CN109283792B - Photosensitive composition, pattern forming method, cured product and display device - Google Patents

Photosensitive composition, pattern forming method, cured product and display device Download PDF

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Publication number
CN109283792B
CN109283792B CN201810791239.3A CN201810791239A CN109283792B CN 109283792 B CN109283792 B CN 109283792B CN 201810791239 A CN201810791239 A CN 201810791239A CN 109283792 B CN109283792 B CN 109283792B
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group
meth
substituent
formula
photosensitive composition
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CN109283792A (en
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片野彰
引田二郎
盐田大
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Tokyo Ohka Kogyo Co Ltd
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Tokyo Ohka Kogyo Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)
  • Indole Compounds (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention provides: a photosensitive composition which has excellent light transmittance and sensitivity to exposure, can form a cured product which is sufficiently cured by exposure, can form a sufficient level difference between a full-tone exposure portion and a halftone exposure portion in a pattern formed when exposure is performed through a halftone mask, and can ensure a sufficient level of the halftone exposure portion; a pattern formation method using the photosensitive composition; a cured product of the photosensitive composition; a photosensitive adhesive containing the photosensitive composition; and a method for bonding an adherend using the photosensitive composition. In the present invention, 2 or more oxime ester compounds having peaks in a wavelength region of 320nm or more and less than 400nm in an absorption spectrum and having different maximum wavelengths of the peaks are used in combination as the photopolymerization initiator (A), and no compound exhibiting a gram absorption coefficient of 10 or more at any wavelength in a wavelength region of 400nm or more is used.

Description

Photosensitive composition, pattern forming method, cured product and display device
Technical Field
The present invention relates to a photosensitive composition, a pattern formation method using the photosensitive composition, a cured product formed using the photosensitive composition, and a display device having the cured product.
Background
In a panel for a display device such as a liquid crystal display device, a material such as an insulating film or a spacer (spacer) needs to efficiently transmit light emitted from a light source such as a backlight. Therefore, in order to form a pattern of an insulating film or a spacer, a photosensitive composition that provides a transparent cured film by exposure to light is used. By selectively exposing such a photosensitive composition, a pattern of a transparent cured film can be formed.
In addition, a patterned light-shielding film such as a black matrix or a black columnar spacer (black column spacer) is often formed on a panel for a display device. In such applications, various photosensitive compositions containing a light blocking agent and a photopolymerization initiator, which can be used for forming a light blocking film, have also been proposed.
Since the photosensitive composition for forming the light-shielding film contains a light-shielding agent, a photopolymerization initiator is required to have higher sensitivity.
For example, as a photosensitive composition containing a photopolymerization initiator excellent in sensitivity, a photosensitive composition containing an oxime ester compound containing a fluorene ring substituted at the 9-position as a main skeleton as a photopolymerization initiator has been proposed (see patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication 2016-218353
Disclosure of Invention
Problems to be solved by the invention
In addition, in the production of a panel for an image display device or the like, elements such as TFTs may be arranged on a layer adjacent to a patterned cured film formed using the photosensitive composition. In this case, too, exposure is often performed through a half tone mask (half tone mask), and patterns of different heights are formed in consideration of the heights of the elements.
However, the photosensitive composition described in patent document 1 has a problem that although it is excellent in sensitivity, it is not always easy to achieve the following object: when exposure is performed through a halftone mask, a sufficient difference in height is formed between the full-tone exposure portion and the halftone exposure portion in the formed pattern, and a sufficient height of the halftone exposure portion is ensured.
The present invention has been made in view of the above-described problems, and an object thereof is to provide: a photosensitive composition which has excellent light transmittance and sensitivity to exposure, can form a cured product which is sufficiently cured by exposure, and can form a sufficient height difference between a full-tone exposure portion and a halftone exposure portion in a pattern formed when exposure is performed through a halftone mask, and can ensure a sufficient height of the halftone exposure portion; a pattern formation method using the photosensitive composition; a cured product of the photosensitive composition; a photosensitive adhesive containing the photosensitive composition; and a method for bonding an adherend using the photosensitive composition.
Means for solving the problems
The inventors of the present application have found that the above-described problems can be solved by using 2 or more oxime ester compounds having peaks in a wavelength region of 320nm or more and less than 400nm in an absorption spectrum and having different maximum wavelengths of the peaks in combination as the photopolymerization initiator (a) in a photosensitive composition containing the photopolymerization initiator (a), and by excluding the photopolymerization initiator (a) from the compounds exhibiting a gram absorption coefficient of 10 or more at any wavelength in the wavelength region of 400nm or more, and completed the present invention.
In accordance with embodiment 1 of the present invention, there is provided a photosensitive composition comprising a photopolymerization initiator (A),
the photopolymerization initiator (A) contains 2 or more oxime ester compounds having a peak in the wavelength region of 320nm or more and less than 400nm in the absorption spectrum,
the photopolymerization initiator (A) does not contain a compound exhibiting a gram absorbance coefficient of 10 or more at any wavelength in a wavelength region of 400nm or more,
the peak maximum wavelength of 2 or more oxime ester compounds is different from each other.
In accordance with embodiment 2 of the present invention, there is provided a method for forming a cured product, comprising the steps of:
forming a coating film using the photosensitive composition according to embodiment 1, and
The coating film is exposed to light.
In accordance with claim 3 of the present invention, the cured product of the photosensitive composition according to claim 1 is obtained.
The 4 th aspect of the present invention is a photosensitive adhesive comprising the photosensitive composition according to the 1 st aspect.
In accordance with a 5 th aspect of the present invention, there is provided a method for bonding bonded surfaces, comprising the steps of:
an adhesive layer formed of the photosensitive adhesive according to the 4 th aspect is formed on one or both of the opposed surfaces to be adhered, and
the adhesive layer is cured by exposure to light.
ADVANTAGEOUS EFFECTS OF INVENTION
By the present invention, it is possible to provide: a photosensitive composition which has excellent light transmittance and sensitivity to exposure, can form a cured product which is sufficiently cured by exposure, and can form a sufficient height difference between a full-tone exposure portion and a halftone exposure portion in a pattern formed when exposure is performed through a halftone mask, and can ensure a sufficient height of the halftone exposure portion; a pattern formation method using the photosensitive composition; a cured product of the photosensitive composition; a photosensitive adhesive containing the photosensitive composition; and a method for bonding an adherend using the photosensitive composition.
Detailed Description
Photosensitive composition
The photosensitive composition of the present invention contains a photopolymerization initiator (a).
The photopolymerization initiator (A) contains 2 or more oxime ester compounds having a peak in the wavelength region of 320nm or more and less than 400nm in the absorption spectrum.
Wherein the maximum wavelengths of the peaks are different with respect to 2 or more oxime ester compounds.
Therefore, when the photosensitive composition is exposed to light, the exposure light can be easily used sufficiently, and the sensitivity of the photosensitive composition is excellent.
The maximum wavelength at the longest wavelength side among the maximum wavelengths of the peaks of 2 or more oxime ester compounds is denoted as lambda max-r The maximum wavelength at the shortest wavelength side is denoted as lambda max-b Lambda is at the time max-r And lambda is max-b The difference is preferably 20nm or more. The upper limit is, for example, 70nm or less, preferably 50nm or less.
In addition, lambda max-r Preferably in the range of 350nm to 400nm, lambda max-b Preferably in the range of 320nm to 360 nm.
In this case, even when the wavelength region of the exposure light used for exposing the photosensitive composition is wide, the energy of the exposure light is easily and efficiently used for curing, and good sensitivity is easily achieved regardless of the light source.
The photopolymerization initiator (A) does not contain a compound having a gram absorbance of 10 or more at any wavelength in the wavelength region of 400nm or more. The photopolymerization initiator preferably does not contain a compound exhibiting a gram absorbance coefficient of 5 or more at any wavelength in a wavelength region of 400nm or more, more preferably does not contain a compound exhibiting a gram absorbance coefficient of 1 or more.
When the photopolymerization initiator (a) contains a compound having a gram absorbance of 10 or more at any wavelength in a wavelength region of 400nm or more, the light transmittance of the photosensitive composition tends to be low.
Therefore, the sensitivity as a photosensitive composition may be lowered, or it may be difficult to form a pattern having a desired height by halftone exposure.
However, the photosensitive composition described above is excellent in light transmittance because it does not contain a compound that exhibits a gram absorption coefficient of 10 or more at any wavelength in a wavelength region of 400nm or more as the photopolymerization initiator (a). As a result, it is easy to fully utilize the exposure light, and it is easy to form a pattern having a desired height by halftone exposure.
In addition, when the photosensitive composition is used as a photosensitive adhesive, the photosensitive adhesive is often applied thickly. However, since the photosensitive adhesive containing the photosensitive composition containing the photopolymerization initiator (a) is excellent in light transmittance as described above, the photosensitive adhesive cures well even if applied to a relatively thick surface.
In addition, when a pattern is formed by halftone exposure using the photosensitive composition, a sufficient level difference is easily formed between the full tone exposure portion and the halftone exposure portion in the formed pattern.
As described above, the photopolymerization initiator (a) contains 2 or more photopolymerization initiators in combination. Wherein, as described above, the photopolymerization initiator (a) must contain 2 or more oxime ester compounds. The content of each photopolymerization initiator contained in the photopolymerization initiator (a) is not particularly limited within a range that does not hinder the object of the present invention.
The content ratio of each photopolymerization initiator to the mass of the photopolymerization initiator (a) is preferably 1 mass% or more, more preferably 5 mass% or more, further preferably 10 mass% or more, and particularly preferably 20 mass% or more.
The content ratio of each photopolymerization initiator to the mass of the photopolymerization initiator (a) is preferably 99 mass% or less, more preferably 95 mass% or less, further preferably 90 mass% or less, and particularly preferably 80 mass% or less.
In addition, the composition has lambda relative to the mass of the photopolymerization initiator (A) max-r The content ratio of the oxime ester compound is preferably 1% by mass or more and 99% by mass or less, more preferably 5% by mass or more and 95% by mass or less, still more preferably 10% by mass or more and 90% by mass or less, particularly preferably 15% by mass or more and 80% by mass or less.
Having lambda relative to the mass of the photopolymerization initiator (A) max-b The content ratio of the oxime ester compound is preferably 1% by mass or more and 99% by mass or less, more preferably 5% by mass or more and 95% by mass or less, still more preferably 10% by mass or more and 90% by mass or less, particularly preferably 20% by mass or more and 85% by mass or less.
Has a molecular weight not belonging to lambda in the range of 320nm or more and less than 400nm relative to the mass of the photopolymerization initiator (A) max-r And lambda (lambda) max-b The ratio of the content of the other oxime ester initiator having the maximum wavelength is preferably 0 mass% or more and 98 mass% or less, more preferably 0 mass% or more and 90 mass% or less, still more preferably 0 mass% or more and 80 mass% or less, particularly preferably 0 mass% or more and 65 mass% or less.
When the photopolymerization initiator (A) is formed of the 1 st oxime ester compound and the 2 nd oxime ester compound, the ratio M1/M2 of the mass M1 of the 1 st oxime ester compound to the mass M2 of the 2 nd oxime ester compound is preferably 1/9 or more and 9/1 or less, more preferably 2/8 or more and 8/2 or less, particularly preferably 3/7 or more and 7/3 or less.
Hereinafter, each component contained in the photosensitive composition will be described.
Photopolymerization initiator (A) >)
As described above, the photopolymerization initiator (a) contains 2 or more oxime ester compounds having peaks in the wavelength region of 320nm or more and less than 400nm in the absorption spectrum.
The photopolymerization initiator (A) does not contain a compound having a gram absorbance of 10 or more at any wavelength in the wavelength region of 400nm or more.
The photopolymerization initiator (a) may contain other photopolymerization initiators other than the oxime ester compound. The amount of the oxime ester compound in the photopolymerization initiator (a) is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, further more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass.
When the photopolymerization initiator (a) includes other photopolymerization initiators other than the oxime ester compound, the photopolymerization initiator (a) may include 2 or more other photopolymerization initiators in combination.
Other photopolymerization initiators than oxime ester compounds are known photopolymerization initiators, and compounds exhibiting a gram absorbance of 10 or more at any wavelength in the wavelength region of 400nm or more can be used.
