CN110760257A - Curable composition, cured film and color filter substrate - Google Patents

Curable composition, cured film and color filter substrate Download PDF

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Publication number
CN110760257A
CN110760257A CN201910490180.9A CN201910490180A CN110760257A CN 110760257 A CN110760257 A CN 110760257A CN 201910490180 A CN201910490180 A CN 201910490180A CN 110760257 A CN110760257 A CN 110760257A
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compound
curable composition
polyfunctional
cured film
carboxyl
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CN110760257B (en
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堀田佑策
木村佑希
洼内希恵
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JNC Corp
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/16—Polyester-imides
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    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
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    • C08G59/4042—Imines; Imides
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    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G02F1/133519—Overcoatings
    • 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
    • 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
    • G03F7/0387—Polyamides or polyimides
    • G—PHYSICS
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Abstract

The present invention relates to a curable composition, a cured film, and a color filter substrate, wherein the curable composition comprises an imide compound (A) which is a reaction product obtained by using an acid anhydride (a1) having a polymerizable double bond and an alkoxysilyl compound (a2) having an amino group as essential raw materials, a polyfunctional carboxyl compound (B) which is a compound having three or more carboxyl groups per molecule, and a polyfunctional epoxy compound (C) which is a compound having three or more epoxy groups per molecule. The curable composition of the present invention has low viscosity and high planarization. By using the curable composition of the present invention, a cured film having high transparency, heat resistance and photo-alignment properties can be obtained.

Description

Curable composition, cured film and color filter substrate
Technical Field
The present invention relates to a curable composition for providing a color filter protective film having photo-alignment properties, a cured film formed from the curable composition, and a color filter substrate including the cured film.
Background
A display element for color display or the like includes a color filter substrate. The color filter substrate includes a coloring body of red (R), green (G) and blue (B) or a black matrix for preventing color mixing, and a level difference is present on the surface of the color filter substrate. In order to make the cell gap of the liquid crystal display element uniform in the plane or make the film thickness of the optical function film formed on the color filter substrate uniform, a color filter protective film having a function of flattening the level difference on the surface of the color filter substrate is used. In addition, an alignment film having a function of controlling the alignment direction of liquid crystal molecules is included in order to control the alignment direction of liquid crystal molecules in a liquid crystal display device or to control the alignment direction of polymerizable liquid crystal molecules when an optical functional film is formed using a polymerizable liquid crystal composition. In order to reduce the thickness and weight of a liquid crystal display device, a color filter protective film having both functions performed by the two films and having alignment properties has been developed.
Examples of the color filter protective film having alignment properties include a color filter protective film having a rubbing alignment property described in patent document 1 and a color filter protective film having a photo alignment property described in patent document 2. The composition for providing the former protective film is a curable composition containing polyimide and an epoxy compound, and the method for aligning the former protective film is a rubbing method. The composition for providing the latter protective film is a curable composition comprising a polymer having a photo-alignment group such as a cinnamoyl group and a crosslinkable group such as an epoxy group, and a crosslinking component which is a polyesteramic acid, and the latter alignment treatment is performed by irradiation with linearly polarized ultraviolet rays. In order to improve the display quality of a liquid crystal display element, an alignment treatment step has been advanced to replace the rubbing method, which causes static electricity due to direct contact with a film, with non-contact linearly polarized ultraviolet irradiation, and a color filter protective film having photo-alignment properties and a composition for providing the color filter protective film have been desired.
However, in order to meet the recent demand for a display element with lower power consumption and longer life, the color filter protective film having photo-alignment properties described in patent document 2 is required to have two types of characteristics. The first is to improve the transparency of the protective film for the purpose of improving the light transmittance of the liquid crystal display element. The second is improvement of the heat resistance of the protective film (reduction of the amount of decrease in the amount of heat weight at the time of additional heating) for the purpose of reducing the influence on other members of the liquid crystal display element due to outgassing from the protective film.
As a composition used for forming a color filter protective film having photo-alignment properties, it is conceivable to use a composition for a photo-alignment film (for example, patent document 3). However, the composition for a photo-alignment film described in patent document 3 has high viscosity (a coating film obtained by applying the composition and removing the composition with a solvent is easily sticky). Therefore, there are problems as follows: when forming the color filter protective film with photo-alignment property, the foreign matter is adhered; or the fingers of the operator touch the surface of the coating film to cause the coating film to have marks. Further, there are problems as follows: the composition for a photo-alignment film has poor planarization properties when formed with a film thickness (e.g., 100nm) used as a general photo-alignment film, and has poor planarization properties and low display quality of a liquid crystal display element even when formed with a film thickness (e.g., 1.5 μm) used as a general color filter protective film.
From the above, development of a curable composition having low viscosity and high planarization property, which provides a cured film having high transparency, heat resistance and photo-alignment property, has been desired.
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent laid-open No. Hei 9-230364
[ patent document 2] Japanese patent laid-open No. 2014-84355
[ patent document 3] Japanese patent laid-open No. 2015-
Disclosure of Invention
[ problems to be solved by the invention ]
The invention provides a curable composition which provides a cured film having high transparency, heat resistance and photo-alignment properties, low in viscosity and high in planarization, a cured film obtained from the curable composition, and a color filter substrate including the cured film.
[ means for solving problems ]
The present inventors have made extensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned object can be achieved by a curable composition comprising an imide compound (a) which is a reaction product obtained by using as essential raw materials an acid anhydride (a1) having a polymerizable double bond and an alkoxysilyl compound (a2) having an amino group, a polyfunctional carboxyl compound (B) which is a compound having three or more carboxyl groups per molecule, and a polyfunctional epoxy compound (C) which is a compound having three or more epoxy groups per molecule, and a cured film obtained by curing the curable composition.
[1] A curable composition comprising an imide compound (A), a polyfunctional carboxyl compound (B) and a polyfunctional epoxy compound (C),
the imide compound (A) is a reaction product derived from raw materials which are essential for an acid anhydride (a1) having a polymerizable double bond and an alkoxysilyl compound (a2) having an amino group,
the polyfunctional carboxyl compound (B) is a compound having three or more carboxyl groups per molecule,
the polyfunctional epoxy compound (C) is a compound having three or more epoxy groups per molecule.
[2] The curable composition according to [1], wherein the imide compound (A) is 5 to 80% by weight in 100% by weight of the total amount of the imide compound (A), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C);
the amount of the polyfunctional carboxyl compound (B) is 20 to 80 wt% based on 100 wt% of the total amount of the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C).
[3] The curable composition according to [1], wherein the imide compound (A) is 15 to 60% by weight in 100% by weight of the total amount of the imide compound (A), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C);
the amount of the polyfunctional carboxyl compound (B) is 40 to 75 wt% based on 100 wt% of the total amount of the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C).
[4] The curable composition according to any one of [1] to [3], wherein the acid anhydride (a1) having a polymerizable double bond is at least one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2).
Figure BDA0002086737890000031
In the formula (1), R1And R2Each independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms.
Figure BDA0002086737890000032
In the formula (2), R3Is hydrogen or C1-5 alkyl.
[5] The curable composition according to any one of [1] to [4], wherein the acid anhydride (a1) having a polymerizable double bond is at least one selected from maleic anhydride, citraconic anhydride and itaconic anhydride.
[6] The curable composition according to any one of [1] to [5], wherein the alkoxysilane-based compound having an amino group (a2) is at least one selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminophenyltrimethoxysilane and 4-aminophenyltriethoxysilane.
[7] The curable composition according to any one of [1] to [6], wherein the polyfunctional carboxyl compound (B) is a polyesteramic acid comprising a tetracarboxylic dianhydride, a diamine and a polyvalent hydroxyl compound as essential raw materials.
[8] A cured film obtained by curing the curable composition according to any one of [1] to [7 ].
[9] A color filter substrate comprising the cured film according to item [8 ].
[ Effect of the invention ]
The curable composition according to a preferred embodiment of the present invention is a curable composition which provides a cured film having high transparency, heat resistance and photo-alignment properties, and has low viscosity and high planarization properties. The cured film obtained from the curable composition is useful as a color filter protective film. Since the cured film has high transparency, the curable composition has high planarization properties, and the curable composition has low viscosity, adhesion of foreign matter is reduced when the cured film is formed, and thus, when the cured film is used as a color filter protective film, the display quality of a liquid crystal display element is high. Since the cured film has high heat resistance, the display element including the cured film has little influence on other members due to degassing from the cured film. Further, since the cured film has high photo-alignment properties, alignment control of liquid crystal molecules can be performed without using an alignment film.
Detailed Description
In the present specification, the term "(meth) acrylic acid" may be used to indicate one or both of "acrylic acid" and "methacrylic acid". Similarly, the term "(meth) acrylate" may be used to indicate one or both of "acrylate" and "methacrylate", and the term "(meth) acryloyloxy" may be used to indicate one or both of "acryloyloxy" and "methacryloyloxy".
< 1. curable composition of the present invention
The curable composition of the present invention comprises an imide compound (A), a polyfunctional carboxyl compound (B) and a polyfunctional epoxy compound (C).
In the curable composition of the present invention, there are preferred blending ratios of the imide compound (a), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C). In order to obtain a cured film having high photo-alignment properties, the blending ratio of the imide compound (a) in 100 wt% of the total amount of the imide compound (a), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C) is preferably 5 wt% or more, and more preferably 15 wt% or more. In order to obtain a curable composition having low viscosity and high planarization properties, the blending ratio of the imide compound (a) in 100 wt% of the total amount of the imide compound (a), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C) is preferably 80 wt% or less, and more preferably 60 wt% or less. In order to obtain a cured film having high heat resistance and high photo-alignment properties, the blending ratio of the polyfunctional carboxyl compound (B) to the polyfunctional epoxy compound (C) is preferably 20 to 80% by weight, more preferably 40 to 75% by weight, based on 100% by weight of the total amount of the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C).
In the present specification, the imide compound (a), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C) may be collectively referred to as "main components", and the total amount of the imide compound (a), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C) may be collectively referred to as "main component amount".
< 1-1. imide Compound (A) >
The imide compound (a) used in the present invention is a reaction product derived from raw materials which are essential for the acid anhydride (a1) having a polymerizable double bond and the alkoxysilyl compound (a2) having an amino group.
Regarding the raw material of the imide compound (a), the preferable content ratio of the acid anhydride (a1) having a polymerizable double bond and the alkoxysilyl compound (a2) having an amino group is 0.8 or more and 1.2 or less, and more preferably the content ratio is 0.9 or more and 1.1 or less, in terms of the molar ratio (acid anhydride group/amino group) of the acid anhydride (a1) having a polymerizable double bond to the amino group of the alkoxysilyl compound (a2) having an amino group. If the content ratio is the above, the amount of exposure required for the photo-alignment property is small.
