Resin Co., Ltd.) and the like;
As the phenol novolak type epoxy resin, Epicote 152, Copper 154, Copper 157S65 (above, Japan Epoxy Resins Co., Ltd.), EPPN201, Copper 202 (above, Nippon Kayaku Co., Ltd.) and the like;
Examples of cresol novolak epoxy resins include EOCN102, Copper 103S, Copper 104S, Copper 1020, Copper 1025, Copper 1027 (available from Nippon Kayaku Co., Ltd.), Epikote 180S75 (Japan Epoxy Resins Co., Ltd.) and the like;
As the polyphenol type epoxy resin, Epikote 1032H60 and XY-4000 (above, Japan Epoxy Resin Co., Ltd.) and the like;
As cyclic aliphatic epoxy resins, CY-175, 177, 179, araldite CY-182, copper 192, copper 184 (manufactured by BASF), ERL-4234, copper- (UCC), SHOWDYNE 509 (Showa Denko), EPICLON 200, and Copper 400 (Dainippon Inkusha), Epicote 871, Copper 872 (or more) , Japan Epoxy Resins Co., Ltd.), ED-5661, 5662 (trade name, manufactured by Serraniz Coatings Co., Ltd.);
As the aliphatic polyglycidyl ether, EPOLIGHT 100MF (Kyoeisha Kagaku Co., Ltd.) and EPIOL TMP (Nippon Yushi Co., Ltd.) and the like can be mentioned.
Among them, bisphenol A type epoxy resin and phenol novolak type epoxy resin are preferable.
The content of the [H] epoxy compound is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, based on 100 parts by mass of the [A] alkali-soluble resin. If the amount of the [H] epoxy compound used exceeds 50 parts by mass, the storage stability of the radiation-sensitive resin composition tends to be lowered.
[[I] storage stabilizer]
[I] Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitroso compounds and the like, and more specifically, 4-methoxyphenol, N-nitroso N-phenylhydroxylamine aluminum and the like.
The content of the [I] storage stabilizer is preferably 3.0 parts by mass or less, more preferably 1.0 parts by mass or less based on 100 parts by mass of the [A] alkali-soluble resin. If the content of the [I] storage stabilizer exceeds 3.0 parts by mass, the sensitivity of the radiation sensitive resin composition may be lowered and the pattern shape may be deteriorated.
≪ Preparation method of radiation-sensitive resin composition >
The radiation sensitive resin composition may contain, in addition to the [A] alkali-soluble resin, the [B] polymerizable compound, the [C] photopolymerization initiator and the [D] By weight. The radiation-sensitive resin composition is preferably dissolved in a suitable solvent and used in a solution state.
Examples of the solvent used in the preparation of the radiation sensitive resin composition include a mixture of the alkali-soluble resin [A], the polymerizable compound [B], the photopolymerization initiator [C], the compound [D] Or dissolving or dispersing in the solvent, so as not to react with each component.
From the viewpoints of, for example, solubility of each component, reactivity with each component, ease of forming a coating film, and the like,
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- -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- Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl 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, Diethylene glycol mono-n-propyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, Acetic acid (poly) alkylene glycol monoalkyl ethers such as methoxybutyl;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran;
Methylhexanone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan- Ketones;
Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate and 1,6-hexanediol diacetate;
Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Propyl acetate, n-butyl acetate, n-pentyl formate, i-pentyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylacetate , N-butyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, Ethoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate , Other esters such as ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate and ethyl 2-oxobutyrate;
Aromatic hydrocarbons such as toluene and xylene;
Amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetoamide.
Of 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, Butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methylpentyl glycol diethyl ether, diethylene glycol methyl ether, cyclohexanone, Methyl 3-methoxybutyl propionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, methyl iodide, , N-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate and ethyl pyruvate are preferable, and propylene glycol monomethyl ether acetate is more preferable Do. The solvent may be used alone or in combination of two or more.
Further, in order to increase the in-plane uniformity of the film thickness together with the solvent, a high boiling point solvent may be used in combination. Examples of the high-boiling solvent include organic solvents such as benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, Diethyl maleate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate and the like. The high boiling point solvent may be used alone or in combination of two or more.