Specific examples of the known photopolymerization initiator other than the oxime ester compound include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [ 4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-dimethoxy-1, 2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [ 4- (methylthio) phenyl ] -2-morpholino (morpholino) propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino) butan-1-one, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, 4-benzoyl-4 '-dimethylbenzoyl-4' -dimethylbenzoic acid, 4-dimethylaminoethyl benzoate, 4-dimethylbenzoate, 4-dimethylaminoethyl benzoate and 4-dimethylbenzoate, 4-dimethylamino-2-isopentylbenzoic acid, benzil-beta-methoxyethyl acetal, benzil dimethyl ketal, benzoyl-benzoic acid methyl ester, 2, 4-diethylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthone, 2-chlorothioxanthone, 2, 4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-ethylanthraquinone, octamethylanthraquinone, 1, 2-benzanthraquinone, 2, 3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide (cumene hydroperoxide), 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-bis (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, 2- (2-mercaptoimidazole, 2 '-dimethoxybenzophenone, 2, 4' -dimethylbenzophenone, michler's ketone), 4' -bis-diethylaminobenzophenone (i.e., ethyl Michler's ketone), 4' -dichlorobenzophenone, 3, 3-dimethyl-4-methoxybenzophenone, benzil, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2-diethoxyacetophenone, p-dimethyl acetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, alpha-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthixanthone, 2-isopropylthioxanthone, dibenzosuberone (dibenzosuberone), 4-dimethylaminobenzyl benzoate, 9-phenylacridine, 1, 7-bis- (9-acridinyl) heptane, 1, 5-bis- (9-acridinyl) pentane, 1, 3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4, 6-trichloromethyl-triazine, 2-methyl-2-chlorotriazine-2-methyl-2-chlorotriazine, 2-o-methyl-2-chlorotriazine, 2-chlorotrifluoromethyl-2-o-2-chlorotriazine, 6-methyl-o-2-chlorotrifluoromethyl-2-chlorotriazine 2- [2- (4-diethylamino-2-methylphenyl) vinyl ] -4, 6-bis (trichloromethyl) s-triazine, 2- [2- (3, 4-dimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) s-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-ethoxystyryl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-n-butoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2, 4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl s-triazine, 2, 4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl s-triazine, 2, 4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl s-triazine, 2, 4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl s-triazine, and the like.
The other photopolymerization initiator may be selected from the above group of compounds, based on measurement of gram absorbance in a wavelength region of 400nm or more.
The combination of the plurality of oxime ester compounds in the photopolymerization initiator (a) is not particularly limited as long as the aforementioned conditions concerning the photopolymerization initiator (a) are satisfied.
The preferable combination of the oxime ester compounds is a combination of an oxime ester compound (A1) represented by the following formula (A1) and an oxime ester compound (A2) represented by the following formula (A2).
The photopolymerization initiator (a) may contain 1 or 2 or more oxime ester compounds (A1), and 1 or 2 or more oxime ester compounds (A2).
Hereinafter, the oxime ester compound (A1) and the oxime ester compound (A2) will be described.
[ oxime ester Compound (A1) ]
The oxime ester compound (A1) is a compound represented by the following formula (A1) and satisfying at least 1 condition in the following (1) to (3).
[ chemical formula 1]
(in the formula (a 1), R 1 Is a monovalent organic group, R 2 Is a hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent, R 3 Is a monovalent organic group which is a group of organic atoms,R 4 is a monovalent organic group, R 5 And R is 6 Each independently is a benzene ring which may have a substituent, or a naphthalene ring which may have a substituent, and m1, m2, and m3 are each 0 or 1. )
(1)R 1 comprising-OR 7 A group represented by R 7 Is haloalkyl.
(2) m2 is 1, R 4 comprising-OR 7 A group represented by R 7 Is haloalkyl.
(3)R 3 Is a branched alkyl group which may have a substituent.
In the formula (a 1), R 5 And R is 6 Is a benzene ring which may have a substituent or a naphthalene ring which may have a substituent.
The inclusion and R shown in formula (a 1) 3 The ring of the bonded nitrogen atom is condensed with the benzene ring or naphthalene ring by sharing any carbon-carbon bond in the benzene ring or naphthalene ring.
Accordingly, the inclusion in formula (a 1) is as follows 3 The ring of bound nitrogen atoms being derived from R 5 And from 2 carbon atoms of R 6 Five-membered ring having 2 carbon atoms as ring structure atoms.
That is, the compound represented by the formula (a 1) has a structure represented by R 5 And R is 6 And a condensed ring of three to five rings formed with the five-membered ring as a central skeleton.
R 5 And/or R 6 In the case of naphthalene ring, comprises a group R 3 The form of the five-membered ring of the bonded nitrogen atom and the condensed form of the naphthalene ring are not particularly limited.
R 5 And R is 6 When at least one of them is naphthalene ring, R is 5 And R is 6 And comprises and R 3 The condensed ring formed by the above five-membered ring of the bonded nitrogen atom may be any of the following.
[ chemical formula 2]
As R 5 And R is 6 Benzene or naphthalene of (2)When the ring has a substituent, the kind and number of the substituent are not particularly limited within a range that does not hinder the object of the present invention.
Preferable examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, a halogen atom, and a cyano group.
As R 5 And R is 6 When the benzene ring or naphthalene ring has a substituent, the number of the substituent is not limited within a range that does not interfere with the object of the present invention, and is preferably 1 to 4. When the number of substituents is plural, the plural substituents may be the same or different.
R 5 When having substituents, R 5 The substituents may be as defined for R 1 Or R is 3 Bonding to form a ring.
In addition, R 6 When having substituents, R 6 The substituents may be as defined for R 3 Bonding to form a ring.
R 5 Has substituent and R 1 The ring formed by bonding may be a hydrocarbon ring or a heterocyclic ring. The hetero atom contained in the heterocycle is not particularly limited. Preferable examples of the hetero atom include N, O, S.
R 5 And/or R 6 Has substituent and R 3 The ring formed by bonding other than R 3 Other heteroatoms may be included in addition to the bonded nitrogen atoms. The hetero atom contained in the heterocycle is not particularly limited. Preferable examples of the hetero atom include N, O, S.
R 5 Having substituents or R 6 Has substituent and R 3 When the compounds are bonded to form a ring, the compounds represented by the formula (a 1) are preferably represented by the following formulas (a 1-1-a) to (a 1-1-h)The compounds shown.
[ chemical formula 3]
(in the formulae (a 1-1-a) to (a 1-1-h), R 1 、R 2 、R 4 Like formula (a 1), m1, m2, and m3, R 8 Is alkyl. )
As R 8 The alkyl group of (2) may be linear or branched. As R 7 The number of carbon atoms of the alkyl group of (a) is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10.
R 5 Has substituent and R 1 When bonded to form a ring, in formula (a 1), m1 is preferably 0. In this case, the compound represented by the formula (a 1) is preferably a compound represented by the following formulas (a 1-1-i) to (a 1-1-l).
[ chemical formula 4]
(in the formulae (a 1-1-i) to (a 1-1-l), R 2 、R 3 、R 4 Like formula (a 1), m2 and m3 are R 8 Is an alkyl group having 1 to 20 carbon atoms. )
As R 8 The alkyl group of (2) may be linear or branched.
In view of R as described hereinabove 5 And R is R 6 The compound represented by the formula (a 1) is preferably a compound represented by the following formulas (a 1-I) to (a 1-IV), more preferably a compound represented by the formula (a 1-II) or (a 1-III), and particularly preferably a compound represented by the formula (a 1-III).
[ chemical formula 5]
(A1In any of (a 1-IV), R 1 、R 2 、R 3 、R 4 M1, m2, and m3 are the same as in formula (a 1). )
The compounds represented by the above-mentioned formulas (a 1-I) to (a 1-IV) are preferably compounds represented by the following formulas (a 1-I-a) to (a 1-IV-a), more preferably compounds represented by the formula (a 1-II-a) or formula (a 1-III-a), and particularly preferably compounds represented by the formula (a 1-III-a).
[ chemical formula 6]
The compounds represented by the above-mentioned formulae (a 1-I-a) to (a 1-IV-a) are preferably compounds represented by the following formulae (a 1-I-b) to (a 1-IV-b), more preferably compounds represented by the following formulae (a 1-II-b) or (a 1-III-b), and particularly preferably compounds represented by the following formulae (a 1-III-b).
[ chemical formula 7]
Regarding preference as R 1 Examples of the monovalent organic group of (a) include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group (cycloalkoxy), a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoxyoxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amino group which is substituted with 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group, and the like.
R 1 In the case of alkyl, the alkyl isThe number of carbon atoms of the group is preferably 1 to 20, more preferably 1 to 6. In addition, R 1 When alkyl is used, the alkyl may be straight-chain or branched. As R 1 Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl. In addition, R 1 When alkyl, the alkyl group may contain an ether linkage (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.
R 1 In the case of an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 6. In addition, R 1 When the alkoxy group is a straight chain or branched chain. As R 1 Specific examples of the alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, isopentyloxy, sec-pentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isononyl, n-decyloxy, isodecyloxy and the like. In addition, R 1 In the case of alkoxy groups, the alkoxy groups may contain ether linkages (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, and methoxypropyloxy groups.
R 1 In the case of cycloalkyl or cycloalkoxy, the number of carbon atoms of the cycloalkyl or cycloalkoxy is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. As R 1 Specific examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptylRadical, and cyclooctyl, and the like. As R 1 Specific examples of the cycloalkoxy group include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy.
R 1 When the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is used, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, more preferably 2 to 7. As R 1 Specific examples of the saturated aliphatic acyl group include acetyl, propionyl, n-butyryl, 2-methylpropanoyl, n-pentanoyl, 2-dimethylpropionyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecanoyl, and n-hexadecanoyl. As R 1 Specific examples of saturated aliphatic acyloxy groups include acetyloxy, propionyloxy, n-butyryloxy, 2-methylpropanoyloxy, n-pentanoyloxy, 2-dimethylpropionyloxy, n-hexanoyloxy, n-heptanoyloxy, n-octanoyloxy, n-nonanoyloxy, n-decanoyloxy, n-undecanoyloxy, n-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanoyloxy, and n-hexadecanoyloxy.
R 1 In the case of an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. As R 1 Specific examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyloxycarbonyl.
R 1 In the case of the phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. In addition, R 1 In the case of the naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less. As R 1 Specific examples of the phenylalkyl group include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. As R 1 Specific examples of the naphthylalkyl group include an α -naphthylmethyl group, a β -naphthylmethyl group, a 2- (α -naphthyl) ethyl group, and a 2- (β -naphthyl) ethyl group. R is R 1 R is phenylalkyl or naphthylalkyl 1 The phenyl group or the naphthyl group may have a further substituent.
R 1 When the heterocyclic group is a heterocyclic group, the heterocyclic group is a five-membered or six-membered monocyclic ring containing 1 or more N, S, O, or is a heterocyclic group in which the monocyclic rings are condensed with each other or the monocyclic rings are condensed with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, and the like. R is R 1 When the heterocyclic group is a heterocyclic group, the heterocyclic group may further have a substituent.
R 1 In the case of a heterocyclylcarbonyl group, the heterocyclic group contained in the heterocyclylcarbonyl group is represented by R 1 The same applies to the case of heterocyclic groups.
R 1 When the amino group is substituted with 1 or 2 organic groups, preferable examples of the organic groups include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 21 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, and a carbon which may have a substituentPhenylalkyl groups having 7 to 20 atoms, naphthyl groups which may have substituents, naphthoyl groups which may have substituents, naphthylalkyl groups which may have substituents and have 11 to 20 carbon atoms, heterocyclic groups, and the like. Specific examples of these preferred organic groups and R 1 Likewise, the same is true. Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, phenylamino, naphthylamino, acetylamino, propionylamino, n-butyrylamino, n-pentanoylamino, n-hexanoylamino, n-heptanoylamino, n-octanoylamino, n-decanoylamino, benzoylamino, α -naphthoylamino, β -naphthoylamino and the like.
As R 1 Examples of the substituent when the phenyl group, the naphthyl group, and the heterocyclic group included in (a) further have a substituent(s) include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl, halogen, nitro, cyano and the like. R is R 1 When the phenyl group, the naphthyl group, and the heterocyclic group included in the (b) have further substituents, the number of the substituents is not limited within a range that does not hinder the object of the present invention, and is preferably 1 to 4. R is R 1 When the phenyl group, the naphthyl group, and the heterocyclic group included in (a) have a plurality of substituents, the plurality of substituents may be the same or different.
In addition, as R 1 Cycloalkyl alkyl, phenoxyalkyl which may have a substituent on the aromatic ring, phenylthioalkyl which may have a substituent on the aromatic ring are also preferable. Phenoxyalkyl and phenylthio Substituted alkyl and R 1 The substituents which the phenyl groups contained in (a) may have are the same.
In monovalent organic groups, R is 1 Preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, a phenylthioalkyl group which may have a substituent on an aromatic ring. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. Among phenyl groups which may have a substituent, methylphenyl is preferable, and 2-methylphenyl is more preferable. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among cycloalkylalkyl groups, cyclopentylethyl is preferred. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among phenylthioalkyl groups which may have a substituent on the aromatic ring, 2- (4-chlorophenylthio) ethyl is preferable.
As described above, the compound represented by the formula (a 1) needs to satisfy at least 1 condition in the following (1) to (3).
(1)R 1 comprising-OR 7 A group represented by R 7 Is haloalkyl.
(2) m2 is 1, R 4 comprising-OR 7 A group represented by R 7 Is haloalkyl.
(3)R 3 Is a branched alkyl group which may have a substituent.
Thus, R is 1 Preferably by-OR 7 The indicated substituents are substituted. R is R 7 Is haloalkyl. R is R 1 is-OR 7 R when the indicated group is substituted 1 comprises-OR 7 The number of the groups represented is not particularly limited. R is R 1 is-OR 7 R when the indicated group is substituted 1 comprises-OR 7 The number of groups represented is preferably 1 or 2, more preferably 1.
In addition, the compound represented by the formula (a 1) has-OR 7 The number of groups represented is also preferably 1 or 2, more preferably 1.