< 1-1-1. acid anhydride (a1) >, having polymerizable double bond
In the present invention, as a raw material for obtaining the imide compound (a), an acid anhydride (a1) having a polymerizable double bond is used.
In view of the availability of raw materials and the solubility of the imide compound (A) to be obtained in a solvent, preferred acid anhydrides (a1) having a polymerizable double bond are compounds represented by the following formula (1) and compounds represented by the following formula (2).
Figure BDA0002086737890000041
In the formula (1), R1And R2Each independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms.
Figure BDA0002086737890000042
In the formula (2), R3Is hydrogen or C1-5 alkyl.
In the formula (1), R1And R2Each independently is preferably hydrogen or methyl; more preferably R1And R2Both hydrogen (the compound represented by the formula (1) is maleic anhydride) and R1And R2One is hydrogen and the other is methyl (the compound represented by formula (1) is citraconic anhydride).
In the formula (2), R3Preferably hydrogen or methyl; more preferably R3Is hydrogen (the compound represented by formula (2) is itaconic anhydride).
The acid anhydride (a1) having a polymerizable double bond is particularly preferably citraconic anhydride. Citraconic anhydride is low in reactivity of a polymerizable double bond in producing the imide compound (A), and the imide compound (A) can be easily produced.
< 1-1-2 > alkoxysilyl compound having amino group (a2) >
In the present invention, as a raw material for obtaining the imide compound (a), an alkoxysilane-based compound (a2) having an amino group is used.
Specific examples of the alkoxysilyl compound (a2) having an amino group are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminophenyltrimethoxysilane, 4-aminophenyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane and 3- (2-aminoethylamino) propyltriethoxysilane. More than one of these compounds may be used.
In view of reactivity and easiness of obtaining raw materials, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane and 3-aminopropylmethyldiethoxysilane are preferable, and 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane are more preferable.
< 1-1-3. method for synthesizing imide Compound (A)
The method for reacting the imide compound (a) is not particularly limited, but is preferably a reaction in a solution using a solvent. In the present specification, the solvent used in the synthesis to obtain the imide compound (a) is simply referred to as "synthesis solvent". The acid anhydride (a1) having a polymerizable double bond and the alkoxysilyl compound (a2) having an amino group are easily reacted by stirring in a solution at room temperature to form an amic acid. Since the temperature in the system rises due to the heat of reaction when the amic acid is produced, the temperature in the system can be easily controlled by carrying out the reaction in solution.
Thereafter, the amic acid is heated and imidized to obtain the imide compound (A). The obtained imide compound (a) has a group having a polymerizable double bond and an imide structure, and has an unreacted alkoxysilane group.
The heating temperature for the imidization is 60 to 150 ℃ and preferably 80 to 130 ℃. An alkali catalyst may also be added as the imidization catalyst. Examples of base catalysts are pyridine, triethylamine, trimethylamine, tributylamine and trioctylamine. Further, a polymerization inhibitor may be used in combination for the purpose of inhibiting polymerization of the photopolymerizable group initiated in the reaction. Examples of polymerization inhibitors are 2,2,6, 6-tetramethylpiperidyl-1-oxyl, 4-hydroxy-2, 2,6, 6-tetramethylpiperidyl-1-oxyl, triphenyltetrazinyl (verdazyl), p-methoxyphenol, hydroquinone and dibutylhydroxytoluene.
The synthesis solvent is not particularly limited as long as it can dissolve the acid anhydride (a1) having a polymerizable double bond, the alkoxysilyl compound (a2) having an amino group, and the imide compound (a) which are raw materials. By selecting a solvent having a hydroxyl group as the synthesis solvent, the reaction rate of the hydrolytic condensation of the alkoxysilane group portion can be reduced in the synthesis of the imide compound (a).
In addition to selecting a solvent having a hydroxyl group as the synthesis solvent, the reaction rate of the hydrolytic condensation of the alkoxysilane group site can be controlled when synthesizing the imide compound (A) by adjusting the concentration of the raw material or the heating temperature during the synthesis.
When the starting material is used at a high concentration and heated at a high temperature during the synthesis, the amic acid itself formed in the initial reaction functions as an acid catalyst, and the hydrolysis reaction of the alkoxysilane group is initiated by water formed by imidization of the amic acid, thereby increasing the molecular weight. The heating temperature during the reaction is preferably 100 to 150 ℃. Further, the molecular weight can be further increased by adding water and an acid catalyst such as formic acid, heating, and distilling off low boiling point components.
< 1-1-4. specific examples of synthetic solvents
Specific examples of the synthesis solvent include glycol compounds such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, and triethylene glycol;
monoethers of glycol compounds such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (hereinafter abbreviated as "PGME"), propylene glycol monoethyl ether, propylene glycol monobutyl ether (hereinafter abbreviated as "PGBE"), butylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and triethylene glycol monomethyl ether;
diethers of glycol compounds such as ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether (hereinafter abbreviated as "EDM"), diethylene glycol butyl methyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, and triethylene glycol dimethyl ether;
monoether monoesters of glycol compounds such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA"), propylene glycol monoethyl ether acetate, butylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol monomethyl ether acetate;
diesters of glycol compounds such as ethylene glycol diacetate and propylene glycol diacetate;
monoesters of monocarboxylic acid compounds such as butyl acetate, butyl propionate, methyl butyrate, ethyl butyrate, and butyl butyrate;
monoether monoesters of monohydroxycarboxylic acid compounds such as methyl methoxyacetate, ethyl methoxyacetate, methyl 3-methoxypropionate (hereinafter abbreviated as "MMP"), ethyl 3-ethoxypropionate, and methyl 4-methoxybutyrate;
diester bodies of dicarboxylic acid compounds such as dimethyl succinate and diethyl succinate;
monoamide compounds of monocarboxylic acid compounds such as N, N-dimethylacetamide and N, N-dimethylpropionamide;
dialkyl ketone compounds such as methyl isobutyl ketone, methyl n-butyl ketone, diethyl ketone, ethyl isobutyl ketone, diisobutyl ketone, and di-n-butyl ketone;
cyclic ether compounds such as hexane (hexamethylene oxide) and 1, 4-dioxane;
β -propiolactone, gamma-butyrolactone, delta-valerolactone and other cyclic ester compounds;
cyclic amide compounds such as 2-pyrrolidone and N-methyl-2-pyrrolidone; and
cyclic ketone compounds such as cyclopentanone (hereinafter abbreviated as "CPN"), cyclohexanone and cycloheptanone. More than one of these compounds may be used.
Among these specific examples of the synthesis solvent, the monoether of the glycol compound, the diether of the glycol compound, the monoether monoester of the glycol compound, and the monoether monoester of the monohydroxycarboxylic acid compound are preferable in terms of high solubility of the imide compound (a).
< 1-1-5. molecular weight of imide Compound (A) >
The weight average molecular weight of the imide compound (A) obtained is preferably 500 to 500,000, more preferably 1,000 to 50,000. When the content is in the above range, the compatibility of the imide compound (A) with the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C) is good.
The weight average molecular weight in the present specification is a value in terms of polystyrene determined by Gel Permeation Chromatography (GPC) (column temperature: 35 ℃ C., flow rate: 1 mL/min). The standard polystyrene is measured using polystyrene having a molecular weight of 645 to 132,900 (e.g., calibration kit (calibration kit) PL2010-0102) from Agilent Technologies, Inc., and a column using PLGel MIXED-D (trade name, Agilent Technologies, Inc.), and tetrahydrofuran as a mobile phase. In the present specification, the weight average molecular weight of a commercially available product is a value described in a catalog (catalog).
< 1-2. polyfunctional carboxyl compound (B) >
The polyfunctional carboxyl compound (B) used in the present invention is a compound having three or more carboxyl groups per molecule.
A preferable example of the polyfunctional carboxyl compound (B) is polyesteramic acid (B1) obtained by reacting tetracarboxylic dianhydride (B11), diamine (B12), and polyhydroxyl compound (B13) as essential raw materials. The raw material of the compound is easily obtained or the compound is easily produced, and the curable composition containing the compound has good compatibility with the imide compound (A) and the polyfunctional epoxy compound (C).
< 1-2-1 polyester amic acid (B1) >
The polyesteramic acid (B1) used in the present invention is a reaction product obtained by reacting a tetracarboxylic dianhydride (B11), a diamine (B12) and a polyvalent hydroxyl compound (B13) as essential raw materials. Further, in addition to these components, one or more selected from the group consisting of the monohydric alcohol (b14) and the styrene-maleic anhydride copolymer (b15) may be added to the raw material.
The method of adding the polyesteramic acid (B1) to the curable composition of the present invention may be a method of adding the solution after the polymerization reaction as it is, or a method of adding only the solid component by concentrating the solution to remove the solid component.
< 1-2-1-1. tetracarboxylic dianhydride (b11) >
Examples of the tetracarboxylic dianhydride (b11) used in the present invention are aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aliphatic tetracarboxylic dianhydride.
Specific examples of the aromatic tetracarboxylic acid dianhydride include 3,3',4,4' -benzophenonetetracarboxylic acid dianhydride, 2',3,3' -benzophenonetetracarboxylic acid dianhydride, 2,3,3',4' -benzophenonetetracarboxylic acid dianhydride, 3,3',4,4' -diphenylsulfonetetracarboxylic acid dianhydride, 2',3,3' -diphenylsulfonetetracarboxylic acid dianhydride, 2,3,3',4' -diphenylsulfonetetracarboxylic acid dianhydride, 3,3',4,4' -diphenylethertetracarboxylic acid dianhydride, 2',3,3' -diphenylethertetracarboxylic acid dianhydride, 2,3,3',4' -diphenylethertetracarboxylic acid dianhydride, 2- [ bis (3, 4-dicarboxyphenyl) ] hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate); specific examples of the alicyclic tetracarboxylic dianhydride include cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, and cyclohexanetetracarboxylic dianhydride; specific examples of the aliphatic tetracarboxylic acid dianhydride include ethane tetracarboxylic acid dianhydride and butane tetracarboxylic acid dianhydride.
Among these tetracarboxylic acid dianhydrides, 3',4,4' -diphenylsulfone tetracarboxylic acid dianhydride, 3',4,4' -diphenylether tetracarboxylic acid dianhydride, 2- [ bis (3, 4-dicarboxyphenyl) ] hexafluoropropane dianhydride, ethylene glycol bis (anhydrotrimellitate) and butane tetracarboxylic acid dianhydride are preferable, and 3,3',4,4' -diphenylsulfone tetracarboxylic acid dianhydride, 3',4,4' -diphenylether tetracarboxylic acid dianhydride and butane tetracarboxylic acid dianhydride are more preferable. The cured film obtained from the curable composition containing polyesteramic acid (B1) obtained from a raw material containing one or more selected from these tetracarboxylic dianhydrides has high transparency.