The content of the solvent is not limited, but from the viewpoints of coatability, stability, and the like of the resulting radiation-sensitive resin composition, the amount of the radiation-sensitive resin composition in which the total density of each component other than the solvent is 5% by mass to 50% By mass, more preferably 10% by mass to 40% by mass. When the radiation sensitive resin composition is prepared in the form of a solution, the solid concentration (component other than the solvent occupying the composition solution) may be any density (for example, 5 mass% 50% by mass). The preferable solid content concentration differs depending on the method of forming the coating film on the substrate, which will be described later. The thus prepared composition solution may be filtered after using a millipore filter having a pore diameter of about 0.5 mu m and then provided for use.
≪ Method of forming cured film for display element >
The radiation sensitive resin composition is preferably used for forming a cured film for a display element. The present invention preferably includes a cured film for a display element formed of the radiation sensitive resin composition.
The method for forming a cured film for a display element of the present invention is characterized in that,
(1) a step of forming a coating film on a substrate using the 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) 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 excellent in compression performance, transmittance, light resistance, voltage holding ratio, developing 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 non-alkali glass, resin substrates made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and polyimide have.
Examples of the transparent conductive film formed on one surface of the transparent substrate include an NESA film made of tin oxide (SnO 2 ) (registered trademark of US PPG), an ITO film made of indium tin oxide (In 2 O 3 -SnO 2 ), and the like. Can be mentioned.
When forming a coating film by the apply | coating method, after apply | coating the solution of the said radiation sensitive resin composition on the said transparent conductive film, Preferably, a coating film can be formed by heating (prebaking) an application surface. The solid content concentration of the composition solution used in the coating method is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and particularly preferably 15% by mass to 35% by mass. Examples of the application method of the radiation sensitive resin composition include a coating method such as a spraying method, a roll coating method, a rotation coating method (spin coating method), a slit coating method (slit die coating method), a bar coating method, An appropriate method can be adopted. Among these, a spin coating method or a slit coating method is preferable.
The prebaking conditions are preferably 70 ° C to 120 ° C, and preferably about 1 minute to 15 minutes, depending on the kind of each component, blending ratio, and the like. The thickness of the coating film after pre-baking is preferably 0.5 to 10 mu m, more preferably 1.0 to 7.0 mu m.
[Step (2)]
In this step, at least a part of the formed coating film is irradiated with radiation. At this time, when irradiating only a part of the coating film, for example, a method of irradiating with a photomask having a predetermined pattern may be employed. Examples of the radiation used for the irradiation include visible light, ultraviolet light, and far ultraviolet light. Among these, the radiation whose wavelength is in the range of 250 nm-550 nm is preferable, and the radiation which contains the ultraviolet-ray of 365 nm is more preferable.
The radiation dose (exposure dose) is preferably from 100 J / m 2 to 5,000 J / m 2, as measured by a light meter (OAI model 356, manufactured by Optical Associates Inc.) at a wavelength of 365 nm of the irradiated radiation, More preferably from 200 J / m 2 to 3,000 J / m 2.
The radiation sensitive resin composition of the present invention is superior in sensitivity to a conventionally known composition and has a desired film thickness, good shape, excellent adhesive property and high hardness even when the radiation dose is not more than 700 J / m 2, and more desirably not more than 600 J / A cured film for a display element can be obtained.
[Step (3)]
In this step, unnecessary portions are removed by developing the coated film after irradiation with radiation to form a predetermined pattern. Examples of the developing solution used in the development include aqueous solutions of alkaline compounds such as inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, . You may add a suitable amount of water-soluble organic solvents, such as methanol and ethanol, and / or surfactant to the aqueous solution of the said alkaline compound.
As the developing method, any of a puddle method, a dipping method and a shower method may be used, and the developing time is preferably about 10 seconds to 180 seconds at room temperature. Following the development treatment, for example, water washing is carried out for 30 seconds to 90 seconds, followed by air drying with compressed air or compressed nitrogen to obtain a desired pattern.