Examples of the halogen atom contained in the haloalkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The haloalkyl group may contain 1 halogen atom or may contain 2 or more halogen atoms in combination.
The number of halogen atoms possessed by the haloalkyl group is not particularly limited insofar as it does not interfere with the object of the present invention. The number of halogen atoms in the haloalkyl group is preferably 1 or more, more preferably 2 or more, and particularly preferably 3 or more. The upper limit of the number of halogen atoms in the haloalkyl group is preferably 7 or less, more preferably 6 or less, and particularly preferably 5 or less, from the viewpoint of good compatibility between the compound represented by the formula (a 1) and other components in the photosensitive composition.
The number of halogen atoms contained in the compound represented by the formula (a 1) is preferably 1 or more, more preferably 2 or more, particularly preferably 3 or more, preferably 7 or less, more preferably 6 or less, particularly preferably 5 or less.
The number of carbon atoms of the haloalkyl group is not particularly limited within a range that does not hinder the object of the present invention. The number of carbon atoms of the haloalkyl group is preferably 1 or more, more preferably 2 or more, and particularly preferably 3 or more. The upper limit of the number of carbon atoms in the haloalkyl group is preferably 10 or less, more preferably 7 or less, and particularly preferably 5 or less.
As the haloalkyl group, a fluoroalkyl group is particularly preferable. As a preferred specific example of the haloalkyl group, examples thereof include 2, 3-tetrafluoropropyl group 2, 2-trifluoroethyl group, 3-trifluoropropyl group 2, 2-trifluoroethyl group 3, 3-trifluoropropyl group. Among these, 2, 3-tetrafluoropropyl is preferable in terms of ease of production of the compound represented by formula (a 1) and the like.
Regarding R as 1 Is preferably benzene substituted with 1 or 2 haloalkyl groupsA base. Specifically, as R 1 The haloalkyl-substituted group of (a) is preferably a group represented by the following formula (a 1-01).
[ chemical formula 8]
(in the formula (a 1-01), R 7 As described above, R 9 As R 1 Wherein m4 is 1 or 2, and m4+m5 is an integer of 1 to 5 inclusive. )
As R 9 The alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms are preferable, the alkyl group having 1 to 6 carbon atoms is more preferable, the methyl group and the ethyl group are more preferable, and the methyl group is particularly preferable.
m5 is preferably 1.
In addition, R 1 May be a group represented by the following formula (a 1-02).
[ chemical formula 9]
(in the formula (a 1-02), R 1 、R 2 、R 3 、R 4 、R 5 、R 6 Like formula (a 1), m1, m2, and m3, R 10 Is a divalent organic group. )
As R 10 The divalent organic group of (2) is not particularly limited insofar as it does not interfere with the object of the present invention. Regarding R as 10 Preferable examples of the divalent organic group of (a) include an alkanediyl group having 1 to 10 carbon atoms (e.g., methylene, ethane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl) and arylene group (p-phenylene, m-phenylene, o-phenylene, 1 '-biphenyl-4, 4' -diyl).
As R 1 Specific examples of the compound represented by the formula (a 1) when the compound represented by the formula (a 1-02) is a group represented by the formula (a 1) are given below Is a compound of (a).
[ chemical formula 10]
R as described hereinabove 1 In (3), a group represented by the following formula is preferable.
[ chemical formula 11]
In the formula (a 1), R 2 Is a hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent. The hydrocarbon group which may have a substituent is preferably an alkyl group having 1 or more and 11 or less carbon atoms which may have a substituent, or an aryl group which may have a substituent. The aryl group is preferably a phenyl group or a naphthyl group, and preferably a phenyl group. As R 2 Examples of the "substituent" which may be included in the alkyl group may include a phenyl group and a naphthyl group. In addition, as R 2 The substituent which may be present in the case of the aryl group is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom or the like.
R 2 In the case of a heterocyclic group, the heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. R is R 2 When the heterocyclic group is a heterocyclic group, the heterocyclic group is a five-membered or six-membered monocyclic ring containing 1 or more N, S, O, or is a heterocyclic group in which the monocyclic rings are condensed with each other or the monocyclic rings are condensed with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is 3 or less. Examples of the heterocycle constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran, and the like.
R 2 In the case of a heterocyclic group, examples of substituents which may be included in the heterocyclic group include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, and the like.
As R 2 Methyl, phenyl, and thienyl are preferred, and methyl is more preferred.
In the formula (a 1), R 3 Is a monovalent organic group. R is R 3 Can be selected from various organic groups within a range that does not hinder the object of the present invention. As R 3 Examples of the preferable group include an alkyl group which may have a substituent having 1 to 20 carbon atoms, a cycloalkyl group which may have a substituent having 3 to 20 carbon atoms, a saturated aliphatic acyl group which may have a substituent having 2 to 20 carbon atoms, an alkoxycarbonyl group which may have a substituent having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group which may have a substituent having 7 to 20 carbon atoms, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylalkyl group which may have a substituent having 11 to 20 carbon atoms, a heterocyclic group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.
R 3 In these, an alkyl group having 1 to 20 carbon atoms is preferable. The alkyl group may be linear or branched. R is a compound represented by the formula (a 1) in terms of good solubility in the photosensitive composition 3 The number of carbon atoms of the alkyl group is preferably 2 or more, more preferably 5 or more, and particularly preferably 7 or more. In addition, R is a compound represented by the formula (a 1) in the photosensitive composition, in terms of good compatibility with other components 3 The number of carbon atoms of the alkyl group of (a) is preferably 15 or less, more preferably 10 or less.
R 3 When the substituent is present, preferable examples of the substituent include a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, and a carbon atomAlkoxy having 1 to 20 carbon atoms, aliphatic acyl having 2 to 20 carbon atoms, aliphatic acyloxy having 2 to 20 carbon atoms, phenoxy, benzoyl, benzoyloxy, -PO (OR) 2 A group represented by (R is an alkyl group having 1 to 6 carbon atoms), a halogen atom, a cyano group, a heterocyclic group, or the like. Preferred examples of the heterocyclic group as the substituent and R 2 The same applies to the preferred examples of the heterocyclic group.
As described above, the compound represented by the formula (a 1) needs to satisfy at least 1 condition in the following (1) to (3).
(1)R 1 comprising-OR 7 A group represented by R 7 Is haloalkyl.
(2) m2 is 1, R 4 comprising-OR 7 A group represented by R 7 Is haloalkyl.
(3)R 3 Is a branched alkyl group which may have a substituent.
Thus, R is 3 Branched alkyl groups which may have a substituent are preferable.
In addition, as R 3 The following formula (a 1-03) is possible:
[ chemical formula 12]
(in the formula (a 1-03), R 1 、R 2 、R 4 、R 5 、R 6 Like formula (a 1), m1, m2, and m3, R 11 Is a divalent organic group. )
As R 11 The divalent organic group of (2) is not particularly limited insofar as it does not interfere with the object of the present invention. Regarding R as 11 Preferable examples of the divalent organic group of (a) include alkanediyl groups having 1 to 10 carbon atoms (e.g., methylene, ethane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, heptane-1, 7-diyl, octane-1, 8-diyl), arylene groups (p-phenylene, m-phenylene, o-phenylene, 1 '-biphenyl-4, 4' -diyl)Etc.).
In addition, the following groups are also preferred as divalent organic groups R 11 . In the following formula, R 12 Is an alkylene group having 1 to 20 carbon atoms. Regarding R as 12 Preferred alkylene groups are methylene, ethane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, heptane-1, 7-diyl and octane-1, 8-diyl.
[ chemical formula 13]
As R 3 Specific examples of the compound represented by the formula (a 1) when the group represented by the formula (a 1-03) is given below are compounds of the following formula.
[ chemical formula 14]
As R described hereinabove 3 Preferable specific examples of (a) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, pentan-3-yl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, and 2-ethylhexyl.
As described above, due to R 3 Branched alkyl groups are preferred, and among the above alkyl groups, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, pentan-3-yl, sec-pentyl, tert-pentyl, and 2-ethylhexyl are preferred.
In addition, from the viewpoint of good solubility of the compound represented by formula (a 1) in the photosensitive composition, n-octyl and 2-ethylhexyl are preferable, and 2-ethylhexyl is more preferable.
R in formula (a 1) 4 Is a monovalent organic group. Regarding R as 4 Examples of monovalent organic groups of (2) include R 1 Identical to the monovalent organic groups of (2)A group.
R 4 By R 4 -(CO) m3 -the form of the group represented is bonded to the main skeleton of the compound represented by formula (a 1). As R 4 -(CO) m3 Preferred examples of the group represented by the following formula are given. In the following formula, m3 is 1 or 0 as in the formula (a 1).
[ chemical formula 15]
[ chemical formula 16]
[ chemical formula 17]
R as described above 4 -(CO) m3 Of the preferred examples of radicals represented, particular preference is given to 1,3, 5-trimethylbenzoyl.
As described above, the compound represented by the formula (a 1) needs to satisfy at least 1 condition in the following (1) to (3).
(1)R 1 comprising-OR 7 A group represented by R 7 Is haloalkyl.
(2) m2 is 1, R 4 comprising-OR 7 A group represented by R 7 Is haloalkyl.
(3)R 3 Is a branched alkyl group which may have a substituent.
Thus, R is 4 Preferably by-OR 7 The indicated substituents are substituted. R is R 7 Is haloalkyl. With respect to R 7 As described above.
Regarding R as 4 Preferably phenyl substituted with 1 or 2 haloalkyl groups. Specifically, with R as 1 Similarly, the haloalkyl-substituted group is preferably a group represented by the aforementioned formula (a 1-01).
In addition, as R 4 Also preferred are groups represented by the following formulas (a 1-04).
[ chemical formula 18]
(in the formula (a 1-04), R 1 、R 3 、R 5 、R 6 M1, m2 and m3 are the same as those of formula (a 1), R 13 Is a divalent organic group. )
As R 13 The divalent organic group of (2) is not particularly limited insofar as it does not interfere with the object of the present invention. Regarding R as 13 Preferable examples of the divalent organic group of (a) include alkanediyl groups having 1 to 10 carbon atoms (e.g., methylene, ethane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, heptane-1, 7-diyl, octane-1, 8-diyl, etc.), arylene groups (p-phenylene, m-phenylene, o-phenylene, 1 '-biphenyl-4, 4' -diyl, etc.).
In addition, the following groups are also preferred as divalent organic groups R 13 . In the following formula, R 13 Is an alkylene group having 1 to 20 carbon atoms which may be substituted with a halogen atom. Regarding R as 14 Preferred alkylene groups are methylene, ethane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, heptane-1, 7-diyl and octane-1, 8-diyl.
In addition, a group in which all hydrogen atoms in these alkylene groups are substituted with halogen atoms, particularly fluorine atoms, is also preferable as R 14 。
[ chemical formula 19]
In the formula (a 1), m1, m2, and m3 are each 0 or 1. M1 is preferably 0. M2 is preferably 1, and m3 is preferably 1.
The following compounds are preferred specific examples of the compound represented by the formula (a 1) described above.
[ chemical formula 20]
[ chemical formula 21]
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[ chemical formula 22]
[ chemical formula 23]
[ chemical formula 24]
[ chemical formula 25]
[ chemical formula 26]
[ oxime ester Compound (A2) ]
The oxime ester compound (A2) is a compound represented by the following formula (A2).
[ chemical formula 27]
(in the formula (a 2), CR is a group represented by the following formula (a 2 a) or the following formula (a 2 b), R a4 Is a monovalent organic group, R a5 An aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, n2 is 0 or 1,
[ chemical formula 28]
R a1 Is a hydrogen atom, a nitro group or a monovalent organic group, R a2 And R is a3 Each is a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, R a2 And R is R a3 Can be bonded to each other to form a ring, and n1 is an integer of 0 to 4 inclusive. )
From the synthesis of the oxime ester compound represented by the formula (a 2), the starting ease, the easiness of passing R a2 And R is a3 In view of the selection of the oxime ester compound to adjust the characteristics thereof, CR in the formula (a 2) is preferably a group represented by the formula (a 2 a).
R in the group represented by formula (a 2 a) or formula (a 2 b) as CR in formula (a 2) a1 Is a hydrogen atom, a nitro group or a monovalent organic group. R is R a1 And- (CO) bonded to the condensed ring in the formula (a 2 a) or the formula (a 2 b) n2 -a six-membered aromatic ring different from the aromatic ring to which the represented group is bonded. In the formula (a 2 a) or (a 2 b), R a1 The bonding position of (c) is not particularly limited. The compound represented by the formula (a 2) has 1 or more R a1 In this case, 1 or more R is preferable from the viewpoint of easy synthesis of the compound represented by the formula (a 2) a1 Is bonded to a position represented by the following structures represented by the formulas (a 2 a-1) and (a 2 b-1).
[ chemical formula 29]
R a1 When there are a plurality of R a1 May be the same or different.
R a1 When the compound is an organic group, R a1 The organic group is not particularly limited insofar as it does not interfere with the object of the present invention, and may be appropriately selected from various organic groups. As R a1 Examples of the organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group.
R a1 In the case of an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 6. In addition, R a1 When alkyl is used, the alkyl may be straight-chain or branched. As R a1 Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl. In addition, R a1 When alkyl, the alkyl group may contain an ether linkage (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group,Ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, methoxypropyl, and the like.