The tetracarboxylic dianhydride (b11) may be used alone or in combination of two or more.
< 1-2-1-2. diamine (b12) >
Examples of the diamine (b12) used in the present invention are a diamine having two benzene rings and a diamine having four benzene rings.
Specific examples of the diamine having two benzene rings are 3,3' -diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfone and 3,4' -diaminodiphenyl sulfone; specific examples of diamines having four benzene rings are bis [4- (4-aminophenoxy) phenyl ] sulfone, bis [4- (3-aminophenoxy) phenyl ] sulfone, bis [3- (4-aminophenoxy) phenyl ] sulfone, [4- (4-aminophenoxy) phenyl ] [3- (4-aminophenoxy) phenyl ] sulfone, [4- (3-aminophenoxy) phenyl ] [3- (4-aminophenoxy) phenyl ] sulfone and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane.
Among these diamines, 3' -diaminodiphenyl sulfone is preferable. The polyester amic acid (B1) obtained from the starting material comprising the diamine has good solubility in solvents.
The diamine (b12) may be used alone or in combination of two or more.
< 1-2-1-3. polyhydroxy compound (b13) >
Specific examples of the polyhydric hydroxyl compound (b13) used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol having a weight average molecular weight of 1,000 or less, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 2-pentanediol, 1, 5-pentanediol, 2, 4-pentanediol, 1,2, 5-pentanetriol, 1, 2-hexanediol, 1, 6-hexanediol, 2, 5-hexanediol, 1,2, 6-hexanetriol, 1, 2-heptanediol, 1, 7-heptanediol, 1, 2-octanediol, 1, 8-octanediol, 1, 2-octanediol, 1, 4-octanediol, 3, 6-octanediol, 1,2, 8-octanetriol, 1, 2-nonanediol, 1, 9-nonanediol, 1,2, 9-nonanetriol, 1, 2-decanediol, 1, 10-decanediol, 1,2, 10-decanetriol, 1, 2-dodecanediol, 1, 12-dodecanediol, glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, bisphenol A, bisphenol S, bisphenol F, diethanolamine and triethanolamine.
Of these compounds, ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, and 1, 8-octanediol are preferable, and 1, 4-butanediol, 1, 5-pentanediol, and 1, 6-hexanediol are more preferable. The polyester amic acid (B1) obtained from a raw material containing one or more selected from these compounds has good solubility in solvents.
The polyhydric hydroxyl compound (b13) may be used alone or in combination of two or more.
< 1-2-1-4. Monool (b14) >
In the synthesis of polyesteramic acid (B1), in addition to tetracarboxylic dianhydride (B11), diamine (B12), and polyhydroxyl compound (B13), monohydric alcohol (B14) may be further reacted.
Specific examples of the monohydric alcohol (b14) are methanol, ethanol, 1-propanol, isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, phenol, borneol (borneel), maltitol (maltol), linalool (linalool), terpineol (terpineol), dimethylbenzyl methanol, 3-ethyl-3-hydroxymethyl oxetane.
Of these compounds, preferred are isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether and 3-ethyl-3-hydroxymethyloxetane, and more preferred is benzyl alcohol. The polyester amic acid (B1) obtained from a raw material containing one or more selected from these compounds has good compatibility with the polyfunctional epoxy compound (C).
The monool (b14) may be used alone or in combination of two or more.
< 1-2-1-5. styrene-maleic anhydride copolymer (b15) >
In the synthesis of polyesteramic acid (B1), in addition to tetracarboxylic dianhydride (B11), diamine (B12), and polyhydroxyl compound (B13), styrene-maleic anhydride copolymer (B15) may be reacted.
The compatibility of the polyesteramic acid (B1) with respect to the polyfunctional epoxy compound (C) can be improved by the addition of the styrene-maleic anhydride copolymer (B15). The styrene/maleic anhydride molar ratio is 0.5 to 4, preferably 1 to 3, more preferably about 1, about 2 or about 3, still more preferably about 1 or about 2, and particularly preferably about 1.
Specific examples of commercially available products of the styrene-maleic anhydride copolymer (b15) are SMA1000, SMA2000 and SMA3000 (both trade names, kawasaki oil chemical Co., Ltd.). Among these specific examples, SMA1000 having good solubility in a solvent is preferable.
The styrene-maleic anhydride copolymer (b15) may be used alone or in combination of two or more.
< 1-2-1-6. polymerization method of polyester amic acid (B1)
The polyesteramic acid (B1) used in the present invention can be produced by a known polymerization method (for example, described in Japanese patent laid-open No. 2015-163685). A preferred polymerization method is solution polymerization using a solvent (hereinafter, referred to as "polymerization solvent") used in the polymerization reaction.
< 1-3. polyfunctional epoxy compound (C) >
The polyfunctional epoxy compound (C) used in the present invention is a compound having three or more epoxy groups per molecule.
Examples of the polyfunctional epoxy compound (C) used in the present invention are
A compound having three or more glycidyl groups such as a phenol novolac type epoxy compound, a cresol novolac type epoxy compound, a bisphenol a novolac type epoxy compound, a biphenyl type polyfunctional epoxy compound, a polyfunctional epoxy compound having a siloxane bonding site, 2- [4- (2, 3-epoxypropoxy) phenyl ] -2- [4- [1, 1-bis [4- (2, 3-epoxypropoxy) phenyl ] ethyl ] phenyl ] propane, 1, 3-bis [4- [1- [4- (2, 3-epoxypropoxy) phenyl ] -1-methylethyl ] phenyl ] ethyl ] phenoxy ] -2-propanol, and α -2, 3-epoxypropoxyphenyl- ω -hydropoly [2- (2, 3-epoxypropoxy) benzylidene-2, 3-epoxypropoxyphenylene ];
compounds having three or more glycidyl ester groups such as homopolymers of glycidyl methacrylate and copolymers of glycidyl methacrylate and polymerizable compounds other than glycidyl methacrylate; and
and a1, 2-epoxy-4- (2-oxetanyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol, and the like having three or more oxetanyl groups.
The curable composition containing a compound having three or more glycidyl ether groups provides a cured film having good heat resistance, the curable composition containing a compound having three or more glycidyl ester groups also provides a cured film having good chemical resistance at a low calcination temperature, and the curable composition containing a compound having three or more oxetanyl groups provides a cured film having good UV resistance.
Of the compounds having three or more glycidyl ether groups, bisphenol A novolak type epoxy compounds which provide a cured film having particularly good heat resistance, 2- [4- (2, 3-epoxypropoxy) phenyl ] -2- [4- [1, 1-bis [4- (2, 3-epoxypropoxy) phenyl ] ethyl ] phenyl ] propane, 1, 3-bis [4- [1- [4- (2, 3-epoxypropoxy) phenyl ] -1-methylethyl ] phenyl ] ethyl ] phenoxy ] -2-propanol and α -2, 3-epoxypropoxyphenyl-omega-hydropoly [2- (2, 3-epoxypropoxy) benzylidene-2, 3-epoxypropoxyphenylene ] are particularly preferable.
Specific examples of commercially available products of phenol novolak type epoxy compounds are EPPN-201 (trade name, Japan chemical Co., Ltd.) and jER 152, jER 154 (trade name, Mitsubishi chemical Co., Ltd.), specific examples of commercially available products of cresol novolak type epoxy compounds are EOCN-102-103S, EOCN-104S, EOCN-1020 (trade name, Japan chemical Co., Ltd.), specific examples of commercially available products of bisphenol A novolak type epoxy compounds are jER157S65, jER157S 70 (trade name, Mitsubishi chemical Co., Ltd.), specific examples of commercially available products of biphenyl type multifunctional epoxy compounds are NC-3000, NC-3000-L, NC-3000-H, NC-567-011 (trade name, Japan chemical Co., Ltd.), specific examples of commercially available products of multifunctional epoxy compounds having a siloxane bond site are CoatOSIL MP200 (trade name, Japan Material (Moatman high-grade Material (Momamen) and MP2 (trade name, Molluma) and EP-3-354-PP 2- (isopropyl) and EP-3-ethyl propoxy-2-1-propoxy-1-5-200 (trade name, Japan chemical Co., Ltd.), specific examples of bis-ethyl propoxy-3-propyl-propoxy-2-3-ethyl-3- (meth-propoxy-3-1-3-propyl-3-ethyl-3-1-3-500) and specific examples of bis-propyl-2-ethyl-3-2-propyl-3-2-propyl-2-3-2-3-2-3-2-3-2-3-2-3-2-3-2-3-2.
< 1-4 > additive (D) >
The curable composition of the present invention may further contain an additive (D). The additive (D) optionally added to the curable composition of the present invention may be added to improve the properties of the curable composition of the present invention such as coating uniformity, adhesion, stability, chemical resistance, and low-temperature curing properties.
Examples of the additive (D) are anionic, cationic, nonionic and fluorine-based surfactants; a silicone resin coating property improving agent; adhesion improving agents such as silane coupling agents; anti-coagulating agents such as sodium polyacrylate; high molecular dispersants such as acrylic, styrene, polyethyleneimine and urethane; antioxidants such as hindered phenols; crosslinking agents such as epoxy compounds other than the polyfunctional epoxy compound (C), melamine compounds and diazide compounds; a photoacid generator; a polyfunctional (meth) acrylate compound; and a photopolymerization initiator.