[Step (4)]
In this step, the resulting patterned coating film is heated by a suitable heating apparatus such as a hot plate or an oven to obtain a cured film for a display element. The heating temperature is about 100 ° C to 250 ° C. The heating time is, for example, about 5 minutes to 30 minutes on a hot plate and about 30 minutes to 180 minutes in an oven.
<Manufacturing Method of Display Element>
The present invention suitably includes a display element having the cured film for a display element. As a manufacturing method of a display element, a pair (two sheets) of transparent substrates having a transparent conductive film (electrode) on one surface are prepared, and the radiation sensitive resin composition is applied onto a transparent conductive film of one of the substrates , A spacer or a protective film or both are formed according to the above-described method. Subsequently, an alignment film having liquid crystal aligning ability is formed on the transparent conductive film and the spacer or the protective film of these substrates. These substrates were placed face to face with a certain gap (cell gap) so that the liquid crystal alignment directions of the respective alignment films were orthogonal or anti-parallel with the side of the side on which the alignment film was formed as the inside, The liquid crystal is filled in the cell gap defined by the spacer, and the filling hole is sealed to constitute the liquid crystal cell. The display device of the present invention is obtained by joining a polarizing plate on both outer surfaces of the liquid crystal cell so that the polarizing direction thereof coincides with or orthogonal to the liquid crystal alignment direction of the alignment film formed on one side of the substrate.
As another method, a pair of transparent substrates on which a transparent conductive film, an interlayer insulating film, a protective film or a spacer, and an orientation film are formed is prepared in the same manner as the above method. Thereafter, an ultraviolet curable sealant is applied to the end of one of the substrates using a dispenser. Subsequently, the liquid crystal is dropped into a minute droplet shape using a liquid crystal dispenser, and bonding of both substrates is performed under vacuum. Then, the above sealing agent is irradiated with ultraviolet rays using a high pressure mercury lamp to seal both substrates. Finally, the polarizing plate is bonded to both outer surfaces of the liquid crystal cell to obtain the display element of the present invention.
Examples of the liquid crystal used in each of the above methods include a nematic liquid crystal and a smectic liquid crystal. Moreover, as a polarizing plate used on the outer side of a liquid crystal cell, the polarizing plate which interposed the polarizing film called "H film | membrane" which absorbed iodine while extending | stretching polyvinyl alcohol, the cellulose acetate protective film, or the polarizing plate which consists of H film itself, etc. Can be mentioned.
(Example)
Hereinafter, although this invention is explained based on an Example, this invention is not interpreted limitedly to this Example.
<[A] Synthesis of alkali-soluble resin>
Synthesis Example 1
5 parts by mass of 2,2-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate were added to a 500 ml flask equipped with a cooling tube and a stirrer, and 18 parts by mass of methacrylic acid, 5.2 parts by mass of methacrylic acid tricyclo [5.2 .1.0 2.6 ] decane-8-yl, 5 parts by mass of styrene, 30 parts by mass of hydroxyethyl methacrylate and 22 parts by mass of benzyl methacrylate were charged and replaced with nitrogen, and while stirring was continued gently, Lt; RTI ID = 0.0 > 80 C. < / RTI > This temperature was maintained for 5 hours and polymerized to obtain a copolymer solution having a solid content concentration of 28.8% by mass.
The weight average molecular weight (Mw) of the obtained copolymer solution was measured using GPC-101 (trade name: manufactured by Showa Denko K.K.), and Mw = 10,000.
Next, 14 parts by mass of 2-methacryloyloxyethyl isocyanate (trade name: CALENS MOI, manufactured by Showa Denko K.K.) and 0.1 part by mass of 4-methoxyphenol were added, and the mixture was stirred at 40 ° C for 1 hour, At 60 ° C for 2 hours. The end point of the reaction was the disappearance of a peak near 2270 cm -1 derived from the isocyanate group of 2-methacryloyloxyethyl isocyanate. The solid concentration of the obtained resin solution was 30.0 mass% and Mw = 12000. This copolymer solution was designated as (A-1).