R a1 In the case of an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 6. In addition, R a1 When the alkoxy group is a straight chain or branched chain. As R a1 Specific examples of the alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, isopentyloxy, sec-pentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isononyl, n-decyloxy, isodecyloxy and the like. In addition, R a1 In the case of alkoxy groups, the alkoxy groups may contain ether linkages (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, and methoxypropyloxy groups.
R a1 In the case of cycloalkyl or cycloalkoxy, the number of carbon atoms of the cycloalkyl or cycloalkoxy is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. As R a1 Specific examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. As R a1 Specific examples of the cycloalkoxy group include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy.
R a1 When the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is used, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, more preferably 2 to 7. As R a1 Specific examples of the saturated aliphatic acyl group include acetyl, propionyl, n-butyryl, 2-methylpropanoyl, n-pentanoyl, 2-dimethylpropionyl, n-hexanoyl and n-hexanoyl Heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecanoyl, n-hexadecanoyl, and the like. As R a1 Specific examples of saturated aliphatic acyloxy groups include acetyloxy, propionyloxy, n-butyryloxy, 2-methylpropanoyloxy, n-pentanoyloxy, 2-dimethylpropionyloxy, n-hexanoyloxy, n-heptanoyloxy, n-octanoyloxy, n-nonanoyloxy, n-decanoyloxy, n-undecanoyloxy, n-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanoyloxy, and n-hexadecanoyloxy.
R a1 In the case of an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. As R a1 Specific examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyloxycarbonyl.
R a1 In the case of the phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. In addition, R a1 In the case of the naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less. As R a1 Specific examples of the phenylalkyl group include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. As R a1 Specific examples of the naphthylalkyl group include an α -naphthylmethyl group, a β -naphthylmethyl group, a 2- (α -naphthyl) ethyl group, and a 2- (β -naphthyl) ethyl group. R is R a1 R is phenylalkyl or naphthylalkyl a1 The phenyl group or the naphthyl group may have a further substituent.
R a1 When the heterocyclic group is a heterocyclic group, the heterocyclic group is a five-membered or six-membered monocyclic ring containing 1 or more N, S, O, or is a heterocyclic group in which the monocyclic rings are condensed with each other or the monocyclic rings are condensed with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran, and the like. R is R a1 When the heterocyclic group is a heterocyclic group, the heterocyclic group may further have a substituent.
R a1 In the case of a heterocyclylcarbonyl group, the heterocyclic group contained in the heterocyclylcarbonyl group is represented by R a1 The same applies to the case of heterocyclic groups.
R a1 When the amino group is substituted with 1 or 2 organic groups, preferable examples of the organic groups include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 21 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms and a heterocyclic group. Specific examples of these preferred organic groups and R a1 Likewise, the same is true. Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino N-octylamino, n-nonylamino, n-decylamino, phenylamino, naphthylamino, acetylamino, propionylamino, n-butyrylamino, n-pentanoylamino, n-hexanoylamino, n-heptanoylamino, n-octanoylamino, n-decanoylamino, benzoylamino, α -naphthoylamino, β -naphthoylamino and the like.
As R a1 Examples of the substituent when the phenyl group, the naphthyl group, and the heterocyclic group included in (a) further have a substituent(s) include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl, halogen, nitro, cyano and the like. R is R a1 When the phenyl group, the naphthyl group, and the heterocyclic group included in the (b) have further substituents, the number of the substituents is not limited within a range that does not hinder the object of the present invention, and is preferably 1 to 4. R is R a1 When the phenyl group, the naphthyl group, and the heterocyclic group included in (a) have a plurality of substituents, the plurality of substituents may be the same or different.
Of the groups described hereinabove, R is the group a1 Is nitro or R a6 The sensitivity tends to be improved when the group represented by-CO-is used, and this is preferable. R is R a6 The organic group is not particularly limited insofar as it does not interfere with the object of the present invention, and may be selected from various organic groups. Regarding preference as R a6 Examples of the group(s) include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclic group which may have a substituent. Of these groups, R is a6 Particularly preferred are 2-methylphenyl, thiophen-2-yl and α -naphthyl.
In addition, R a1 In the case of a hydrogen atom, transparency tends to be good, and is preferable. R is as follows a1 Is hydrogenAnd R is an atom a3 When the group represented by the following formula (a 2-a) or (a 2-b) is used, transparency tends to be more excellent.
In the formula (a 2 a), R a2 And R is a3 Each is a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R is R a2 And R is R a3 Can be bonded to each other to form a ring. Of these groups, R is a2 And R is a3 A chain alkyl group which may have a substituent is preferable. R is R a2 And R is a3 When the alkyl group is a chain alkyl group which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched alkyl group.
R a2 And R is a3 In the case of a chain alkyl group having no substituent, the number of carbon atoms of the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, particularly preferably 1 to 6. As R a2 And R is a3 Specific examples of the chain alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl. In addition, R a2 And R is a3 When alkyl, the alkyl group may contain an ether linkage (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.
R a2 And R is a3 In the case of a substituted chain alkyl group, the number of carbon atoms of the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, particularly preferably 1 to 6. In this case, the number of carbon atoms of the chain alkyl group does not include the number of carbon atoms of the substituent. The substituted chain alkyl group is preferably linear.
The substituent that the alkyl group may have is not particularly limited insofar as it does not interfere with the object of the present invention. As substituentsPreferable examples of (a) include cyano groups, halogen atoms, cyclic organic groups, and alkoxycarbonyl groups. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, fluorine atom, chlorine atom and bromine atom are preferable. Examples of the cyclic organic group include cycloalkyl, aromatic hydrocarbon, and heterocyclic groups. As a specific example of cycloalkyl, R a1 The same applies to cycloalkyl groups. Specific examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, anthryl, phenanthryl, and the like. As a specific example of the heterocyclic group, R a1 The same applies to the heterocyclic group. R is R a1 In the case of an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group included in the alkoxycarbonyl group is preferably 1 to 10, more preferably 1 to 6.
When the chain alkyl group has a substituent, the number of substituents is not particularly limited. The number of preferred substituents varies depending on the number of carbon atoms of the chain alkyl group. The number of substituents is typically 1 to 20, preferably 1 to 10, more preferably 1 to 6.
R a2 And R is a3 In the case of a linear alkoxy group having no substituent, the number of carbon atoms of the linear alkoxy group is preferably 1 to 20, more preferably 1 to 10, particularly preferably 1 to 6. As R a2 And R is a3 Specific examples of the chain alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, isopentyloxy, sec-pentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isononyl oxy, n-decyloxy, isodecyloxy and the like. In addition, R a2 And R is a3 In the case of alkoxy groups, the alkoxy groups may contain ether linkages (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethylOxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, methoxypropyloxy and the like.
R a2 And R is a3 In the case of a substituted chain alkoxy group, the alkoxy group may have a substituent and R a2 And R is a3 The same applies to the case of chain alkyl.
R a2 And R is a3 When the cyclic organic group is an alicyclic group, the cyclic organic group may be an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group. R is R a2 And R is a3 In the case of a cyclic organic group, the cyclic organic group may have a substituent and R a2 And R is a3 The same applies to the case of chain alkyl.
R a2 And R is a3 In the case of an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably a phenyl group, a group in which a plurality of benzene rings are bonded through carbon-carbon bonds, or a group in which a plurality of benzene rings are fused. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or fusing a plurality of benzene rings, the number of rings of the benzene ring contained in the aromatic hydrocarbon group is not particularly limited, and is preferably 3 or less, more preferably 2 or less, and particularly preferably 1. Preferred examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, anthryl, phenanthryl and the like.
R a2 And R is a3 In the case of the aliphatic cyclic hydrocarbon group, the aliphatic cyclic hydrocarbon group may be a single ring or multiple rings. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 or more and 20 or less, more preferably 3 or more and 10 or less. Examples of the monocyclic cyclic hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, tetracyclododecyl, and adamantyl groups.
R a2 And R is a3 When the heterocyclic group is a heterocyclic group, the heterocyclic group is a five-membered or six-membered monocyclic ring containing 1 or more N, S, O, or is a heterocyclic group in which the monocyclic rings are condensed with each other or the monocyclic rings are condensed with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran, and the like.
R a2 And R is R a3 Can be bonded to each other to form a ring. Comprising R a2 And R is R a3 The group of the ring formed is preferably cycloalkylene (cycloalkylidene group). R is R a2 And R is R a3 When the cycloalkylene group is formed by bonding, the ring constituting the cycloalkylene group is preferably a five-membered ring to a six-membered ring, more preferably a five-membered ring.
R a2 And R is R a3 When the group formed by bonding is a cycloalkylene group, the cycloalkylene group may be condensed with 1 or more other rings. Examples of the ring which can be condensed with the cycloalkylene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, a pyrazine ring, and a pyrimidine ring.
R as described hereinabove a2 And R is a3 Examples of the preferable group include the formula-A 1 -A 2 A group represented by the formula (I). In the formula, there may be mentioned: a is that 1 Is a linear alkylene group, A 2 Is an alkoxy group, a cyano group, a halogen atom, a haloalkyl group, a cyclic organic group, or an alkoxycarbonyl group.
A 1 The number of carbon atoms of the linear alkylene group is preferably 1 to 10, more preferably 1 to 6. A is that 2 In the case of an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 to 10, more preferably 1 to 6. A is that 2 When the halogen atom is a halogen atom, it is preferably a fluorine atom, a chlorine atom or a bromine atomThe atom and iodine atom are more preferably a fluorine atom, a chlorine atom and a bromine atom. A is that 2 In the case of a haloalkyl group, the halogen atom contained in the haloalkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom, a chlorine atom or a bromine atom. The haloalkyl group may be linear or branched, and is preferably linear. A is that 2 In the case of a cyclic organic group, examples of cyclic organic groups and R a2 And R is a3 The cyclic organic group which is provided as a substituent is the same. A is that 2 In the case of alkoxycarbonyl, examples of alkoxycarbonyl and R a2 And R is a3 The same applies to alkoxycarbonyl groups which are substituted.
As R a2 And R is a3 Specific examples of the preferable groups include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl; alkoxyalkyl groups such as 2-methoxyethyl, 3-methoxy-n-propyl, 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-methoxy-n-hexyl, 7-methoxy-n-heptyl, 8-methoxy-n-octyl, 2-ethoxyethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl, 5-ethoxy-n-pentyl, 6-ethoxy-n-hexyl, 7-ethoxy-n-heptyl, and 8-ethoxy-n-octyl; cyanoalkyl groups such as 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n-pentyl group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group, and 8-cyano-n-octyl group; phenylalkyl groups such as 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and 8-phenyl-n-octyl; cycloalkylalkyl groups such as 2-cyclohexylethyl group, 3-cyclohexyln-propyl group, 4-cyclohexyln-butyl group, 5-cyclohexyln-pentyl group, 6-cyclohexyln-hexyl group, 7-cyclohexyln-heptyl group, 8-cyclohexyln-octyl group, 2-cyclopentylethyl group, 3-cyclopentylethyl group, 4-cyclopentylen-butyl group, 5-cyclopentylen-pentyl group, 6-cyclopentylen-hexyl group, 7-cyclopentylen-heptyl group, and 8-cyclopentylen-octyl group; 2-methoxycarbonylethyl, 3-methoxycarbonyln-propyl, 4-methoxycarbonyln-butyl, 5-methoxycarbonyln-pentyl, 6-methoxycarbonyln-hexyl, 7-methoxycarbonyln-heptyl, 8-methoxycarbonyln-octyl, 2-ethoxycarbonylethyl, 3-ethoxycarbonyln-propyl, Alkoxycarbonylalkyl groups such as 4-ethoxycarbonyl n-butyl, 5-ethoxycarbonyl n-pentyl, 6-ethoxycarbonyl n-hexyl, 7-ethoxycarbonyl n-heptyl, and 8-ethoxycarbonyl n-octyl; 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro-n-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl, 8-chloro-n-octyl, 2-bromoethyl, 3-bromo-n-propyl 4-bromo-n-butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl, 7-bromo-n-heptyl, 8-bromo-n-octyl haloalkyl such as 3, 3-trifluoropropyl, 3,4, 5-heptafluoro-n-pentyl, and the like.
As R a2 And R is a3 Preferred groups in the above are ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl 2-cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl 2-bromoethyl, 3-trifluoropropyl and 3,4, 5-heptafluoro-n-pentyl.
As R a4 Examples of preferred organic radicals of (2) are as follows a1 Similarly, examples thereof include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group, and the like. Specific examples of these groups and R a1 And the same is said. In addition, as R a4 Cycloalkyl alkyl, phenoxyalkyl which may have a substituent on the aromatic ring, phenylthioalkyl which may have a substituent on the aromatic ring are also preferable. Phenoxyalkyl, phenylthioalkyl and R may have a substituent a1 The phenyl groups contained therein may haveThe substituents are the same.
In the organic radical, R is a4 Preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, a phenylthioalkyl group which may have a substituent on an aromatic ring. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. Among phenyl groups which may have a substituent, methylphenyl is preferable, and 2-methylphenyl is more preferable. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among cycloalkylalkyl groups, cyclopentylethyl is preferred. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among phenylthioalkyl groups which may have a substituent on the aromatic ring, 2- (4-chlorophenylthio) ethyl is preferable.