< 1-4-1. surfactant >
The curable composition of the present invention may further contain a surfactant from the viewpoint of further improving coating uniformity. Specific examples of the surfactant are Polyflow No.75, Polyflow No.90, Polyflow No.95, Dipper (DISPERBYK) -161, Dipper (DISPERBYK) -162, Dipper (DISPERBYK) -163, Dipper (DISPERBYK) -164, Dipper (DISPERBYK) -166, Dipper (DISPERBYK) -170, Dipper (DISPERBYK) -180, Dipper (DISPERBYK) -181, Dipper (DISPERBYK) -182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-361, BYK-35 361N, BYK, UV-3500, Japan chemical Co., Japan, UV-W-78, UV-8970, and Japan chemical trademarks, KP-341, KP-368, KF-96-50CS, KF-50-100CS (all trade names, shin-Etsu Chemical industries, Inc.), Shafu-long (Surflon) S611 (trade names, AGC Seimi Chemical, Inc.), Fu Ji (Ftergent)222F, Fu Ji (Ftergent)208G, Fu Ji (Ftergent)251, Fu Ji (Ftergent)710FL, Fu Ji (Ftergent)710FM, Fu Ji (Ftergent)710FS, Fu Ji (Ftergent)601AD, Fu Ji (Ftergent)650A, FTX-218 (all trade names, Nioos (Neos) Inc.), Mei Fac (Megafac) F-171, Mei Fac (Megafac) F-177, Mei Fac (Megac-410, Mei-410F-475, Mei Fac (Megac-475F, Mei Fac) 444, Mei-410, Megafac (Megafac) F-477, Megafac (Megafac) F-552, Megafac (Megafac) F-553, Megafac (Megafac) F-554, Megafac (Megafac) F-555, Megafac (Megafac) F-556, Megafac (Megafac) F-558, Megafac (Megafac) F-559, Megafac (Megafac) R-94, Megafac (Megafac) RS-75, Megafac (Megafac) RS-72-K, Megafac (Megafac) RS-76-NS, Megafac (Megafac) DS-21 (all trade names, Diesen (DIC) GmbH), TeGOTwain (Tegowsin) 4000, Tegowy (Tegowy) 0, Tegudion (Tegowsi) DS-440, Tegudion Gmby (Teguqigon) Wo (Tegowsi, Teguqifa) 450, all trade names, Gefao (Teguqifa) F-450, Gefac (Gefac) F-Hfac) RS-450, and Higudao (Skawasp-Gefag-Gec) RS-K, Fluoroalkyl benzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglyceryl tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethylammonium salt, fluoroalkyl sulfamate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, fluoroalkyl iodide, fluoroalkyl betaine, and fluoroalkyl betaine, Polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate and alkyl diphenyl ether disulfonate. More than one of these surfactants may be used.
Among these specific examples of the surfactant, at least one selected from BYK-306, BYK-342, BYK-346, KP-341, KP-368, Shafu Long (Surflon) S611, Forgelite (Ftergent)710FL, Forgelite (Ftergent)710FM, Forgelite (Ftergent)710FS, Forgelite (Ftergent)650A, Meijia (Megafac) F-477, Meijiafa (Megafac) F-556, Meijiafa (Megafac) RS-72-K, Meijiafac (Megafac) DS-21, Diggin (TEGO Twin)4000, fluoroalkyl benzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl sulfonate, fluoroalkyl trimethylammonium salt, and fluoroalkyl sulfamate is preferable because of these surfactants, the effect of improving the coating uniformity of the curable composition is large.
The amount of the surfactant added to the curable composition of the present invention is preferably 0.01 to 0.1 parts by weight based on 100 parts by weight of the main component.
< 1-4-2 > adhesion improver
From the viewpoint of further improving the adhesion of the formed cured film to the substrate, the curable composition of the present invention may further contain an adhesion improving agent. Examples of the adhesion improving agent include silane-based coupling agents, aluminum-based coupling agents, and titanate-based coupling agents other than the imide compound (a). Specific examples of silane-based coupling agents other than the imide compound (A) are 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane (e.g., sala-Ace S510; trade name, Jienwis (JNC) incorporated by reference), 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane (e.g., sala-Ace S530; trade name, Jiemiz (JNC) incorporated by reference), 3-trimethoxysilylpropyl methacrylate (e.g., sala-Ace S710; trade name, Jienwis (JNC) incorporated by reference), 3-mercaptopropyltrimethoxysilane (e.g., sala-Ace S810; trade name, jienzhi (JNC) corporation), a specific example of the aluminum-based coupling agent is aluminum acetyl alkoxy diisopropoxide, and a specific example of the titanate-based coupling agent is tetraisopropyl bis (dioctyl phosphite) titanate. One or more of these adhesion improving agents may be used.
Among these specific examples of the adhesion improving agent, 3-glycidoxypropyltrimethoxysilane and 3-trimethoxysilylpropyl methacrylate are preferable because they have a large effect of improving the adhesion of the cured film to the substrate.
The amount of the adhesion improver added to the curable composition of the present invention is preferably 0.1 to 20 parts by weight per 100 parts by weight of the main component.
< 1-4-3. anti-coagulant
The curable composition of the present invention may further contain an anti-coagulating agent from the viewpoint of being compatible with a solvent to prevent coagulation. The anti-coagulation agent is used to prevent coagulation by being dissolved in a solvent. Specific examples of the anti-coagulation agent optionally added to the curable composition of the present invention are Dipper (DISPERBYK) -145, Dipper (DISPERBYK) -161, Dipper (DISPERBYK) -162, Dipper (DISPERBYK) -163, Dipper (DISPERBYK) -164, Dipper (DISPERBYK) -182, Dipper (DISPERBYK) -184, Dipper (DISPERBYK) -185, Dipper (DISPERBYK) -2163, Dipper (DISPERBYK) -20154, BYK-220S, Dipper (DISPERBYK) -191, Dipper (DISPERBYK) -199, Dipper (DISPERBYK) -Chebyk (BYK) -2164, Japanese chemical (BYK) -216, Japanese chemical company, Japanese company name of Japan, Japanese name of Brandt, Japan, and F & f &, nioos (Neos) Inc.), Floron (Flowen) G-600, and Floron (Flowen) G-700 (both trade names, Kyoeisha chemical Co., Ltd.). One or more of these anti-agglomeration agents may be used.
< 1-4-4 > antioxidant
The curable composition of the present invention may further contain an antioxidant from the viewpoint of preventing yellowing of the cured film when exposed to high temperature. Specific examples of the antioxidant include Ixol-best (Irganox)1010, Ixol-best (Irganox)1010FF, Ixol-best (Irganox)1035FF, Ixol-best (Irganox)1076FD, Ixol-best (Irganox)1098, Ixol-best (Irganox)1135, Ixol-best (Irganox)1330, Ixol-best (Irganox)1726, Ixol-best (Irganox)1425, Ixol-best (Irganox)1520L, Ixol-best (Irganox)245FF, Ixol-best (Irganox) 311259, Ixol-best (Irganox)1520, Ixol-best (Irganox)565, Ixol-best (Irganox) 565B-Ixol-best (ADganox) pro B-Ixol-pro B, Ixol-Ixol 3115, Ixol (Irganox) and Ixol-Ixol (Irganox)565, Ixol-x, Addicotabo (ADK STAB) AO-60 and Addicotabo (ADK STAB) AO-80 (both trade names, Addick (ADEKA) Co., Ltd.). One or more of these antioxidants may be used.
Specific examples of these antioxidants are preferably xylophilus (Irganox)1010 and Addicusta wave (ADKSTAB) AO-60.
The amount of the antioxidant added to the curable composition of the present invention is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the main component.
< 1-4-5. crosslinking agent >
The curable composition of the present invention may further contain a crosslinking agent such as an epoxy compound other than the polyfunctional epoxy compound (C), a melamine compound or a diazide compound, from the viewpoint of improving heat resistance, chemical resistance, uniformity within the film surface, flexibility and elasticity.
Examples of the epoxy compound other than the polyfunctional epoxy compound (C) include compounds having two glycidyl ether groups such as bisphenol a type epoxy compounds, bisphenol F type epoxy compounds, biphenyl type bifunctional epoxy compounds, and bifunctional epoxy compounds having a siloxane bonding site; compounds having two glycidyl ester groups such as diglycidyl terephthalate, diglycidyl phthalate, and diglycidyl 1, 2-cyclohexanedicarboxylate; and compounds having two alicyclic epoxy groups such as 3',4' -epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate. More than one of these compounds may be used.
Specific examples of commercially available products of bisphenol A type epoxy compounds are jER 828, jER 1004, jER 1009 (both trade names, Mitsubishi chemical Co., Ltd.); specific examples of commercially available products of bisphenol F type epoxy compounds are jER 806, jER 4005P (both trade names, Mitsubishi chemical Co., Ltd.); examples of commercially available biphenyl type difunctional epoxy compounds are jERYX4000, jER YX4000H, jER YL6121H (all trade names, Mitsubishi chemical Co., Ltd.); a commercially available product of a bifunctional epoxy compound having a siloxane bonding site is exemplified by TSL9906 (trade name, Japan maiden Performance Materials Japan, llc); specific examples of commercially available products of diglycidyl terephthalate are danacol (Denacol) EX-711 (trade name, tradename of rice-traded chemical industry (Nagase chemteX) corporation); specific examples of commercially available products of diglycidyl phthalate are danacol (Denacol) EX-721 (trade name, tradename of rice-traded chemical industry (Nagase chemteX) corporation); a specific example of a commercially available product of 3',4' -epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate is Celloxide 2021P (trade name, Daicel, Inc.).
The amount of the epoxy compound other than the polyfunctional epoxy compound (C) added to the curable composition of the present invention is preferably 1 to 20 parts by weight based on 100 parts by weight of the main component.
< 1-4-6. photoacid generator
The curable composition of the present invention may further contain a photoacid generator from the viewpoint of patterning by exposure and development. Examples of the photoacid generator are 1, 2-quinonediazide compounds.