Synthesis Example 2
4 parts by mass of 2,2'-azobisisobutyronitrile and 300 parts by mass of diethylene glycol methyl ethyl ether were placed in a flask equipped with a stirrer, a cooling tube and a stirrer, and then (a1) methacrylic acid 23 10 parts by mass of styrene, 32 parts by mass of benzyl methacrylate and 35 parts by mass of methyl methacrylate, and 2.7 parts by mass of? -Methylstyrene dimer as a molecular weight regulator were added to the mixture while gently stirring , The temperature of the solution was raised to 80 DEG C, the temperature was maintained for 4 hours, the temperature was raised to 100 DEG C, and this temperature was maintained for 1 hour to polymerize to obtain a solution containing the copolymer (solid content concentration = 24.9 mass%). The Mw of the obtained copolymer was 12,500.
Subsequently, 1.1 parts by mass of tetrabutylammonium bromide and 0.05 part by mass of 4-methoxyphenol as a polymerization inhibitor were added to the solution containing the copolymer, and the mixture was stirred at 90 캜 for 30 minutes in an air atmosphere. Thereafter, glycidyl methacrylate 16 (A-2) was obtained (solid content concentration = 29.0 mass%) by reacting the mixture at 90 占 폚 for 10 hours. The Mw of the copolymer (A-2) was 14,200. (A3) of glycidyl methacrylate was determined by 1 H-NMR analysis on the resolidified resin solid content by performing reprecipitation purification by dropping the solution containing the copolymer (A-2) in hexane, The generation rate of the structural unit) was calculated. The ratio of the peak derived from the methacryl group of glycidyl methacrylate to the proton of the aromatic ring near 6.8 ppm to 7.4 ppm derived from the structural unit of the copolymer of benzyl methacrylate at about 6.1 ppm and around 5.6 ppm From the comparison, 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
7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 250 parts by mass of diethylene glycol methyl ethyl ether were put in a flask equipped with a cooling tube and a stirrer, and 18 mass parts of methacrylic acid 32 parts by mass of methacrylic acid tricyclo [5.2.1.0 2,6 ] decane-8, 5 parts by mass of styrene, 5 parts by mass of butadiene and 40 parts by mass of glycidyl methacrylate were charged, , The temperature of the solution was raised to 70 캜 while maintaining this temperature for 5 hours, thereby obtaining a copolymer solution having a solid content concentration of 31.0% by mass. With respect to the obtained copolymer solution, Mw was measured by GPC and found to be Mw = 11,000. This copolymer solution was designated as (A-3).
Synthesis Example 4
A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate were placed. Subsequently, 20 parts by mass of styrene, 18 parts by mass of methacrylic acid, 20 parts by mass of methacrylic acid tricyclo [5.2.1.0 2,6 ] decan-8-yl and 3 parts of 3-ethyl-3-methacryloyloxymethyloxetane And 42 parts by mass of the mixture were purged with nitrogen, and stirring was started gently. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a copolymer solution. The solid concentration of the obtained polymer solution was 33.0% by mass, and Mw was measured by GPC, and found to be Mw = 24,000. This copolymer solution was designated as (A-4).
<Preparation of radiation sensitive resin composition>
Details of each component used in Examples and Comparative Examples are shown below.