In addition, as R a4 ，-A 3 -CO-O-A 4 The radicals indicated are also preferred. A is that 3 Is a divalent organic group, preferably a divalent hydrocarbon group, preferably an alkylene group. A is that 4 The monovalent organic group is preferably a monovalent hydrocarbon group.
A 3 In the case of an alkylene group, the alkylene group may be linear or branched, and is preferably linear. A is that 3 In the case of an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, particularly preferably 1 to 4.
As A 4 Preferable examples of (a) include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkylalkyl group having 4 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. As A 4 Is superior to (1)Specific examples of the compounds selected are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, phenyl, naphthyl, benzyl, phenethyl, a-naphthylmethyl, β -naphthylmethyl and the like.
as-A 3 -CO-O-A 4 Preferred examples of the group represented include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propyloxycarbonyl ethyl, 2-n-butyloxycarbonyl ethyl, 2-n-pentyloxycarbonylethyl, 2-n-hexyloxycarbonyl ethyl, 2-benzyloxycarbonyl ethyl, 2-phenoxycarbonylethyl, 3-methoxycarbonyln-propyl, 3-ethoxycarbonyln-propyl, 3-n-propyloxycarbonyl-n-propyl, 3-n-butyloxycarbonyl-n-propyl, 3-n-pentyloxycarbonyln-propyl, 3-n-hexyloxycarbonyl-n-propyl, 3-benzyloxycarbonyl-n-propyl, 3-phenoxycarbonyl-n-propyl and the like.
Above, for R a4 Is illustrated as R a4 Preferably, the group represented by the following formula (a 2-a) or (a 2-b).
[ chemical formula 30]
(in the formulae (a 2-a) and (a 2-b), R a7 And R is a8 Each is an organic group, n3 is an integer of 0 to 4, R a7 And R is a8 When present at adjacent positions on the benzene ring, R a7 And R is R a8 Can be bonded to each other to form a ring, n4 is an integer of 1 to 8, n5 is an integer of 1 to 5, n6 is an integer of 0 to (n5+3), R a9 Is an organic group. )
R in formula (c 2-a) a7 And R is a8 Examples of organic radicals of (2) and R a1 Likewise, the same is true. As R a7 Preferably alkyl or phenyl. R is R a7 In the case of an alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. Namely, R a7 Most preferably methyl. R is R a7 And R is R a8 When bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. As R a7 And R is R a8 Preferred examples of the group represented by the formula (c 2-a) in which the ring is formed include naphthalen-1-yl, 1,2,3, 4-tetrahydronaphthalen-5-yl and the like. In the above formula (c 2-a), n3 is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.
In the above formula (a 2-b), R a9 Is an organic group. Examples of the organic group include R a1 And the organic groups described are the same. Among the organic groups, alkyl groups are preferred. The alkyl group may be linear or branched. The carbon number of the alkyl group is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3. As R a9 The methyl group is preferably exemplified by methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc., and among these, methyl group is more preferred.
In the above formula (a 2-b), n5 is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2. In the above formula (a 2-b), n6 is an integer of 0 to (n5+3), preferably 0 to 3, more preferably 0 to 2, and particularly preferably 0. In the above formula (a 2-b), n4 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.
In the formula (a 2), R a5 An aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. As R a5 The substituent which may be present in the case of an aliphatic hydrocarbon group is preferably a phenyl group or a naphthyl group. In addition, as R a1 The substituent which may be present in the case of the aryl group is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom or the like.
In the formula (a 2), R is a5 Preferred examples thereof include a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-cyclopentylethyl group, 2-cyclobutylethyl group, cyclohexylmethyl group, phenyl group, benzyl group, methylphenyl group, and naphthyl group, and more preferred examples thereof are methyl group and benzene groupA base.
Preferable specific examples of the compound represented by the formula (a 2) include the following compounds.
[ chemical formula 31]
[ chemical formula 32]
[ chemical formula 33]
[ chemical formula 34]
[ chemical formula 35]
The content of the photopolymerization initiator (a) in the photosensitive composition is not particularly limited within a range that does not hinder the object of the present invention. The content of the photopolymerization initiator (a) is preferably 0.1% by mass or more and 50% by mass or less, more preferably 0.3% by mass or more and 30% by mass or less, and particularly preferably 0.5% by mass or more and 20% by mass or less, based on the mass of the solid content of the photosensitive composition. By using the photopolymerization initiator (a) in an amount within the above range, the desired effect due to the use of the photopolymerization initiator (a) can be easily obtained without impairing the mechanical properties, solvent resistance, chemical resistance, and the like of the cured product.
< polymerizable base material component (B) >)
The photosensitive composition may further contain a polymerizable base component (B). The polymerizable base material component (B) (hereinafter also referred to as a "(B) component") is a component that imparts photopolymerization and film forming ability to the photosensitive composition. The polymerizable base component (B) is not particularly limited as long as it is a component capable of producing a photosensitive composition that contains a component capable of polymerizing with the photopolymerization initiator (a) and can form a film. The polymerizable base component (B) may be used alone or in combination of 2 or more.
Typically, the polymerizable base material component (B) contains the photopolymerizable compound (B1), or the photopolymerizable compound (B1) and the resin (B2). The photopolymerizable compound (B1) may be a low-molecular compound or a high-molecular compound. The photopolymerizable compound (B1) and the resin (B2) may be used singly or in combination of 2 or more.
The photopolymerizable compound (B1) and the resin (B2) can be distinguished, for example, by: a polymer having a weight average molecular weight of 1000 or more, which is formed from 1 or 2 or more monomer compounds, is used as the resin (B2), and a compound having a photopolymerizable functional group, which is not the resin (B2), is used as the photopolymerizable compound (B1).
From the viewpoint of photopolymerization, the polymerizable base material component (B) preferably contains a low molecular weight photopolymerizable compound (B1) that is not a polymer, and a crosslinkable group-containing resin as the resin (B2) in combination.
In the case where the polymerizable base material component (B) contains the resin (B2), the resin (B2) preferably contains an alkali-soluble resin from the viewpoint of developability. The alkali-soluble resin may contain a crosslinking group. From the viewpoints of both photopolymerization and alkali developability, an alkali-soluble resin containing a crosslinkable group (containing a crosslinkable group as a substituent in a structural unit) is preferable.
Hereinafter, the photopolymerizable compound (B1) and the resin (B2) will be described in this order.
[ photopolymerizable Compound (B1) ]
As the photopolymerizable compound (B1) contained in the photosensitive composition, a compound having an ethylenically unsaturated double bond can be preferably used. Preferable examples of the compound having an ethylenically unsaturated double bond include monofunctional monomers and polyfunctional monomers.
As the monofunctional monomer, there is used, examples thereof include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, t-butyl acrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, di (meth) acrylate, amino (meth) acrylate, 2-glycidyl (meth) acrylate 2, 3-tetrafluoropropyl (meth) acrylate, half (meth) acrylate of phthalic acid derivatives, and the like. These monofunctional monomers may be used alone or in combination of 2 or more.
On the other hand, examples of the polyfunctional monomer include 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, 1, 12-dodecanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropyl (meth) acrylate, dipentaerythritol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, poly (ethylene-propylene) glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, ethoxylated bisphenol a di (meth) acrylate, propoxylated bisphenol a di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and tetra (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerol triacrylate, polyglycidyl ether poly (meth) acrylate, urethane (urethane (meth)) (i.e., toluene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, or a reactant of 1, 6-hexamethylene diisocyanate with 2-hydroxyethyl (meth) acrylate), methylenebis (meth) acrylamide, (meth) acrylamide methylene ether, a condensate of a polyhydric alcohol with N-methylol (meth) acrylamide, 1,3, 5-triacrylhexahydro-1, 3, 5-triazine (triacrylform), 2,4, 6-trioxohexahydro-1, 3, 5-triazine-1, 3, 5-triethanolamine triacrylate, 2,4, 6-trioxohexahydro-1, 3, 5-triazine-1, 3, 5-triethanolamine diacrylate, and the like. These polyfunctional monomers may be used alone or in combination of 2 or more.
Among these compounds having an ethylenically unsaturated double bond, a polyfunctional monomer having 3 or more functions is preferable from the viewpoint of obtaining a photosensitive composition that provides a cured product excellent in strength and adhesion to a substrate.
From the viewpoint of controlling the glass transition temperature (Tg), a monofunctional monomer or a 2-functional monomer may be used in combination with a polyfunctional monomer having 3 or more functions, and among these, 1, 6-hexanediol di (meth) acrylate is preferable.
The content of the photopolymerizable compound (B1) is preferably 5 mass% or more and 97 mass% or less, more preferably 10 mass% or more and 95 mass% or less, with respect to the solid content of the photosensitive composition. The content of the photopolymerizable compound (B1) in the photosensitive composition is in the above range, thereby improving curability. Further, if the content of the photopolymerizable compound (B1) is 60 mass% or less (preferably 5 mass% or more and 40 mass% or less) relative to the solid content of the photosensitive composition, the balance of sensitivity, developability, and resolution of the photosensitive composition tends to be easily obtained.
[ resin (B2) ]
The photosensitive composition preferably contains not only the photopolymerizable compound (B1) but also the resin (B2) as the polymerizable base material component (B). The resin (B2) is not particularly limited insofar as it does not interfere with the object of the present invention, and a resin component conventionally blended in various photosensitive compositions can be used.
Hereinafter, a preferred example of the resin (B2) will be described.
(crosslinkable group-containing resin)
When the photosensitive composition contains a resin containing a crosslinkable group as the resin (B2), the formation of a cured product using the photosensitive composition tends to be easier. The crosslinkable group-containing resin is a crosslinkable group-containing resin, and preferably contains a unit derived from a (meth) acrylate having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a functional group capable of crosslinking a resin containing a crosslinkable group mainly by heating, and an epoxy group or an ethylenically unsaturated double bond is preferable. For example, the crosslinkable group can be introduced into the resin containing the crosslinkable group by containing at least 1 selected from the group consisting of a unit derived from a (meth) acrylate having an epoxy group and a unit having an ethylenically unsaturated double bond.
The crosslinkable group-containing resin is preferably a resin containing a unit derived from a (meth) acrylate having an epoxy group. By having the above units, adhesion to a substrate and mechanical strength of a cured film formed using the photosensitive composition can be improved.
The (meth) acrylate having an epoxy group may be a (meth) acrylate having a chain aliphatic epoxy group or may be a (meth) acrylate having an alicyclic epoxy group as described later.
The (meth) acrylate having an epoxy group may have an aromatic group. In the present specification, an aromatic group is a group having an aromatic ring. Examples of the aromatic ring constituting the aromatic group include benzene ring and naphthalene ring. Examples of the (meth) acrylic acid ester having an aromatic group and an epoxy group include 4-glycidyloxyphenyl (meth) acrylate, 3-glycidyloxyphenyl (meth) acrylate, 2-glycidyloxyphenyl (meth) acrylate, 4-glycidyloxyphenyl methyl (meth) acrylate, 3-glycidyloxyphenyl methyl (meth) acrylate, and 2-glycidyloxyphenyl methyl (meth) acrylate.
When transparency is required for a film formed using the photosensitive composition, the (meth) acrylic acid having an epoxy group preferably has no aromatic group.
Examples of the (meth) acrylate having a chain aliphatic epoxy group include (meth) acrylate in which a chain aliphatic epoxy group such as an epoxy alkyl (meth) acrylate or an epoxy alkyl oxy alkyl (meth) acrylate is bonded to an oxy group (-O-) in an ester group (-O-CO-). The chain aliphatic epoxy group possessed by such a (meth) acrylate may contain 1 or more oxygen groups (-O-) in the chain. The number of carbon atoms of the chain aliphatic epoxy group is not particularly limited, but is preferably 3 or more and 20 or less, more preferably 3 or more and 15 or less, and particularly preferably 3 or more and 10 or less.
Specific examples of the (meth) acrylic acid ester having a chain aliphatic epoxy group include alkylene oxide (meth) acrylates such as glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, and 6, 7-epoxyheptyl (meth) acrylate; epoxy alkyl oxy (meth) acrylates such as 2-glycidyloxy ethyl (meth) acrylate, 3-glycidyloxy n-propyl (meth) acrylate, 4-glycidyloxy n-butyl (meth) acrylate, 5-glycidyloxy n-hexyl (meth) acrylate, and 6-glycidyloxy n-hexyl (meth) acrylate.
Specific examples of the (meth) acrylate having an alicyclic epoxy group include compounds represented by the following formulas (d 2-1) to (d 2-16). Among these, in order to make the developability of the photosensitive composition appropriate, the compounds represented by the following formulas (d 2-1) to (d 2-6) are preferable, and the compounds represented by the following formulas (d 2-1) to (d 2-4) are more preferable.
In the above-mentioned compounds, the bonding site of the oxygen atom of the ester group to the alicyclic ring is not limited to the site described herein, and may include a part of positional isomers.