Specific examples of the 1, 2-quinonediazide compound are 2,3, 4-trihydroxybenzophenone-1, 2-naphthoquinonediazide-4-sulfonate, 2,3, 4-trihydroxybenzophenone-1, 2-naphthoquinonediazide-5-sulfonate (for example, trade name, NT-200, Toyo Synthesis chemical industry), 2,4, 6-trihydroxybenzophenone-1, 2-naphthoquinonediazide-4-sulfonate, 2,4, 6-trihydroxybenzophenone-1, 2-naphthoquinonediazide-5-sulfonate; 2,2',4,4' -tetrahydroxybenzophenone-1, 2-naphthoquinone diazide-4-sulfonate, 2',4,4' -tetrahydroxybenzophenone-1, 2-naphthoquinone diazide-5-sulfonate, 2,3,3', 4-tetrahydroxybenzophenone-1, 2-naphthoquinone diazide-4-sulfonate, 2,3,3', 4-tetrahydroxybenzophenone-1, 2-naphthoquinone diazide-5-sulfonate, 2,3,4,4 '-tetrahydroxybenzophenone-1, 2-naphthoquinone diazide-4-sulfonate, 2,3,4,4' -tetrahydroxybenzophenone-1, 2-naphthoquinone diazide-5-sulfonate; bis (2, 4-dihydroxyphenyl) methane-1, 2-naphthoquinone diazide-4-sulfonate, bis (2, 4-dihydroxyphenyl) methane-1, 2-naphthoquinone diazide-5-sulfonate, bis (p-hydroxyphenyl) methane-1, 2-naphthoquinone diazide-4-sulfonate, bis (p-hydroxyphenyl) methane-1, 2-naphthoquinone diazide-5-sulfonate; tris (p-hydroxyphenyl) methane-1, 2-naphthoquinone diazide-4-sulfonate, tris (p-hydroxyphenyl) methane-1, 2-naphthoquinone diazide-5-sulfonate, 1,1, 1-tris (p-hydroxyphenyl) ethane-1, 2-naphthoquinone diazide-4-sulfonate, 1,1, 1-tris (p-hydroxyphenyl) ethane-1, 2-naphthoquinone diazide-5-sulfonate; bis (2,3, 4-trihydroxyphenyl) methane-1, 2-naphthoquinone diazide-4-sulfonate, bis (2,3, 4-trihydroxyphenyl) methane-1, 2-naphthoquinone diazide-5-sulfonate, 2-bis (2,3, 4-trihydroxyphenyl) propane-1, 2-naphthoquinone diazide-4-sulfonate, 2-bis (2,3, 4-trihydroxyphenyl) propane-1, 2-naphthoquinone diazide-5-sulfonate; 1,1, 3-tris (2, 5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1, 2-naphthoquinone diazide-4-sulfonate, 1, 3-tris (2, 5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1, 2-naphthoquinone diazide-5-sulfonate, 4'- [1- [4- [1- [ 4-hydroxyphenyl ] -1-methylethyl ] phenyl ] ethylene ] bisphenol-1, 2-naphthoquinone diazide-4-sulfonate, 4' - [1- [4- [1- [ 4-hydroxyphenyl ] -1-methylethyl ] phenyl ] ethylene ] bisphenol-1, 2-naphthoquinone diazide-5-sulfonate ester; bis (2, 5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1, 2-naphthoquinonediazide-4-sulfonate, bis (2, 5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1, 2-naphthoquinonediazide-5-sulfonate, 3,3,3',3' -tetramethyl-1, 1' -spirobiindan-5, 6,7,5',6',7' -hexanol-1, 2-naphthoquinone diazide-4-sulfonate ester, 3,3,3',3' -tetramethyl-1, 1' -spirobiindan-5, 6,7,5',6',7' -hexanol-1, 2-naphthoquinone diazide-5-sulfonate ester; 2,2, 4-trimethyl-7, 2',4' -trihydroxyflavan-1, 2-naphthoquinonediazide-4-sulfonic acid ester and 2,2, 4-trimethyl-7, 2',4' -trihydroxyflavan-1, 2-naphthoquinonediazide-5-sulfonic acid ester. One or more of these photoacid generators may be used.
The amount of the photoacid generator added to the curable composition of the present invention is preferably 1 to 20 parts by weight based on 100 parts by weight of the main component.
< 1-4-7 > polyfunctional (meth) acrylate compound
The curable composition of the present invention may further contain a polyfunctional (meth) acrylate compound from the viewpoint of improving scratch resistance.
Examples of the polyfunctional (meth) acrylate compound are a compound having two (meth) acryloyl groups per molecule and a compound having three or more (meth) acryloyl groups per molecule.
Specific examples of the compound having two (meth) acryloyl groups per molecule include ethylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, ethylene oxide-modified bisphenol F di (meth) acrylate, and ethylene oxide-modified bisphenol S di (meth) acrylate Di (meth) acrylate of diol compounds such as esters;
di (meth) acrylate bodies of triol compounds such as glycerin acrylate methacrylate, glycerin di (meth) acrylate and ethoxylated isocyanuric acid diacrylate;
di (meth) acrylate bodies of bisphenol compounds such as bisphenol a di (meth) acrylate, bisphenol F di (meth) acrylate, and bisphenol S di (meth) acrylate; and
epichlorohydrin-modified ethylene glycol di (meth) acrylate, epichlorohydrin-modified 1, 6-hexanediol di (meth) acrylate, epichlorohydrin-modified diethylene glycol di (meth) acrylate, epichlorohydrin-modified triethylene glycol di (meth) acrylate, epichlorohydrin-modified tetraethylene glycol di (meth) acrylate, epichlorohydrin-modified polyethylene glycol di (meth) acrylate, epichlorohydrin-modified propylene glycol di (meth) acrylate, epichlorohydrin-modified dipropylene glycol di (meth) acrylate, epichlorohydrin-modified tripropylene glycol di (meth) acrylate, epichlorohydrin-modified tetrapropylene glycol di (meth) acrylate, epichlorohydrin-modified polypropylene glycol di (meth) acrylate, a (meth) acrylic acid adduct of a bisphenol a type epoxy compound, a (meth) acrylic acid adduct of a bisphenol F type epoxy compound, and a (meth) acrylic acid adduct of a bisphenol S type epoxy compound An adduct of a carboxylic acid with a carboxylic acid. More than one of these compounds may be used.
Specific examples of the compound having three or more (meth) acryloyl groups per molecule include trifunctional (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate, trimethylolpropane Ethylene Oxide (EO) modified tri (meth) acrylate, trimethylolpropane Propylene Oxide (PO) modified tri (meth) acrylate, glycerol EO modified tri (meth) acrylate, glycerol PO modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated isocyanurate tri (meth) acrylate, and epsilon-caprolactone modified tri- (2- (meth) acryloyloxyethyl) isocyanurate;
tetrafunctional (meth) acrylate compounds such as di-trimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol alkoxy tetra (meth) acrylate, and diglycerol EO-modified tetraacrylate;
pentafunctional (meth) acrylate compounds such as dipentaerythritol penta (meth) acrylate;
hexafunctional (meth) acrylate compounds such as dipentaerythritol hexaacrylate; and
a polyfunctional (meth) acrylate compound having a carboxyl group. More than one of these compounds may be used.
Specific examples of commercially available products of trimethylolpropane triacrylate as the trifunctional acrylate compound are NK ESTER (NK ESTER) TMPT (trade name, new zhongcun chemical industry co., ltd.), TMPTA (trade name, xylonite (Daicel Allnex) co., ltd.), and aninesia (Aronix) M-309 (trade name, synthetic east asia co., ltd.);
specific examples of commercially available trimethylolpropane EO-modified triacrylate are TMPEOTA (trade name, celluloid ornex, inc.), rhonizus (Aronix) M-350, rhonizus (Aronix) M-360 (both trade names, available from tokyo synthesis gmbh);
specific examples of commercially available trimethylolpropane PO-modified triacrylate include Albizzia (EBECRYL)135 (trade name, Daicel Allnex, Inc.), Aronix (Aronix) M-310, and Aronix (Aronix) M-321 (both trade names, Toyo Synthesis Co., Ltd.);
a specific example of a commercially available product of glycerin PO modified triacrylate is OTA 480 (trade name, xylonite alonos (Daicel Allnex) inc.);
specific examples of commercially available ethoxylated isocyanuric acid triacrylate are NK ESTER (NK ESTer) A-9300 (trade name, Ningmura chemical industries, Ltd.);
a specific example of a commercially available product of ε -caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate is NK ester (NKESTer) A-9300-1CL (trade name, Ningmura chemical industries, Ltd.).
A specific example of a commercially available product of trimethylolpropane trimethacrylate as a trifunctional methacrylate compound is NK ESTER (NK ESTer) TMPT (trade name, Ningmura chemical industries, Ltd.).
Specific examples of commercially available products of di-trimethylolpropane tetraacrylate, which is a tetrafunctional acrylate compound, are NK ESTER (NK ESTER) AD-TMP (trade name, newmura chemical industry, ltd.), EBECRYL (EBECRYL)140 and EBECRYL (EBECRYL)1142 (both trade names, celluloid oxonos (Daicel Allnex) ltd.), and bronis (Aronix) M-408 (trade name, east asia synthetic member ltd);
specific examples of commercially available products of ethoxylated pentaerythritol tetraacrylate are NK ESTER (NK ESTER) ATM-35E (trade name, Ningmura chemical industries, Ltd.);
specific examples of commercially available products of pentaerythritol tetraacrylate are NK ESTER (NK ESTER) A-TMMT (trade name, Ningmura chemical industries, Ltd.);
specific examples of commercially available products of pentaerythritol alkoxytetraacrylate are EBECRYL 40 (trade name, cello alones (Daicel Allnex) corporation);
a specific example of a commercially available diglycerin EO-modified tetraacrylate is Aronix M-460 (trade name, manufactured by Toyo Seisakusho Co., Ltd.).
Specific examples of commercially available products of dipentaerythritol hexaacrylate as the hexafunctional acrylate compound are NK ESTER (NK ESTER) a-DPH (trade name, new zhongcun chemical industry co., ltd.) and DPHA (trade name, celluloid ornos (Daicel Allnex) co., ltd.).
Specific examples of commercially available products of the multifunctional acrylate compound having a carboxyl group are Aronix M-510 and Aronix M-520 (both trade names, manufactured by Toyo Synthesis Ltd.).
A specific example of a commercially available product of a mixture of an ethoxylated isocyanuric acid triacrylate as a trifunctional acrylate compound and an ethoxylated isocyanuric acid diacrylate as a difunctional acrylate compound is Aronix M-315(3 to 13 wt%) (trade name, manufactured by Toyo Synthesis Ltd., the content in parentheses is a value listed as the content of the ethoxylated isocyanuric acid diacrylate in the mixture).
Specific examples of commercially available products of a mixture of pentaerythritol triacrylate as a trifunctional acrylate compound and pentaerythritol tetraacrylate as a tetrafunctional acrylate compound are PETIA, PETRA and PETA (both trade names, Daicel allonex corporation), arinex M-306(65 to 70 wt%), arinex M-305(55 to 63 wt%), and arinex M-450 (less than 10 wt%) (both trade names; east asia synthetic gmbh, the content in parentheses is a value listed as the content of pentaerythritol triacrylate in the mixture).
Specific examples of commercially available products of a mixture of dipentaerythritol pentaacrylate as a pentafunctional acrylate and dipentaerythritol hexaacrylate as a hexafunctional acrylate are aronia (Aronix) M-403(50 to 60 wt%), aronia (Aronix) M-400(40 to 50 wt%), aronia (Aronix) M-402(30 to 40 wt%), aronia (Aronix) M-404(30 to 40 wt%), aronia (Aronix) M-406(25 to 35 wt%) and aronia (Aronix) M-405(10 to 20 wt%) (trade name, product name, east asia synthetic products limited company, content in parentheses is a catalog value of content of pentaerythritol pentaacrylate in the mixture).
The amount of the polyfunctional (meth) acrylate compound added to the curable composition of the present invention is preferably 1 to 20 parts by weight based on 100 parts by weight of the main component.
< 1-4-8. photopolymerization initiator
The curable composition of the present invention may further contain a photopolymerization initiator from the viewpoint of improving the low-temperature curability. In the case of adding a photopolymerization initiator, the calcination temperature can be lowered by performing an ultraviolet irradiation step in combination with a polyfunctional (meth) acrylate compound.