≪ [B] Polymerizable compound >
B-1: A 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: Viscoat 802 (mixture of tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate, Yukiko Kakako, Osaka)
≪ [C] Photopolymerization initiator >
C-2: The compound represented by the above formula (C-2)
C-3: The compound represented by the above formula (C-3)
C-6: A compound represented by the above formula (C-6)
C-8: A compound represented by the 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 (Adecastab AO-20,
D-4: 1,3,5-Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (Adecastab AO-
D-5: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (TINUVIN 770 BASF)
D-6: distearyl pentaerythritol diphosphite (adecastab PEP-8, Adeca)
D-7: pentaerythritol tetrakis (3-laurylthiopropionate) (adecastab AO-412S, Adeca)
≪ [E] Compound >
E-1: 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (IRGACURE 907, Chiba Specialty Chemicals)
E-2: Ethanol-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O- acetyloxime) (Irgacure OXE02, Chiba Specialty · Chemical companies)
E-3: 1,2-Octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (Irgacure OXE01, Chiba Specialty Chemicals)
E-4: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-
E-5: 4,4'-bis (diethylamino) benzophenone
<[F] Adhesion preparation>
F-1:? -Glycidoxypropyltrimethoxysilane
<[G] surfactant>
G-1: FTX-218 (NEOS)
Example 1
100 parts by mass of [A] the copolymer solution (A-1) as the alkali-soluble resin in terms of solid content, 100 parts by mass of (B-1) as the polymerizable compound [B] 5 parts by mass of (F-1) as an adhesion promoter and 0.5 part by mass of (G-1) as a surfactant were mixed and propylene glycol monomethyl ether acetate (PGMEA) was added thereto so as to have a solid content concentration of 30% And then filtered through a Millipore filter having a pore diameter of 0.5 탆 to prepare a radiation-sensitive resin composition.
[Examples 2 to 9 and Comparative Examples 1 to 2]
Each of the radiation sensitive resin compositions was prepared in the same manner as in Example 1 except that the components of the type and content shown in Table 1 were mixed. In Table 1, "-" indicates that the corresponding component was not used.
<Evaluation>
The following evaluations were carried out using each of the prepared radiation sensitive resin compositions. Specifically, for Examples 1 to 4 and Comparative Example 1, a cured film for a display element was formed using each radiation-sensitive resin composition, and the resolution, sensitivity, and compression performance as a spacer were evaluated. For Examples 5 to 9 and Comparative Example 2, a cured film for a display element was formed using each radiation-sensitive resin composition, and the transmittance, light resistance, and voltage holding ratio as an interlayer insulating film were evaluated. The results are shown in Table 2.
[Resolution (탆)]
Each of the radiation sensitive resin composition solutions was coated on a non-alkali glass substrate with a spinner and prebaked on a hot plate at 100 DEG C for 2 minutes to form a coating film having a film thickness of 4.0 mu m. Subsequently, a photomask having a plurality of circular residue patterns having different sizes in a range of 8 mu m to 20 mu m in diameter was interposed between the obtained coating film and an exposure amount of 200 J / m < 2 > to 1,000 J / And irradiated with the radiation. Thereafter, a shower phenomenon was carried out by using 0.40 mass% aqueous potassium hydroxide solution at 23 占 폚 as a developing solution at a developing pressure of 1 kgf / cm2 and a nozzle diameter of 1 mm, followed by pure water cleaning for 1 minute. Further, post-baking was performed in an oven at 230 캜 for 30 minutes to form a pattern-forming coating film. At this time, the minimum pattern size to be formed was defined as the resolution (占 퐉). If a pattern with a size of 12 mu m or less is formed in the photomask of 12 mu m or less, it can be judged that the resolution is good.
[Sensitivity (J / m 2)]
An annular residue pattern was formed on the substrate by operating in the same manner as in the above evaluation of the resolution, except that a photomask having a plurality of annular residue patterns having a diameter of 15 mu m was used. The heights of the cyclic residue patterns before and after development were measured using a laser microscope (VK-8500, manufactured by KYENS Corporation). The residual film ratio (%) was obtained from this value and the following formula.
Remaining film ratio (%) = (height after development / height before development) x 100
The minimum exposure amount at which the residual film ratio was 90% or more was defined as the sensitivity (J / m < 2 >). When the exposure amount is 700 J / m 2 or less, it can be judged that the sensitivity is good.
[Compression performance]
An annular residue pattern was formed on the substrate at an exposure amount at which the residual film ratio was 90% or more by operating in the same manner as in the evaluation of the sensitivity. This pattern was subjected to a compressive test with a load of 40 mN using a planar indenter of 50 탆 square shape with a micro compression tester (fischer scope H100C, Fisher Instruments), and the amount of compressive displacement (탆) Respectively. The recovery rate (%) was calculated from the amount of displacement when the load was 40 mN and the amount of displacement when the load of 40 mN was removed. When the recovery rate is 90% or more and the amount of compression displacement at the time of 40 mN is 0.15 탆 or more, it can be judged that the compression performance is good.