[ chemical formula 36]
In the above formula, R d4 Represents a hydrogen atom or a methyl group, R d5 Represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R d6 A divalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 0 to 10. As R d5 Straight-chain or branched alkylene groups such as methylene, ethylene, propylene, 1, 4-butylene, ethylethylene, 1, 5-pentylene, 1, 6-hexylene are preferred. As R d6 For example, methylene, ethylene and propylene are preferred1, 4-butylene, ethylethylene, 1, 5-pentylene, 1, 6-hexylene, phenylene, cyclohexylene, -CH 2 -Ph-CH 2 - (Ph represents phenylene).
When the (meth) acrylate having an epoxy group is such a (meth) acrylate having an alicyclic epoxy group as described above, the crosslinkable group-containing resin containing a unit derived from the (meth) acrylate and the photosensitive composition are excellent in storage stability as compared with the (meth) acrylate having a chain aliphatic epoxy group, and the range of a temperature at which pre-baking can be performed (margin) is preferably widened when forming a cured film.
The crosslinkable group-containing resin may also be a resin containing a unit having an ethylenically unsaturated double bond as a crosslinkable group (in this specification, it is sometimes referred to as "a resin having an ethylenically unsaturated double bond"). The ethylenically unsaturated double bond preferably forms part of a (meth) acryloyloxy group.
Examples of the resin having an ethylenically unsaturated double bond include resins having a (meth) acryloyloxy group.
The resin having a (meth) acryloyloxy group can be produced, for example, by reacting at least a part of a carboxyl group contained in a polymer containing a unit derived from an unsaturated carboxylic acid with the above-mentioned (meth) acrylate having an alicyclic epoxy group and/or the above-mentioned (meth) acrylate having a chain aliphatic epoxy group.
When the crosslinkable group-containing resin is a resin having an ethylenically unsaturated double bond, the resin may be a photopolymerizable resin. By containing the photopolymerizable resin having an ethylenically unsaturated double bond as the resin (B2), the curability of the photosensitive composition can be improved, and the patterning can be easily performed.
In the crosslinkable group-containing resin, the amount of the unit derived from the (meth) acrylate having a crosslinkable group is preferably 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 70% by mass or less, and still more preferably 33% by mass or more and 65% by mass or less, based on the mass of the resin.
The amount of the unit derived from the (meth) acrylate having an epoxy group in the resin containing a crosslinkable group is preferably 10% by mass or more and 90% by mass or less, more preferably 15% by mass or more and 80% by mass or less, still more preferably 20% by mass or more and 70% by mass or less, based on the mass of the resin.
In the crosslinkable group-containing resin, the amount of the unit having an ethylenically unsaturated double bond is preferably 1% by mass or more and 40% by mass or less, more preferably 5% by mass or more and 35% by mass or less, relative to the mass of the resin.
The crosslinkable group-containing resin is preferably a polymer of 1 or more monomers selected from (meth) acrylic acid and (meth) acrylic acid esters, and when the polymer is used, the content of the units derived from the (meth) acrylic acid esters having crosslinkable groups in the polymer is similar to that described above with respect to the mass of the resin.
The crosslinkable group-containing resin may contain both a unit derived from a (meth) acrylate having an epoxy group and a unit having an ethylenically unsaturated double bond, or may contain either a unit derived from a (meth) acrylate having an epoxy group or a unit having an ethylenically unsaturated double bond, and preferably contains only a unit derived from a (meth) acrylate having an epoxy group as a crosslinkable group.
Preferably, the resin containing a crosslinkable group is not only a resin having a crosslinkable group but also an alkali-soluble resin. By blending the alkali-soluble resin in the photosensitive composition, alkali developability can be imparted to the photosensitive composition.
In the present specification, the alkali-soluble resin means: a resin film having a thickness of 1 μm was formed on a substrate by using a resin solution having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate), and when immersed in a KOH aqueous solution having a concentration of 0.05% by mass for 1 minute, the resin film was dissolved in a thickness of 0.01 μm or more.
When the resin containing a crosslinkable group is also an alkali-soluble resin, it generally has an alkali-soluble group. The alkali-soluble group is not particularly limited as long as it is a functional group imparting the above-mentioned solubility in alkali to the resin containing a crosslinking group, and preferably a carboxyl group or a group capable of undergoing deprotection to generate a carboxyl group, for example, an alkali-soluble group can be introduced into the resin containing a crosslinking group by polymerizing a monomer containing a (meth) acrylate imparting an alkali-soluble group, and a unit derived from an unsaturated carboxylic acid, which will be described later, for example. In the present specification, the (meth) acrylate having an alkali-soluble group does not include the (meth) acrylate having a crosslinkable group described above.
When the resin containing a crosslinkable group is also an alkali-soluble resin, the resin may be a resin having no functional group that inhibits or prevents the above-mentioned solubility in alkali (hereinafter, sometimes referred to as "alkali-solubility preventing group" or "dissolution preventing group") of the resin containing a crosslinkable group, but a resin having an alkali-soluble group and a dissolution preventing group is preferable. From the viewpoint of having a function of reducing the solubility of the resin containing a crosslinkable group in a base, the dissolution preventing group is also referred to as a poorly alkali-soluble group. The resin containing a crosslinkable group has an alkali-soluble group and a dissolution preventing group, whereby the solubility in alkali can be adjusted, and thus the alkali developability of the photosensitive composition can be adjusted. Examples of the dissolution-inhibiting group include styrene and styrene derivatives described below; unsaturated imides; (meth) acrylate having an alicyclic skeleton (excluding (meth) acrylate having an epoxy group); and (meth) acrylic esters having an aromatic group such as benzyl (meth) acrylate. In the present specification, the (meth) acrylate to which the dissolution preventing group is added does not include the (meth) acrylate having a crosslinkable group described above.
Among the resins containing crosslinkable groups, polymers of monomers having ethylenically unsaturated double bonds are preferred from the viewpoint of excellent film formability, easy adjustment of the properties of the resins by selection of the monomers, and the like. Examples of the monomer having an ethylenically unsaturated double bond include (meth) acrylic acid; (meth) acrylic esters; (meth) acrylamide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, anhydrides of these dicarboxylic acids; allyl compounds such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, and allyloxyethanol; vinyl ethers such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2, 2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2, 4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthryl ether; vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethylacetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl β -phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate; styrene or styrene derivatives such as styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene; olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-hexene, 4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide.
When the crosslinkable group-containing resin is a polymer of a monomer having an ethylenically unsaturated double bond, the resin generally contains a unit derived from an unsaturated carboxylic acid. Examples of the unsaturated carboxylic acid include (meth) acrylic acid; (meth) acrylamide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, anhydrides of these dicarboxylic acids. The amount of the unit derived from the unsaturated carboxylic acid contained in the polymer of the monomer having an ethylenically unsaturated double bond used as the alkali-soluble resin is not particularly limited as long as the resin has a desired alkali-solubility. The amount of the unit derived from the unsaturated carboxylic acid in the resin used as the alkali-soluble resin is preferably 5 mass% or more and 25 mass% or less, more preferably 8 mass% or more and 16 mass% or less, and particularly preferably the amount when the resin containing the crosslinkable group has a dissolution preventing group described later. When the resin having a crosslinkable group does not have a dissolution inhibiting group described later, the amount of the unit derived from the unsaturated carboxylic acid in the resin is preferably 50% by mass or more and 80% by mass or less, more preferably 60% by mass or more and 70% by mass or less, relative to the mass of the resin.
Among the polymers of monomers having an ethylenically unsaturated double bond as the polymer of 1 or more monomers selected from the above-exemplified monomers, a polymer of 1 or more monomers selected from (meth) acrylic acid and (meth) acrylic esters is preferable. Hereinafter, a polymer of 1 or more monomers selected from (meth) acrylic acid and (meth) acrylic acid esters will be described.
The (meth) acrylic acid ester used for preparing the polymer of 1 or more monomers selected from the group consisting of (meth) acrylic acid and (meth) acrylic acid esters is not particularly limited in the range that does not interfere with the object of the present invention, and may be appropriately selected from known (meth) acrylic acid esters.
Preferable examples of the (meth) acrylic acid ester include (meth) acrylic acid esters of linear or branched alkyl groups such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, pentyl (meth) acrylate, and tert-octyl (meth) acrylate; chloroethyl (meth) acrylate, 2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, furfuryl (meth) acrylate; (meth) acrylic esters having an aromatic group such as benzyl (meth) acrylate; (meth) acrylic esters having an alicyclic skeleton. Details of the (meth) acrylate having an alicyclic skeleton will be described later.
Among the polymers of 1 or more monomers selected from (meth) acrylic acid and (meth) acrylic acid esters, a resin containing a unit derived from a (meth) acrylic acid ester having an alicyclic skeleton is also preferable in view of ease of forming an insulating film having high transmittance by using the photosensitive composition. In the present specification, the (meth) acrylate having an alicyclic skeleton does not include the (meth) acrylate having a crosslinkable group described above.
In the (meth) acrylate having an alicyclic skeleton, the group having an alicyclic skeleton is preferably a group having an alicyclic hydrocarbon group. The alicyclic group constituting the alicyclic skeleton may be a single ring or multiple rings. Examples of the monocyclic alicyclic group include cyclopentyl and cyclohexyl. Examples of the polycyclic alicyclic group include norbornyl, isobornyl, tricyclic nonyl, tricyclic decyl, and tetracyclododecyl.
Among the (meth) acrylic esters having an alicyclic skeleton, the (meth) acrylic esters having an alicyclic hydrocarbon group include, for example, compounds represented by the following formulas (d 1-1) to (d 1-8). Among these, the compounds represented by the following formulas (d 1-3) to (d 1-8) are preferable, and the compounds represented by the following formulas (d 1-3) or (d 1-4) are more preferable.
[ chemical formula 37]
In the above formula, R d1 Represents a hydrogen atom or a methyl group, R d2 Represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R d3 Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As R d2 The alkylene group is preferably a single bond, a linear or branched alkylene group, for example, methylene, ethylene, propylene, 1, 4-butylene, ethylethylene, 1, 5-pentylene, 1, 6-hexylene. As R d3 Methyl and ethyl are preferred.
The crosslinkable group-containing resin is preferably a resin containing a unit derived from 1 or more monomers selected from the group consisting of (meth) acrylic acid and (meth) acrylic acid esters, and a unit derived from (meth) acrylic acid esters having an alicyclic epoxy group. The resin may be a resin further containing a unit derived from a (meth) acrylate having an alicyclic skeleton, and in this case, the amount of the unit derived from the (meth) acrylate having an alicyclic skeleton in the resin may be 10% by mass or more and 35% by mass or less, may be 15% by mass or more and 30% by mass or less, and may be 20% by mass or more and 25% by mass or less.
Among the polymers containing a unit derived from a (meth) acrylate having an alicyclic skeleton and at least 1 monomer selected from the group consisting of (meth) acrylic acid and (meth) acrylate, a resin containing a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylate having an alicyclic epoxy group is preferable. Films formed using the photosensitive composition containing the resin having a crosslinkable group have excellent adhesion to a substrate. In addition, when such a resin is used, there is a possibility that the carboxyl group contained in the resin reacts with the alicyclic epoxy group itself. Therefore, when a photosensitive composition containing such a resin is used, the self-reaction between the carboxyl group and the alicyclic epoxy group occurs by a method of heating the film or the like, whereby the mechanical properties such as the hardness of the formed film can be improved.
In the resin containing a unit derived from (meth) acrylic acid (excluding a unit having a crosslinkable group), and a unit derived from (meth) acrylic acid ester having an alicyclic epoxy group, the amount of the former unit derived from (meth) acrylic acid in the resin is preferably 1% by mass or more and 95% by mass or less, more preferably 10% by mass or more and 70% by mass or less. In the resin containing the unit derived from (meth) acrylic acid and the unit derived from (meth) acrylate having an alicyclic epoxy group, the amount of the unit derived from (meth) acrylate having an alicyclic epoxy group in the resin is preferably 1% by mass or more and 95% by mass or less, more preferably 10% by mass or more and 50% by mass or less.
The polymer containing a unit derived from (meth) acrylic acid and a unit derived from (meth) acrylate having an alicyclic epoxy group, which is 1 or more monomers selected from (meth) acrylic acid and (meth) acrylate, may be a resin containing a unit derived from (meth) acrylic acid, a unit derived from (meth) acrylate having an alicyclic hydrocarbon group, and a unit derived from (meth) acrylate having an alicyclic epoxy group.
In the resin containing a unit derived from (meth) acrylic acid, a unit derived from (meth) acrylate having an alicyclic hydrocarbon group, and a unit derived from (meth) acrylate having an alicyclic epoxy group, the amount of the unit derived from (meth) acrylic acid in the resin is preferably 1% by mass or more and 95% by mass or less, more preferably 10% by mass or more and 50% by mass or less. In the resin containing a unit derived from (meth) acrylic acid, a unit derived from (meth) acrylate having an alicyclic hydrocarbon group, and a unit derived from (meth) acrylate having an alicyclic epoxy group, the amount of the unit derived from (meth) acrylate having an alicyclic hydrocarbon group in the resin is preferably 1% by mass or more and 95% by mass or less, more preferably 10% by mass or more and 70% by mass or less. In the resin containing a unit derived from (meth) acrylic acid, a unit derived from (meth) acrylate having an alicyclic hydrocarbon group, and a unit derived from (meth) acrylate having an alicyclic epoxy group, the amount of the unit derived from (meth) acrylate having an alicyclic epoxy group in the resin is preferably 1% by mass or more and 95% by mass or less, more preferably 30% by mass or more and 80% by mass or less.