Specific examples of the photopolymerization initiator include benzophenone, michaelis ketone, 4 '-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2, 4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4' -isopropylphenylacetone, 1-hydroxycyclohexylphenylketone, isopropyl benzoin ether, isobutyl benzoin ether, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone and 2-methyl-1- [4- (methylthio) phenyl ] ethanone]-2-morpholinopropan-1-one (for example, trade name, Irgacure 907, Basff (BASF Japan) Co., Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (for example, trade name, Irgacure 369, Basf (BASF Japan) Co., Ltd.), ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4 '-di (t-butylperoxycarbonyl) benzophenone, 3,4,4' -tri (t-butylperoxycarbonyl) benzophenone, 1, 2-octanedione, 1- [4- (phenylthio) phenyl ] methyl ethyl ketone]-2- (O-benzoyl oxime) (e.g., trade name, Irgacure (Irgacure) OXE01, BASF Japan Ltd.), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-1- (O-acetyloxime) (for example, trade name, Irgacure (Irgacure) OXE02, Nippon Basf (BASF Japan) Co., Ltd.), Irgacure (Irgacure) OXE03 (trade name, Nippon Basf (BASF Japan) Co., Ltd.), 1, 2-propanedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio ] phenylthio]Phenyl radical]-2- (O-acetyloxime) (for example, trade name, Adeka Kuroz (Adeka Arkls) NCI-930, Adeka (ADEKA) GmbH), Adeka Kuroz (Adeka Arkls) NCI-831 (trade name, Adeka (ADEKA) GmbH), Adeka Oxytma (Adeka Optomer) N-1919 (trade name, Adeka (ADEKA) GmbH), 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2- (4' -methoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (3',4' -dimethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (2',4' -dimethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (2 '-methoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4' -pentyloxyphenylethenyl) -4, 6-bis (trichloromethyl) -s-triazine, 4- [ p-N, N-bis (ethoxycarbonylmethyl)]-2, 6-bis (trichloromethyl) -s-triazine, 1, 3-bis (trichloromethyl) -5- (2' -chlorophenyl) -s-triazine, 1, 3-bis (trichloromethyl) -5- (4' -methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3' -carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (4-ethoxycarbonylphenyl) -1,2' -biimidazole, 2' -bis (2, 4-dichlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2, 4-dibromophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2, 4' -dibromophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biphenylcarbazole, 2' -bis (2, 4' -trichloromethyl) -5- (2' -hydroxy-cyclohexyl) -2, 5,5' -bis (2, 5-dichlorophenyl) -1,2, 5,5' -bis (2, 5-dodecylpropionyl) -2, 2' -bis (2, 5-dodecylmethylchlorobenzoyl) -1, 5-bis (2-dodecylpropionyl) carbazole, 25-2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium. One or more of these photopolymerization initiators can be used.
In a specific example of these photopolymerization initiators, when at least one selected from the group consisting of 1, 2-octanedione, 1- [4- (phenylthio) phenyl ] -2- (O-benzoyloxime) and 1, 2-propanedione, and 1- [4- [4- (2-hydroxyethoxy) phenylthio ] phenyl ] -2- (O-acetyloxime) is used, the effect of improving the low-temperature curability of the curable composition can be exhibited with a smaller amount of exposure. The photopolymerization initiator suitable for exhibiting the above-described effects is added in an amount of 0.1 to 5 parts by weight relative to 100 parts by weight of the main component.
< 1-5. solvent optionally added to curable composition >
The curable composition of the present invention may contain a solvent in addition to the polymerization solvent. The solvent (hereinafter referred to as "diluting solvent (E)") optionally added to the curable composition of the present invention is preferably a solvent capable of dissolving the imide compound (a), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C). When the curable composition contains the additive (D), the diluting solvent (E) is preferably a solvent capable of further dissolving the additive (D).
Specific examples of the diluting solvent (E) are the same as those described as specific examples of the reaction solvent. One or more of these solvents may be used.
< 1-6. storage of curable composition >
The curable composition of the present invention is preferably stored in the range of-30 to 25 ℃ in the shade, because the composition has good stability over time. More preferably, the storage is carried out at-20 ℃ to 5 ℃.
< 2. cured film obtained from curable composition
The curable composition of the present invention can be obtained by: the imide compound (A), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C) are mixed, and the additive (D) and the diluting solvent (E) are further selectively added depending on the desired properties, and these compounds are uniformly mixed and dissolved.
When the curable composition obtained in the above manner is applied to the surface of a substrate and the curable composition contains a solvent for the composition, the solvent for the composition is further removed by a heating step, a pressure reduction step, or the like, whereby a coating film can be formed. Specific examples of the method of applying the curable composition to the surface of the substrate include spin coating, roll coating, dipping, and slit coating. An example of the solvent for removing the composition by the heating step is pre-baking by a hot plate and an oven. The prebaking conditions vary depending on the kind and blending ratio of each component, and are usually 70 to 150 ℃ for 1 to 5 minutes in the case of a hot plate and 5 to 15 minutes in the case of an oven.
Finally, in order to completely cure the coating film, the cured film can be obtained by performing a heat treatment at 100 to 250 ℃, preferably 120 to 230 ℃, for 5 to 60 minutes in the case of a hot plate, or for 20 to 90 minutes in the case of an oven.
When the polyfunctional (meth) acrylate compound as the additive (D) and the photopolymerization initiator are added to the curable composition, the curable composition may be cured not only by heat curing by heat treatment but also by light irradiation with ultraviolet rays. In this case, the coating film before the heat treatment is irradiated with ultraviolet rays. The wavelength of the ultraviolet rays to be irradiated is preferably 350nm or more because the dimerization reaction of light after the formation of the cured film is not affected. The ultraviolet ray used for the photo-curing may be either polarized ultraviolet ray or unpolarized ultraviolet ray.
The cured film obtained in the above manner is subjected to three-dimensional crosslinking caused by condensation of the alkoxysilane group of the imide compound (a) and three-dimensional crosslinking caused by reaction of the carboxyl group of the polyfunctional carboxyl compound (B) and the epoxy group of the polyfunctional epoxy compound (C). In addition, in regard to condensation of the alkoxysilane group of the imide compound (a), the carboxyl group of the polyfunctional carboxyl compound (B) functions as a catalyst for increasing the condensation reaction rate. Therefore, the cured film obtained has high heat resistance and high resistance to a solvent in a polymerizable liquid crystal composition described later.
In addition, the cured film obtained contains a group having a polymerizable double bond of the imide compound (a) and an imide structure. The group having a polymerizable double bond and an imide structure is irradiated with linearly polarized ultraviolet light (313 nm in the example of the wavelength), and the double bonds arranged in a direction parallel to the polarization direction of the linearly polarized ultraviolet light cause a photo-dimerization reaction to impart a liquid crystal alignment ability to the cured film, so that the cured film obtained has photo-alignment properties.
Similarly, the cured film obtained from the curable composition containing a polymer having a cinnamoyl group and an epoxy group and a polyfunctional carboxyl compound described in prior document 2 is also three-dimensionally crosslinked and has photo-alignment properties.
However, the curable composition of the present invention is different from the curable composition described in prior document 2 in the crosslinkability between the compound having photo-alignment properties and the other components in the main component.
Since the crosslinkable group of the imide compound (a) which is a compound having photo-alignment properties contained in the curable composition of the present invention is an alkoxysilyl group, the crosslinkable group of the other component of the main component has low crosslinkability with both the carboxyl group of the polyfunctional carboxyl compound (B) and the epoxy group of the polyfunctional epoxy compound (C).
On the other hand, the curable composition described in prior document 2 has a high crosslinkability between a crosslinkable group, which is an epoxy group, which is a crosslinkable group of a polymer having a cinnamoyl group and an epoxy group, which is a compound having photo-alignment properties, and a carboxyl group of a polyfunctional carboxyl compound, which is another component of the main component.
Therefore, when the curable composition of the present invention is cured, the inhibition of photo-alignment properties due to the crosslinking of the compound having photo-alignment properties and the other component in the main component is small, whereas when the curable composition described in prior document 2 is cured, the inhibition of photo-alignment properties due to the crosslinking of the compound having photo-alignment properties and the other component in the main component is large. Therefore, the curable composition of the present invention can provide a cured film having photo-alignment properties even when the mixing ratio of the component having photo-alignment properties is low. Therefore, when the curable composition containing no component having photo-alignment properties is compared with the curable composition containing a component having photo-alignment properties, the deterioration of properties other than photo-alignment properties due to the addition of the component having photo-alignment properties can be suppressed.
< 3. color filter substrate comprising cured film obtained from curable composition >
The color filter substrate including the cured film of the present invention is a color filter substrate in which the cured film of the present invention is formed on a colored body of the color filter substrate.
Since the curable composition of the present invention has high planarization properties, the provision of the cured film reduces the level difference on the surface of the color filter substrate. Therefore, when the color filter substrate including the cured film of the present invention is used for a display element, the display quality of the display element is high.
[ examples ]
The present invention will be described in detail with reference to synthesis examples, comparative synthesis examples, examples and comparative examples, but the present invention is not limited to these examples at all.
The compounds used in the synthesis examples, comparative synthesis examples, examples and comparative examples are described in advance for each component.
Acid anhydride having polymerizable double bond (a 1):
a 1-1: citraconic anhydride
a 1-2: maleic anhydride
a 1-3: itaconic anhydride
Alkoxysilyl compound having amino group (a 2):
a 2-1: 3-aminopropyltriethoxysilane (hereinafter abbreviated as "APTS")
Synthesis solvent used in synthesis of imide compound (a):
EDM、PGME
polymerization inhibitor used for synthesis of imide compound (a):
dibutylhydroxytoluene (hereinafter abbreviated as "BHT")
Tetracarboxylic dianhydride (b 11):
b 11-1: butanetetracarboxylic dianhydride (trade name, Rikacid BT-100, Nissi Susan Co., Ltd., hereinafter abbreviated as "BT-100")
b 11-2: 3,3',4,4' -Diphenyl Ether tetracarboxylic dianhydride (hereinafter abbreviated as "ODPA")
Diamine (b 12):
b 12-1: 3,3' -diaminodiphenyl sulfone (hereinafter abbreviated as "DDS")
Polyhydric hydroxyl compound (b 13):
b 13-1: 1, 4-butanediol
Monohydric alcohol (b 14):
b 14-1: benzyl alcohol
Styrene-maleic anhydride copolymer (b 15):
b 15-1: SMA1000 (trade name, Chuan crude oil Co., Ltd.)