[Transmittance (%)]
(%) At a wavelength of 400 nm was measured for a cured film for a display element obtained by operating in the same manner as in the evaluation of the above resolution, except that the exposure was performed at an exposure amount of 800 J / m & (150-20 type double beam, Hitachi SEISAKUSHO Co., Ltd.). When the transmittance is 90% or more, it can be judged that transparency is good.
[Light Resistance (%)]
The cured film for a display element was formed in the same manner as in the evaluation of the transmittance. The obtained cured film for a display device was evaluated by irradiating UV light of 500 kJ / m 2 with a UV irradiation device (UVX-02516S1JS01, USHIO, lamp; UVL-4001M3-N1) . When the residual film ratio is 95% or more, it can be judged that the light resistance (%) is good.
[Voltage Conservation Rate (%)]
Each of the radiation-sensitive resin compositions was spin-coated on a soda glass substrate on which an SiO 2 film was formed to prevent dissolution of sodium ions on the surface and an ITO (indium-tin oxide alloy) electrode was deposited in a predetermined shape , And then prebaked in a clean oven at 90 캜 for 10 minutes to form a coating film having a thickness of 2.0 탆. Subsequently, the coated film was exposed at an exposure amount of 500 J / m < 2 > without interposing a photomask. Thereafter, this substrate was immersed in a developer composed of 0.04 mass% aqueous solution of potassium hydroxide at 23 캜 for 1 minute, developed, washed with ultrapure water, air-dried, and further post baked at 230 캜 for 30 minutes, And cured to form a permanent cured film. Subsequently, the substrate on which the pixel was formed and the substrate on which the ITO electrode was simply vapor-deposited in a predetermined shape were bonded to each other with a sealing material mixed with glass beads of 0.8 mm, and then a liquid crystal MLC6608 was injected to prepare a liquid crystal cell did. Subsequently, the liquid crystal cell was placed in a thermostatic chamber at 60 占 폚, and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage preservation rate measuring system (Model VHR-1A, 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 a voltage applied to the liquid crystal cell after 16.7 milliseconds / 0 milliseconds. If the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell can not maintain the applied voltage at a predetermined level for 16.7 milliseconds and can not sufficiently orient the liquid crystal. The "burn- There is a high possibility of causing it.
[Evaluation of Permittivity]
The composition described in Table 1 was applied to each of the polished SUS substrates using a spinner and then baked on a hot plate at 90 DEG C for 2 minutes to form a coating film having a thickness of 3.0 mu m. The obtained coating film was exposed to a total irradiation amount of 3,000 J / m 2 with a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon Inc., and then heated in a clean oven at 220 캜 for 1 hour to form a cured film on the substrate . For each of the cured films, a Pt / Pd electrode pattern was formed by a vapor deposition method to prepare a sample for dielectric constant measurement. The relative dielectric constant of each substrate was measured by the CV method at a frequency of 10 kHz using an HP16451B electrode manufactured by Yokogawa Hewlett Packard Co., Ltd. and an HP4284A Precision LCR Meter (Precision LCR Meter). This result is shown in Table 1. When this value is 3.5 or less, the relative dielectric constant is considered to be good.
In the evaluation of the relative dielectric constant, patterning of the film to be formed is not necessary, so that only the film forming step, the post-exposure step and the heating step are performed for evaluation.
As apparent from the results of Table 2, the radiation sensitive resin composition of the present invention is excellent in resolution, sensitivity and compression performance in the case of spacer evaluation, and has excellent transmittance, light resistance, voltage holding ratio and low dielectric constant when evaluated as an interlayer insulating film .
Claims (11)
[B] a polymerizable compound having an ethylenically unsaturated bond,
[C] at least one photopolymerization initiator selected from the group consisting of compounds represented by the following formulas (C-1) to (C-12), and
[D] One or two or more compounds selected from the group consisting of a compound containing a hindered phenol structure, a compound containing a hindered amine structure and a compound containing an alkyl phosphite structure
A radiation sensitive resin composition containing a.