The weight average molecular weight (Mw: a measurement value obtained by Gel Permeation Chromatography (GPC) and converted to polystyrene; the same applies to the present specification) of the crosslinkable group-containing resin is preferably 2000 to 200000, more preferably 2000 to 18000. When the content falls within the above range, the balance between the film forming ability of the photosensitive composition and the developability after exposure tends to be easily achieved.
(resin having Cardo Structure)
A resin having a Cardo structure (hereinafter, also referred to as "Cardo resin") described below may also be suitably used as the resin (B2).
As the Cardo resin, a resin having a Cardo skeleton in its structure and having a predetermined alkali solubility can be used. The Cardo skeleton is a skeleton in which a 2 nd and a 3 rd ring structures are bonded to 1 st ring carbon atom constituting the 1 st ring structure. The 2 nd and 3 rd ring structures may be the same or different.
As a typical example of the Cardo skeleton, a skeleton formed by bonding 2 aromatic rings (for example, benzene rings) to the carbon atom at the 9-position of the fluorene ring is given.
The resin having a Cardo structure is not particularly limited, and conventionally known resins can be used. Among them, the resin represented by the following formula (b-1) is preferable.
The resin represented by the following formula (b-1) has a carboxyl group, an ethylenically unsaturated double bond, and the like in its structure, and thus functions as an alkali-soluble resin having a crosslinkable group.
[ chemical formula 38]
In the formula (b-1), X b The expression is as followsA group represented by (b-2). t1 represents an integer of 0 to 20 inclusive.
[ chemical formula 39]
In the above formula (b-2), R b11 Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R b12 Each independently represents a hydrogen atom or a methyl group, R b13 Each independently represents a linear or branched alkylene group, t2 represents 0 or 1, W b The group represented by the following formula (b-3).
[ chemical formula 40]
In the formula (b-2), R is b13 The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, particularly preferably an alkylene group having 1 to 6 carbon atoms, and most preferably an ethane-1, 2-diyl group, propane-1, 2-diyl group, and propane-1, 3-diyl group.
Ring A in formula (b-3) b Represents an aliphatic ring which may be condensed with an aromatic ring and may have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring.
Examples of the aliphatic ring include monocycloparaffins, bicycloparaffins, tricycloparaffins, tetracycloparaffins, and the like.
Specifically, monocycloparaffins such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane are mentioned.
The aromatic ring which may be condensed with the aliphatic ring may be an aromatic hydrocarbon ring, or may be an aromatic heterocyclic ring, and is preferably an aromatic hydrocarbon ring. Specifically, benzene rings and naphthalene rings are preferable.
As preferable examples of the divalent group represented by the formula (b-3), the following are given.
[ chemical formula 41]
A divalent group X in the formula (b-1) b By providing residues Z b The tetracarboxylic dianhydride of (2 a) is reacted with a diol compound represented by the following formula (b-2 a) to be introduced into the Cardo resin.
[ chemical formula 42]
In the formula (b-2 a), R b11 、R b12 、R b13 And t2 are the same as those described for formula (b-2). With respect to ring A in formula (b-2 a) b The description is the same as that of the formula (b-3).
The diol compound represented by the formula (b-2 a) can be produced, for example, by the following method.
First, according to need, the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (b-2 b) is replaced with-R according to a conventional method b13 The group represented by-OH is then glycidylated using epichlorohydrin or the like to give an epoxy compound represented by the following formula (b-2 c).
Next, the epoxy compound represented by the formula (b-2 c) is reacted with acrylic acid or methacrylic acid to obtain the diol compound represented by the formula (b-2 a).
In the formula (b-2 b) and the formula (b-2 c), R b11 、R b13 And t2 are the same as those described for formula (b-2). With respect to the ring A in the formula (b-2 b) and the formula (b-2 c) b The description is the same as that of the formula (b-3).
The method for producing the diol compound represented by the formula (b-2 a) is not limited to the above method.
[ chemical formula 43]
As preferable examples of the diol compound represented by the formula (b-2 b), the following diol compounds are given.
[ chemical formula 44]
In the above formula (b-1), R b0 Is a hydrogen atom or-CO-Y b -COOH represents a group. Here, Y b Represents the residue resulting from the removal of the anhydride group (-CO-O-CO-) from the dicarboxylic anhydride. Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride, chlorendic anhydride (Chlorendic Anhydride), methyl tetrahydrophthalic anhydride, glutaric anhydride, and the like.
In the formula (b-1), Z b Represents a residue obtained by removing 2 acid anhydride groups from tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include tetracarboxylic dianhydride represented by the following formula (b-4), pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, and the like.
In the formula (b-1), t1 represents an integer of 0 to 20 inclusive.
[ chemical formula 45]
(in the formula (b-4), R b14 、R b15 And R is b16 Each independently represents 1 selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and t3 represents an integer of 0 to 12. )
Can be selected as R in formula (b-4) b14 The alkyl group of (2) is a C1-10 alkyl groupThe following alkyl groups. By setting the number of carbon atoms of the alkyl group within the above range, the heat resistance of the obtained carboxylic acid ester can be further improved. R is R b14 In the case of the alkyl group, the carbon number is preferably 1 to 6, more preferably 1 to 5, still more preferably 1 to 4, particularly preferably 1 to 3, from the viewpoint of easy obtaining of a Cardo resin excellent in heat resistance.
R b14 In the case of an alkyl group, the alkyl group may be linear or branched.
R as formula (b-4) b14 From the viewpoint of easy availability of Cardo resins excellent in heat resistance, each is more preferably independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R in formula (b-4) b14 More preferably a hydrogen atom, methyl group, ethyl group, n-propyl group or isopropyl group, and particularly preferably a hydrogen atom or methyl group.
From the viewpoint of easy preparation of high-purity tetracarboxylic dianhydride, a plurality of R's in the formula (b-4) b14 Preferably the same groups.
T3 in the formula (b-4) represents an integer of 0 to 12 inclusive. By setting t3 to 12 or less, purification of tetracarboxylic dianhydride can be easily performed.
The upper limit of t3 is preferably 5, more preferably 3, from the viewpoint of easiness in purification of tetracarboxylic dianhydride.
The lower limit of t3 is preferably 1, more preferably 2, from the viewpoint of chemical stability of the tetracarboxylic dianhydride.
T3 in the formula (b-4) is particularly preferably 2 or 3.
Can be selected as R in formula (b-4) b15 And R is b16 An alkyl group having 1 to 10 carbon atoms and optionally R b14 The same applies to alkyl groups having 1 to 10 carbon atoms.
R is from the viewpoint of easiness in purification of tetracarboxylic dianhydride b15 And R is b16 Preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (preferably 1 to 6, more preferably 1 to 5, still more preferably 1 to 4, particularly preferably 1 to 3)Particularly preferred is a hydrogen atom or a methyl group.
Examples of the tetracarboxylic dianhydride represented by the formula (b-4) include norbornane-2-spiro- α -cyclopentanone- α '-spiro-2 "-norbornane-5, 5",6, 6' -tetracarboxylic dianhydride (the alias is "norbornane-2-spiro-2 '-cyclopentanone-5' -spiro-2 '-norbornane-5, 5', 6,6 '-tetracarboxylic dianhydride), methyl norbornane-2-spiro-alpha-cyclopentanone-alpha' -spiro-2 '- (methyl norbornane) -5, 5', 6,6 '-tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclohexanone-alpha' -spiro-2 '-norbornane-5, 5', 6,6 '-tetracarboxylic dianhydride (the alias is" norbornane-2-spiro-2' -cyclohexanone-6 '-spiro-2' -norbornane-5, 5', 6, 6' -Tetracarboxylic dianhydride (alias "norbornane-2-spiro" -2 '-cyclohexanone-6' -spiro-2 "-norbornane-5, 5",6,6 '-tetracarboxylic dianhydride norbornane-2-spiro-alpha-cyclooctanone-alpha' -spiro-2 "-norbornane-5, 5",6,6 '-tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclooctanone-alpha' -spiro-2 '-norbornane-5, 5', 6,6 '-tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclononone-alpha' -spiro-2 '-norbornane-5, 5', 6,6 "-Tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclodecanone-alpha '-spiro-2" -norbornane-5, 5", 6" -Tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cycloundecanone-alpha' -spiro-2 "-norbornane-5, 5",6 "-Tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclododecanone-alpha '-spiro-2" -norbornane-5, 5", 6" -Tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclotridecanone-alpha' -spiro-2 "-norbornane-5, 5",6 "-Tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclotetradecanone-alpha ' -spiro-2 "-norbornane-5, 5",6, 6' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclopentadecanone-alpha ' -spiro-2 ' -norbornane-5, 5', 6,6 "-tetracarboxylic dianhydride, norbornane-2-spiro- α - (methylcyclopentanone) - α ' -spiro-2" -norbornane-5, 5", 6" -tetracarboxylic dianhydride, norbornane-2-spiro- α - (methylcyclohexanone) - α ' -spiro-2 "-norbornane-5, 5",6 "-tetracarboxylic dianhydride, etc.
The weight average molecular weight of the Cardo resin is preferably 1000 to 40000, more preferably 1500 to 30000, and still more preferably 2000 to 10000. When the content falls within the above range, not only good developability but also sufficient heat resistance and film strength can be obtained.
(Novolac resin)
As the resin (B2), a Novolac resin may be used. Novolac resins are alkali soluble resins. When the photosensitive composition contains a Novolac resin as the resin (B2), excessive heat flow of the cured film is easily suppressed when the cured film is post-baked when the cured film is formed using the photosensitive composition.
Therefore, when the black columnar spacers are formed using the photosensitive composition, if the photosensitive composition contains a Novolac resin, the black columnar spacers of a desired shape are easily formed.
As the Novolac resin, various Novolac resins blended in a photosensitive composition in the past can be used. The Novolac resin is preferably obtained by addition-condensing an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenols") with an aldehyde under acid catalysis.
Phenols (phenol)
Examples of phenols that can be used in the production of the Novolac resin include phenol; cresols such as o-cresol, m-cresol, and p-cresol; xylenols such as 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 2, 6-xylenol, 3, 4-xylenol, and 3, 5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol and p-ethylphenol; alkylphenols such as 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol; trialkylphenols such as 2,3, 5-trimethylphenol and 3,4, 5-trimethylphenol; polyhydric phenols such as resorcinol, catechol, hydroquinone monomethyl ether, pyrogallol, and phloroglucinol; alkyl polyphenols such as alkyl resorcinol, alkyl catechol, and alkyl hydroquinone (all alkyl groups have 1 to 4 carbon atoms); alpha-naphthol; beta-naphthol; hydroxybiphenyl (hydroxydiphenyl); bisphenol a, and the like. These phenols may be used alone or in combination of 2 or more.
Among these phenols, m-cresol and p-cresol are preferable, and m-cresol and p-cresol are more preferable in combination. In this case, various properties such as heat resistance of a cured film formed using the photosensitive composition can be adjusted by adjusting the blending ratio of the two.
The mixing ratio of m-cresol to p-cresol is not particularly limited, and is preferably 3/7 or more and 8/2 or less in terms of the molar ratio of m-cresol to p-cresol. By using m-cresol and p-cresol in the above-described ratio, a photosensitive composition capable of forming a cured film excellent in heat resistance can be easily obtained.
In addition, a Novolac resin produced by using m-cresol and 2,3, 5-trimethylphenol in combination is also preferable. When the Novolac resin is used, a photosensitive composition which can form a cured film which is less likely to flow excessively by heating during post baking is particularly easy to obtain.
The mixing ratio of m-cresol and 2,3, 5-trimethylphenol is not particularly limited, and is preferably 70/30 or more and 95/5 or less in terms of the molar ratio of m-cresol/2, 3, 5-trimethylphenol.
Aldehydes
Examples of aldehydes that can be used in the production of the Novolac resin include formaldehyde, paraformaldehyde (paraformaldehyde), furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone or in combination of 2 or more.
Acid catalyst
Examples of the acid catalyst that can be used for producing the Novolac resin include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethyl sulfate and p-toluenesulfonic acid; metal salts such as zinc acetate, and the like. These acid catalysts may be used alone or in combination of 2 or more.
Molecular weight
The weight average molecular weight (Mw; hereinafter also simply referred to as "weight average molecular weight") of the Novolac resin in terms of polystyrene is preferably 2000, more preferably 5000, particularly preferably 10000, further preferably 15000, most preferably 20000, and is preferably 50000, more preferably 45000, further preferably 40000, most preferably 35000, from the viewpoint of resistance to flow by heating of a cured film formed using the photosensitive composition.
As the Novolac resin, at least 2 kinds of Novolac resins having different weight average molecular weights in terms of polystyrene may be used in combination. The use of the combination of the sizes of the Novolac resins having different weight average molecular weights can balance the developability of the photosensitive composition and the heat resistance of the cured film formed using the photosensitive composition.