Polymerization solvent used in the reaction of polyester amic acid (B1):
MMP、PGMEA
polyfunctional epoxy compound (C):
c-1: jER157S 70 (trade name, Mitsubishi chemical corporation, abbreviated as "157S 70" hereinafter) as a compound having three or more glycidyl ether groups
C-2: PGMEA solution (solid content concentration: 50% by weight, weight average molecular weight: 3,000, hereinafter referred to as "PGMA 3000") as a homopolymer of glycidyl methacrylate which is a compound having three or more glycidyl ester groups
C-3: EHPE3150 (trade name, Daicel, Inc.) as a compound having three or more oxetanyl groups
Additive (D):
d-1: addisota (ADK STAB) AO-60 (trade name, Addiso (ADEKA) Co., Ltd., hereinafter abbreviated as "AO-60") as a hindered phenol antioxidant
Solvent for dilution (E):
E-1：PGME
E-2：PGBE
E-3：EDM
E-4：PGMEA
E-5：MMP
E-6：CPN
first, solutions containing an imide compound (a) were synthesized in the following manner (synthesis examples 1 to 3).
Synthesis example 1 Synthesis of solution containing imide Compound (A-1)
In a 500mL four-necked flask equipped with a thermometer, a stirrer, a raw material charge port and a nitrogen gas introduction port, citraconic anhydride as an acid anhydride (a1) having a polymerizable double bond, APTS as an alkoxysilyl compound (a2) having an amino group, and EDM as a synthesis solvent were charged in the following amounts, heated in an oil bath set at 130 ℃ for 3 hours, further set at 145 ℃ and aged for 2 hours, and low boiling components were distilled off under normal pressure.
Citraconic anhydride 64.51g
APTS 127.49g
EDM 48.00g
The reaction solution was cooled to 30 ℃ or lower to obtain a solution containing the imide compound (A-1). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis, and the solid content concentration was measured by a dry weight method. As a result, the weight-average molecular weight was 2,150 and the solid content concentration was 78% by weight. The molar ratio of the acid anhydride group of the acid anhydride having a polymerizable double bond (a1) and the amino group of the alkoxysilyl compound having an amino group (a2) charged as the raw material (acid anhydride group/amino group) was 1.0.
[ Synthesis example 2] Synthesis of a solution containing an imide Compound (A-2)
In a200 mL four-necked flask equipped with a thermometer, a stirrer, a charge port for raw materials and a nitrogen gas inlet, maleic anhydride as an acid anhydride (a1) having a polymerizable double bond, APTS as an alkoxysilane compound (a2) having an amino group, BHT as a polymerization inhibitor and EDM as a synthesis solvent were charged in the following amounts, heated in an oil bath set at 100 ℃ for 3 hours, further set at 120 ℃ and aged for 2 hours, and low boiling components were distilled off under normal pressure.
Figure BDA0002086737890000191
The reaction solution was cooled to 30 ℃ or lower to obtain a solution containing the imide compound (A-2). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis, and the solid content concentration was measured by a dry weight method. As a result, the weight-average molecular weight was 2,850, and the solid content concentration was 58% by weight. The molar ratio of the acid anhydride group of the acid anhydride having a polymerizable double bond (a1) and the amino group of the alkoxysilyl compound having an amino group (a2) charged as the raw material (acid anhydride group/amino group) was 1.0.
Synthesis example 3 Synthesis of solution containing imide Compound (A-3)
In a200 mL four-necked flask equipped with a thermometer, a stirrer, a charge port for raw materials and a nitrogen gas inlet, itaconic anhydride as an acid anhydride having a polymerizable double bond (a1), APTS as an alkoxysilane compound having an amino group (a2), BHT as a polymerization inhibitor and PGME as a synthetic solvent were charged in the following amounts, heated in an oil bath set at 100 ℃ for 3 hours, further set at 120 ℃ and aged for 2 hours, and low boiling components were distilled off under normal pressure.
Figure BDA0002086737890000201
The reaction solution was cooled to 30 ℃ or lower to obtain a solution containing the imide compound (A-3). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis, and the solid content concentration was measured by a dry weight method. As a result, the weight-average molecular weight was 1,100, and the solid content concentration was 49% by weight. The molar ratio of the acid anhydride group of the acid anhydride having a polymerizable double bond (a1) and the amino group of the alkoxysilyl compound having an amino group (a2) charged as the raw material (acid anhydride group/amino group) was 1.0.
Using a raw material containing a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxyl compound, a solution containing a polyesteramic acid was synthesized in the following manner (synthesis examples 4 and 5).
Synthesis example 4 Synthesis of solution containing polyesteramic acid (B1-1)
In a1,000 mL four-necked flask equipped with a thermometer, a stirrer, a raw material charge port and a nitrogen gas inlet, 604.80g of PGMEA as a solvent used in the synthesis reaction, 34.47g of BT-100 as a tetracarboxylic dianhydride, 164.11g of SMA1000 as a styrene-maleic anhydride copolymer, 50.17g of benzyl alcohol as a monohydroxy compound, and 10.45g of 1, 4-butanediol as a polyvalent hydroxy compound were charged, and the mixture was stirred at 130 ℃ for 3 hours under a dry nitrogen gas flow. Thereafter, the reacted solution was cooled to 25 ℃, 10.80g of DDS as a diamine and 25.20g of PGMEA were charged, and stirred at 20 to 30 ℃ for 2 hours, then stirred at 115 ℃ for 1 hour, and cooled to 30 ℃ or lower, thereby obtaining a pale yellow transparent solution containing polyester amic acid (B1-1) having a solid content of 30% by weight. The weight average molecular weight by GPC measurement was 10,000.
Synthesis example 5 Synthesis of solution containing polyesteramic acid (B1-2)
In a1,000 mL four-necked flask equipped with a thermometer, a stirrer, a raw material charge port and a nitrogen gas introduction port, 446.96g of MMP as a solvent used in the synthesis reaction, 31.93g of 1, 4-butanediol as a polyvalent hydroxy compound, 25.54g of benzyl alcohol as a monohydroxy compound, and 183.20g of ODPA as a tetracarboxylic dianhydride were charged, and the mixture was stirred at 130 ℃ for 3 hours under a dry nitrogen gas flow. Thereafter, the reacted solution was cooled to 25 ℃ and 29.33g of DDS as a diamine and 183.04g of MMP were charged, stirred at 20 ℃ to 30 ℃ for 2 hours, then stirred at 115 ℃ for 1 hour, and cooled to 30 ℃ or lower, whereby a pale yellow transparent solution containing polyesteramic acid (B1-2) having a solid content of 30% by weight was obtained. Further, the weight average molecular weight was 4,200 as measured by GPC.
A solution containing a polymer (Z) having a cinnamoyl group and an epoxy group was synthesized using a raw material containing a polymerizable compound having a cinnamoyl group and a polymerizable compound having an epoxy group in the following manner (synthesis example 6).
Synthesis example 6 Synthesis of a solution containing Polymer (Z-1) having a cinnamoyl group and an epoxy group
In a 500mL four-necked flask equipped with a thermometer, a stirrer, a charge port for raw materials, and a nitrogen gas introduction port, 135.00g of 2- {4- [ (1E) -3-methoxy-3-oxo-1-propen-1-yl ] phenoxy } ethyl ═ 2-methyl 2-acrylate as a polymerizable compound having a cinnamoyl group, 15.00g of glycidyl methacrylate as a polymerizable compound having an epoxy group, 15.00g of 2,2' -azobis (2, 4-dimethylvaleronitrile) as a polymerization initiator, and 50.00g of CPN as a reaction solvent were charged, and polymerization was carried out by heating at a polymerization temperature of 90 ℃ for 2 hours. The solution after the reaction was cooled to 30 ℃ or lower, thereby obtaining a solution containing the polymer (Z-1) having a cinnamoyl group and an epoxy group with a solid content concentration of 25 wt%. Further, the weight average molecular weight was 6,400 as measured by GPC.
[ example 1]
The imide compound (A-1) -containing solution obtained in Synthesis example 1 as the imide compound (A) -containing solution, the polyester amic acid (B1-1) -containing solution obtained in Synthesis example 4 as the polyfunctional carboxyl compound (B) -containing solution, 157S70 as the polyfunctional epoxy compound (C), and PGBE, EDM, and PGMEA as the diluting solvent (E) were mixed and dissolved at the ratio (unit: g) described in Table 1, and filtered with a membrane filter (0.2 μm), to obtain a curable composition.
The ratio of the imide compound (A) (unit: wt%, in the table, "100 × (A)/[ (A) + (B) + (C) ]") in the total amount of the imide compound (A), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C) of 100 wt% is shown in Table 1.
The ratio of the polyfunctional carboxyl compound (B) to the total amount of the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C) (unit: weight%, shown in table as "100 × (B)/[ (B) + (C) ]") in 100 wt% is shown in table 1.
TABLE 1
Figure BDA0002086737890000221
TABLE 1 (continuation)
Figure BDA0002086737890000231
In the table, (A-1), (A-2), (A-3), (B1-1), (B1-2) and (Z-1) are the weight of the solution.
The total amount of the solvent contained in the curable composition of example 1 was the total amount of the reaction solvent, i.e., EDM, contained in the solution containing the imide compound (a-1) and the diluting solvent (E), i.e., PGBE, EDM and PGMEA, and the solid content concentration was prepared to be about 25% by weight by the above procedure. The same applies to examples and comparative examples following example 2.
[ production of glass substrate with cured film ]
The obtained curable composition was spin-coated on a glass substrate at 800rpm for 10 seconds and pre-baked on a hot plate at 80 ℃ for 3 minutes, thereby obtaining a substrate with a coating film. Further, the substrate with the cured film was post-baked in an oven at 230 ℃ for 30 minutes, whereby a substrate with a cured film having a film thickness of approximately 1.5 μm was obtained. Hereinafter, the substrate with a cured film obtained is referred to as a "cured film-attached glass substrate".
[ evaluation of tackiness ]
The substrate with the coating film was evaluated as "◎" for the case of no tackiness (no tackiness), as "○" for the case of no tackiness but leaving fingerprints when strongly pressed, as "x" for the case of tackiness, and as "x" for the case of liquid, and the evaluation results are shown in table 1.
[ measurement of light transmittance ]
The light transmittance of only the hardened film at a wavelength of light of 400nm was measured by using an ultraviolet-visible near-infrared spectrophotometer V-670 (trade name, japan spectro corporation) provided with a glass substrate on which no hardened film was formed on the reference side of the ultraviolet-visible near-infrared spectrophotometer and the obtained glass substrate with the hardened film on the sample side. The measured values are shown in table 1.
[ evaluation of transparency ]
The light transmittance was 99.0% or more and the transparency was ◎%, 97.0% or more and less than 99.0% and the transparency was ○%, and less than 97.0% and the transparency was x, and the evaluation results are shown in table 1.