The radiation sensitive resin composition of at least 1 sort (s) which the polymeric group of (a2) structural unit is chosen from an oxiranyl group, an oxetanyl group, and a (meth) acryloyl group.
Wherein the amount of the [C] photopolymerization initiator used ranges from 0.1 to 10 parts by mass based on 100 parts by mass of the [A] alkali-soluble resin.
[B] A radiation-sensitive resin composition wherein the polymerizable compound having an ethylenically unsaturated bond is a polymerizable unsaturated compound having a hydroxyl group or a carboxyl group.
Furthermore, 1 selected from the group which consists of a thioxanthone type compound, an acetophenone type compound, a biimidazole type compound, a triazine type compound, an O-acyl oxime type compound (other than [C] component), and a thiol type compound A radiation sensitive resin composition containing a seed or two or more compounds.
(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
Of the cured film for a display element.
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| JP2013211924A JP2014134763A (en) | 2012-12-11 | 2013-10-09 | Radiation-sensitive resin composition, cured film for display element, method for forming cured film for display element, and display element |
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| JP6195584B2 (en) * | 2015-02-04 | 2017-09-13 | 東京応化工業株式会社 | Colorant dispersion, photosensitive resin composition containing the same, and dispersion aid |
| CN108137443B (en) * | 2015-07-31 | 2021-06-08 | 克美 | Fluorene derivative, photopolymerization initiator containing same, and photoresist composition |
| KR101788399B1 (en) * | 2015-09-23 | 2017-10-19 | (주)경인양행 | Oxime ester compound having improved heat stability, photopolymerization initiator and photoresist composition comprising the same |
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| JP2010015025A (en) * | 2008-07-04 | 2010-01-21 | Adeka Corp | Photosensitive composition containing specific photopolymerization initiator |
| JP2010156879A (en) | 2008-12-29 | 2010-07-15 | Fujifilm Corp | Photosensitive composition, color filter and liquid crystal display |
| KR101067188B1 (en) | 2004-07-20 | 2011-09-22 | 제이에스알 가부시끼가이샤 | Radiation Sensitive Resin Composition, Spacer for Display Panel and Display Panel |
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| JP3101986B2 (en) | 1992-07-24 | 2000-10-23 | ジェイエスアール株式会社 | Heat-resistant radiation-sensitive resin composition |
| JP3994429B2 (en) | 1998-12-01 | 2007-10-17 | Ｊｓｒ株式会社 | Radiation sensitive resin composition for interlayer insulation film |
| JP3965868B2 (en) | 2000-06-12 | 2007-08-29 | Ｊｓｒ株式会社 | Interlayer insulation film and microlens |
| JP4315010B2 (en) | 2004-02-13 | 2009-08-19 | Ｊｓｒ株式会社 | Radiation-sensitive resin composition, display panel spacer and display panel |
| EP2128132B1 (en) | 2006-12-27 | 2014-01-15 | Adeka Corporation | Oxime ester compound and photopolymerization initiator containing the same |
| JP4998735B2 (en) * | 2006-12-28 | 2012-08-15 | Ｊｓｒ株式会社 | Radiation sensitive composition, color filter, black matrix, and liquid crystal display device |
| EP2223910B1 (en) * | 2007-12-25 | 2012-11-07 | Adeka Corporation | Oxime esters and photopolymerization initiators containing the same |
| JP5625460B2 (en) * | 2010-04-15 | 2014-11-19 | Jsr株式会社 | Positive radiation-sensitive composition, interlayer insulating film and method for forming the same |
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| KR101067188B1 (en) | 2004-07-20 | 2011-09-22 | 제이에스알 가부시끼가이샤 | Radiation Sensitive Resin Composition, Spacer for Display Panel and Display Panel |
| JP2010015025A (en) * | 2008-07-04 | 2010-01-21 | Adeka Corp | Photosensitive composition containing specific photopolymerization initiator |
| JP2010156879A (en) | 2008-12-29 | 2010-07-15 | Fujifilm Corp | Photosensitive composition, color filter and liquid crystal display |
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