[ calculation of temperature for 5% weight loss ]
A powder-like measurement sample was cut out from the cured film of the obtained cured film-attached glass substrate. The temperature dependence of the thermogravimetric reduction rate of the obtained sample was measured using a differential thermal balance Thermo plus EVO TG-DTA 8120 (trade name, manufactured by Physics Ltd.). The heating was performed at a temperature rise rate of 10 ℃/min from room temperature, and a temperature at which the weight loss rate became 5%, that is, a "5% weight loss temperature" was calculated based on the heat weight loss rate of 100 ℃. The calculated values are shown in table 1.
[ evaluation of Heat resistance ]
The 5% weight loss temperature of 310 ℃ or higher was evaluated as heat resistance "◎", the temperature of 290 ℃ or higher and less than 310 ℃ was evaluated as heat resistance "○", and the temperature of less than 290 ℃ was evaluated as heat resistance "x", the evaluation results are shown in table 1.
[ preparation of polymerizable liquid Crystal composition ]
The polymerizable liquid crystal composition used in the evaluation was prepared in the following manner. 5.0g of Paliocola (Paliocolor) LC242 (trade name, Nippon Basf (BASF Japan) Co., Ltd.), 0.25g of Irgacure 907 (trade name, Nippon Basf Japan) Co., Ltd.), 0.0050g of BYK361N (trade name, BYK Chemie Japan) and toluene as an organic solvent were added, prepared in such a manner that the organic solvent became 85 wt% of the whole, and mixed and dissolved uniformly. The composition was a polymerizable liquid crystal composition (PLC-1).
[ production of glass substrate with optical functional film ]
The light irradiated by the extra-high pressure mercury lamp is converted into linear polarization by passing through a filter for cutting light of 300nm or less and a wire grid polarizing plate, and the obtained tape is converted into a tape having a thickness of 313nmIrradiation of the glass substrate with the cured film at 500mJ/cm2。
Subsequently, a polymerizable liquid crystal composition (PLC-1) was spin-coated on the substrate at a rotation speed of 1,300rpm for 10 seconds, and pre-baked on a hot plate at 80 ℃ for 1 minute. The substrate was cooled to room temperature, and then irradiated at 300mJ/cm in terms of 365nm2The ultrahigh-pressure mercury lamp (5) can fix the alignment by photo-curing the polymerizable liquid crystal composition. Hereinafter, the substrate obtained is expressed as "glass substrate with an optical functional film".
[ evaluation of photo-alignment Properties ]
The obtained glass substrate with an optical functional film was sandwiched between two linear polarizing plates in an orthogonal (crossed nicols) state, and observed by being irradiated with a backlight from below, and the case where bright and dark display without alignment defect (no light leakage) was possible was evaluated as photo-alignment "◎", the case where almost entire bright and dark display was possible but local alignment defect was observed was evaluated as photo-alignment "○", and the other cases were evaluated as photo-alignment "×", and the evaluation results were shown in table 1.
[ production of color Filter substrate with cured film ]
In addition to changing the glass substrate to the color filter substrate, the color filter substrate with a cured film is obtained according to the manufacturing method of the glass substrate with a cured film. Here, the color filter substrate used in the test is a substrate including red (R), green (G), and blue (B) coloring materials and a black matrix for preventing color mixture on a glass substrate, and the maximum step is 0.60 μm to 0.65 μm.
[ calculation of flattening Rate ]
In the production of a color filter substrate with a cured film, the maximum step (referred to as "TIR") of the color filter substrate before application of the curable composition0") was measured, and the maximum step (referred to as" TIR ") of the obtained color filter substrate with a cured film was measured after the color filter substrate with a cured film was produced1") was measured. From the two obtained maximum steps, the planarization ratio was calculated to be 100% × [ (TIR)0)-(TIR1)]/(TIR0). The calculated values are shown in table 1.
[ evaluation of planarization ]
The case where the planarization rate was 50% or more was evaluated as planarization "○", and the case where the planarization rate was less than 50% was evaluated as planarization "x", and the evaluation results are shown in table 1.
Examples 2 to 11 and comparative examples 1 to 4
The curable composition was obtained by mixing and dissolving the components in the proportions (unit: g) shown in Table 1 by the method of example 1. Comparative examples 2 to 4 do not describe the proportion of the polyfunctional carboxyl compound (B) in 100% by weight of the total amount of the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C). In comparative examples 3 and 4, the ratio (unit: weight%, described as "100 × (Z)/[ (B) + (Z) ]" in the table) of the polymer (Z) having a cinnamoyl group and an epoxy group in 100 wt% of the total amount of the polyfunctional carboxyl compound (B) and the polymer (Z) having a cinnamoyl group and an epoxy group is shown in table 1.
The adhesiveness was evaluated by the method of example 1, the transparency was evaluated from the measured value of the light transmittance, the heat resistance was evaluated from the calculated value of the 5% weight loss temperature, the photo-alignment property was evaluated, and the planarization property was evaluated from the calculated value of the planarization rate. The measured values, calculated values, and evaluation results of the respective components are shown in table 1. Wherein the rotation speed of spin coating the curable composition on the glass substrate is adjusted so that the thickness of the cured film is approximately 1.5 μm.
As is clear from the results shown in table 1: the curable compositions of examples 1 to 11 have low viscosity and excellent planarization properties, and cured films obtained from the curable compositions have excellent transparency, heat resistance, and photo-alignment properties. On the other hand, the cured film obtained from the curable composition of comparative example 1 containing no imide compound (a) had poor photo-alignment properties. The curable composition described in comparative example 2, which did not contain the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C), had high viscosity and poor leveling property. In addition, the cured films obtained from the curable compositions of comparative examples 3 and 4, which are compositions containing the polyfunctional carboxyl compound (B) and the polymer (Z) having a cinnamoyl group and an epoxy group, were poor in transparency and heat resistance.
[ industrial applicability ]
The curable composition of the present invention has low viscosity and excellent planarization properties, and the cured film obtained from the curable composition of the present invention has excellent transparency, heat resistance and photo-alignment properties, and thus can be used as a color filter protective film having photo-alignment properties.

Claims (9)

1. A curable composition comprising an imide compound (A), a polyfunctional carboxyl compound (B) and a polyfunctional epoxy compound (C), and
the imide compound (A) is a reaction product derived from raw materials which are essential for an acid anhydride (a1) having a polymerizable double bond and an alkoxysilyl compound (a2) having an amino group,
the polyfunctional carboxyl compound (B) is a compound having three or more carboxyl groups per molecule,
the polyfunctional epoxy compound (C) is a compound having three or more epoxy groups per molecule.
2. The curable composition according to claim 1, wherein the imide compound (A) is 5 to 80% by weight based on 100% by weight of the total amount of the imide compound (A), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C);
the amount of the polyfunctional carboxyl compound (B) is 20 to 80 wt% based on 100 wt% of the total amount of the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C).
3. The curable composition according to claim 1, wherein the imide compound (A) is 15 to 60% by weight based on 100% by weight of the total amount of the imide compound (A), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C);
the amount of the polyfunctional carboxyl compound (B) is 40 to 75 wt% based on 100 wt% of the total amount of the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C).
4. The curable composition according to any one of claims 1 to 3, wherein the acid anhydride (a1) having a polymerizable double bond is at least one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2);
Figure FDA0002086737880000011
in the formula (1), R1And R2Each independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms;
Figure FDA0002086737880000012
in the formula (2), R3Is hydrogen or C1-5 alkyl.
5. The curable composition according to any one of claims 1 to 4, wherein the acid anhydride (a1) having a polymerizable double bond is at least one selected from maleic anhydride, citraconic anhydride and itaconic anhydride.
6. The curable composition according to any one of claims 1 to 5, wherein the alkoxysilane-based compound (a2) having an amino group is at least one selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminophenyltrimethoxysilane and 4-aminophenyltriethoxysilane.
7. The curable composition according to any one of claims 1 to 6, wherein the polyfunctional carboxyl compound (B) is a polyesteramic acid obtained by using a tetracarboxylic dianhydride, a diamine and a polyvalent hydroxyl compound as essential raw materials.
8. A cured film obtained by curing the curable composition according to any one of claims 1 to 7.
9. A color filter substrate comprising the cured film according to claim 8.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113050212A (en) * 2021-01-12 2021-06-29 苏州群烨新材料科技有限公司 Infrared band-pass filter, preparation method thereof and imaging device with infrared band-pass filter

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01149878A (en) * 1987-12-04 1989-06-12 Shin Etsu Chem Co Ltd Primer composition and usage thereof
JP2003287617A (en) * 2002-03-28 2003-10-10 Toray Ind Inc Thermosetting resin solution composition for color filter, color filter and liquid crystal display device
CN101965542A (en) * 2008-03-10 2011-02-02 旭化成电子材料株式会社 Photosensitive polyorganosiloxane composition
CN105062338A (en) * 2015-08-05 2015-11-18 天长市开林化工有限公司 Weatherproof aqueous alkyd resin/epoxy resin coating
CN105086316A (en) * 2014-05-15 2015-11-25 捷恩智株式会社 Thermosetting compositions, harden film, color filter, liquid crystal displaying element, solid camera shooting element and light emitting diode illuminant

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09230364A (en) 1997-03-18 1997-09-05 Hitachi Ltd Liquid crystal display device
JP5298428B2 (en) * 2006-12-26 2013-09-25 Ｊｎｃ株式会社 Thermosetting resin composition and cured film
JP6079033B2 (en) * 2012-08-07 2017-02-15 Jnc株式会社 Photo / thermosetting composition
JP5994564B2 (en) 2012-10-22 2016-09-21 Jnc株式会社 Thermosetting composition having photo-alignment
JP2015049419A (en) * 2013-09-03 2015-03-16 Jnc株式会社 Composition for optical orientation film
JP6939110B2 (en) * 2016-07-13 2021-09-22 Jnc株式会社 Thermosetting composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01149878A (en) * 1987-12-04 1989-06-12 Shin Etsu Chem Co Ltd Primer composition and usage thereof
JP2003287617A (en) * 2002-03-28 2003-10-10 Toray Ind Inc Thermosetting resin solution composition for color filter, color filter and liquid crystal display device
CN101965542A (en) * 2008-03-10 2011-02-02 旭化成电子材料株式会社 Photosensitive polyorganosiloxane composition
CN105086316A (en) * 2014-05-15 2015-11-25 捷恩智株式会社 Thermosetting compositions, harden film, color filter, liquid crystal displaying element, solid camera shooting element and light emitting diode illuminant
CN105062338A (en) * 2015-08-05 2015-11-18 天长市开林化工有限公司 Weatherproof aqueous alkyd resin/epoxy resin coating

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113050212A (en) * 2021-01-12 2021-06-29 苏州群烨新材料科技有限公司 Infrared band-pass filter, preparation method thereof and imaging device with infrared band-pass filter

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