(modified epoxy resin)
The photosensitive composition may contain, as the resin (B2), a modified epoxy resin which is a polybasic acid anhydride (B-3 c) adduct of an epoxy compound (B-3 a) and a reactant of a carboxylic acid (B-3B) containing an unsaturated group, in terms of easily imparting high fluidity resistance at baking and high water resistance to a cured film formed using the photosensitive composition.
The modified epoxy resin has a carboxyl group, an ethylenically unsaturated double bond, and the like in its structure, and thus functions as an alkali-soluble resin having a crosslinkable group.
In the description and claims of the present application, a compound which satisfies the above definition but does not belong to the aforementioned resin having a Cardo structure is used as the modified epoxy resin.
The epoxy compound (b-3 a), the unsaturated group-containing carboxylic acid (b-3 b), and the polybasic acid anhydride (b-3 c) will be described below.
Epoxide (b-3 a)
The epoxy compound (b-3 a) is not particularly limited as long as it is a compound having an epoxy group, and may be an aromatic epoxy compound having an aromatic group, or may be an aliphatic epoxy compound containing no aromatic group, and preferably an aromatic epoxy compound having an aromatic group.
The epoxy compound (b-3 a) may be a monofunctional epoxy compound, or may be a polyfunctional epoxy compound having 2 or more functions, and is preferably a polyfunctional epoxy compound.
Specific examples of the epoxy compound (b-3 a) include 2-functional epoxy resins such as bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, bisphenol AD-type epoxy resins, naphthalene-type epoxy resins, and biphenyl-type epoxy resins; glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; glycidyl amine type epoxy resins such as tetraglycidyl aminodiphenylmethane, triglycidyl para-aminophenol, tetraglycidyl meta-xylylenediamine, and tetraglycidyl bisaminomethyl cyclohexane; heterocyclic epoxy resins such as triglycidyl isocyanurate; 3-functional epoxy resins such as phloroglucinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenyl methane triglycidyl ether, glycerol triglycidyl ether, 2- [4- (2, 3-glycidoxy) phenyl ] -2- [4- [1, 1-bis [4- (2, 3-glycidoxy) phenyl ] ethyl ] phenyl ] propane, and 1, 3-bis [4- [1- [4- (2, 3-glycidoxy) phenyl ] -1-methylethyl ] phenyl ] ethyl ] phenoxy ] -2-propanol; 4-functional epoxy resins such as tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, and tetraepoxypropoxy biphenyl.
The epoxy compound (b-3 a) is preferably an epoxy compound having a biphenyl skeleton.
The epoxy compound having a biphenyl skeleton preferably has at least 1 or more biphenyl skeletons represented by the following formula (b-3 a-1) in the main chain.
The epoxy compound having a biphenyl skeleton is preferably a multifunctional epoxy compound having 2 or more epoxy groups.
By using an epoxy compound having a biphenyl skeleton, a photosensitive composition having excellent balance between sensitivity and developability and capable of forming a cured film having excellent adhesion to a substrate can be easily obtained.
[ chemical formula 46]
(in the formula (b-3 a-1), R b17 Each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group which may have a substituent, and j is an integer of 1 to 4. )
R b17 When the alkyl group has 1 to 12 carbon atoms, specific examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, a n-nonyl group, an isononyl group, a n-decyl group, an isodecyl group, a n-undecyl group, and a n-dodecyl group.
R b17 In the case of a halogen atom, specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
R b17 In the case of a phenyl group which may have a substituent, the number of substituents on the phenyl group is not particularly limited. The number of substituents on the phenyl group is 0 or more and 5 or less, preferably 0 or 1.
Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aliphatic acyl group having 2 to 4 carbon atoms, a halogen atom, a cyano group, and a nitro group.
The epoxy compound (b-3 a) having a biphenyl skeleton represented by the above formula (b-3 a-1) is not particularly limited, and examples thereof include epoxy compounds represented by the following formula (b-3 a-2).
[ chemical formula 47]
(in the formula (b-3 a-2), R b17 And j is the same as formula (b-3 a-1), k is the average number of repeating structural units in parentheses and is 0 to 10. )
Among the epoxy compounds represented by the formula (b-3 a-2), the compounds represented by the following formula (b-3 a-3) are preferable in that a photosensitive composition excellent in balance between sensitivity and developability is particularly easy to obtain.
[ chemical formula 48]
(in the formula (b-3 a-3), k is the same as that of the formula (b-3 a-2))
(unsaturated group-containing carboxylic acid (b-3 b))
In the preparation of the modified epoxy compound (b-3), the epoxy compound (b-3 a) is reacted with the unsaturated group-containing carboxylic acid (b-3 b).
The unsaturated group-containing carboxylic acid (b-3 b) is preferably a monocarboxylic acid having a reactive unsaturated double bond such as an acrylic group (acryl group) or a methacrylic group (methacryl group) in the molecule. Examples of such unsaturated group-containing carboxylic acids include acrylic acid, methacrylic acid, β -styrylacrylic acid, β -furfurylacrylic acid, α -cyanocinnamic acid, cinnamic acid, and the like. The unsaturated group-containing carboxylic acid (b-3 b) may be used alone or in combination of 2 or more.
The epoxy compound (b-3 a) may be reacted with the unsaturated group-containing carboxylic acid (b-3 b) by a known method. Preferable reaction methods include, for example, the following methods: in the presence of a tertiary amine such as triethylamine or benzylethylamine, a quaternary ammonium salt such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride or benzyltriethylammonium chloride, pyridine or triphenylphosphine as a catalyst, an epoxy compound (b-3 a) is reacted with a carboxylic acid (b-3 b) having an unsaturated group in an organic solvent at a reaction temperature of 50 to 150 ℃ for several hours to several tens of hours.
The ratio of the amount of both the epoxy compound (b-3 a) and the unsaturated group-containing carboxylic acid (b-3 b) used in the reaction is usually preferably 1:0.5 to 1:2, more preferably 1:0.8 to 1:1.25, and particularly preferably 1:0.9 to 1:1.1, in terms of the ratio of the epoxy equivalent of the epoxy compound (b-3 a) to the carboxylic acid equivalent of the unsaturated group-containing carboxylic acid (b-3 b).
The ratio of the amount of the epoxy compound (b-3 a) to the amount of the unsaturated group-containing carboxylic acid (b-3 b) is preferably 1:0.5 to 1:2, and the crosslinking efficiency tends to be improved.
(polybasic acid anhydride (b-3 c))
The polybasic acid anhydride (b-3 c) is an anhydride of a carboxylic acid having 2 or more carboxyl groups.
The polybasic acid anhydride (b-3 c) is not particularly limited, and examples thereof include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, 3-methyl hexahydrophthalic anhydride, 4-methyl hexahydrophthalic anhydride, 3-ethyl hexahydrophthalic anhydride, 4-ethyl hexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyl tetrahydrophthalic anhydride, 4-methyl tetrahydrophthalic anhydride, 3-ethyl tetrahydrophthalic anhydride, 4-ethyl tetrahydrophthalic anhydride, compounds represented by the following formula (b-3 c-1), and compounds represented by the following formula (b-3 c-2). The polybasic acid anhydrides (b-3 c) may be used alone or in combination of 2 or more.
[ chemical formula 49]
(in the formula (b-3 c-2), R b18 An alkylene group which may have a substituent(s) and has 1 to 10 carbon atoms. )
The polybasic acid anhydride (b-3 c) is preferably a compound having 2 or more benzene rings, in view of ease of obtaining a photosensitive composition excellent in balance between sensitivity and developability. The polybasic acid anhydride (b-3 c) more preferably contains at least one of the compound represented by the above formula (b-3 c-1) and the compound represented by the above formula (b-3 c-2).
The method of reacting the epoxy compound (b-3 a) with the unsaturated group-containing carboxylic acid (b-3 b) followed by reacting with the polybasic acid anhydride (b-3 c) can be appropriately selected from known methods.
The ratio of the amount of the epoxy compound (b-3 a) to the unsaturated group-containing carboxylic acid (b-3 b) is usually 1:1 to 1:0.1, preferably 1:0.8 to 1:0.2, in terms of the molar number of OH groups in the component after the reaction and the equivalent ratio of the acid anhydride group of the polybasic acid anhydride (b-3 c). When the content falls within the above range, a photosensitive composition having good developability can be easily obtained.
The acid value of the modified epoxy resin (b-3) is preferably 10 to 150mgKOH/g, more preferably 70 to 110mgKOH/g, in terms of the solid content of the resin. The acid value of the resin is set to 10mgKOH/g or more, whereby sufficient solubility in a developer can be obtained, and the acid value is set to 150mgKOH/g or less, whereby sufficient curability can be obtained and surface properties can be improved.
The weight average molecular weight of the modified epoxy resin (b-3) is preferably 1000 to 40000, more preferably 2000 to 30000. When the weight average molecular weight is 1000 or more, a black columnar spacer excellent in heat resistance and strength can be easily formed. Further, when the weight average molecular weight is 40000 or less, a photosensitive composition exhibiting sufficient solubility in a developer can be easily obtained.
(Polymer containing structural units having a Ring Structure in the Main chain)
The polymer having a structural unit having a ring structure in the main chain is not particularly limited as long as it is a resin having not only a prescribed ring structure but also a prescribed alkali solubility. Preferable examples of the polymer having a structural unit having a ring structure in the main chain include a polymer (hereinafter, also referred to as "polymer (A2)") having a structural unit derived from maleimide (hereinafter, also referred to as "structural unit (A2)") and a polymer (hereinafter, also referred to as "polymer (A1)") having a structural unit represented by the following formula (a-1) (hereinafter, also referred to as "structural unit (A1 a)").
The maleimide-derived structural unit (A2 a) of the polymer (A2) is not particularly limited as long as it is a structural unit obtained by polymerizing a monomer having a maleimide skeleton. Examples of the monomer having a maleimide skeleton include N-benzyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, and the like.
In particular, the photosensitive composition containing the polymer (A1) having the structural unit (A1 a) having a ring structure in the main chain has good solubility in a developer.
[ chemical formula 50]
In the formula (A-1), the ring A is a saturated aliphatic cyclic group having 1 oxygen atom as a ring structure atom and having 4 to 6 carbon atoms. Ring a is preferably a saturated aliphatic cyclic group having 1 oxygen atom as a ring structure atom and having 4 or 5 carbon atoms, more preferably a tetrahydrofuran ring or a tetrahydropyran ring, and still more preferably a tetrahydropyran ring of a structural unit represented by the following formula (a-3) (hereinafter, also referred to as "structural unit (A1)") or a tetrahydrofuran ring of a structural unit represented by the following formula (a-4) (hereinafter, also referred to as "structural unit (A1 a 2)").
[ chemical formula 51]
The polymer (A1)) having a structural unit represented by the above formula (A-1) in the main chain generally has a plurality of structural units (A1 a)) represented by the above formula (A-1) in the main chain. Among the plurality of structural units (A1 a), the rings a contained in each structural unit (A1 a) may be the same or different from each other in one main chain constituting the polymer (A1). Specifically, as the structural unit represented by the above formula (A-1) contained in one main chain constituting the polymer (A1), for example, the structural unit represented by the above formula (A-3) may be contained, the structural unit represented by the above formula (A-4) may be contained, or the structural unit represented by the above formula (A-3) and the structural unit represented by the above formula (A-4) may be contained at the same time.
In the above formula (A-1), formula (A-3) and formula (A-4), R b1 And R is b2 Each independently is a hydrogen atom or-COOR b3 ，R b3 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. R is R b1 And R is b2 preferably-COOR b3 . When one main chain of the polymer (A1)) constituting the polymer (A1)) containing the structural unit represented by the above formula (A-1) contains a plurality of rings A, the-COOR groups bonded to the rings A are bonded b3 Independently of one another, can be identical or different-COOR b3 The groups are bonded to each ring a.
As R b1 And R is b2 The hydrocarbon group having 1 to 25 carbon atoms which may have a substituent is not particularly limited. Specific examples of the hydrocarbon group include straight-chain or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-pentyl, stearyl, lauryl, and 2-ethylhexyl; aryl groups such as phenyl; alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadiene, tricyclodecyl, isobornyl, adamantyl, and 2-methyl-2-adamantyl; alkyl groups substituted with an alkoxy group such as 1-methoxyethyl and 1-ethoxyethyl; aryl-substituted alkyl such as benzyl; etc.
R b1 And R is b2 In the case of the hydrocarbon group, the number of carbon atoms of the hydrocarbon group is preferably 8 or less. The hydrocarbon group having 8 or less carbon atoms is preferably a hydrocarbon group having a free chemical bond at one end thereof bonded to a primary carbon atom or a secondary carbon atom, since the hydrocarbon group is less likely to be stripped by acid or heat. The hydrocarbon group is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 5 carbon atoms.
Specific examples of such hydrocarbon groups include methyl, ethyl, cyclohexyl, benzyl, and the like, and methyl is preferred.
When a plurality of structural units (A1 a) are contained in one main chain of a polymer (A1)) constituting a polymer (structural unit (A1 a)) containing structural units (structural unit (A1 a)) represented by the above formula (A-1), R bonded to each structural unit (A1 a) b1 And R is b2 The structural units (A1 a) may be the same or different from each other.
When the ring A is contained, R is the same or different between the structural units (A1 a) b1 And R is b2 Independent of the type of ring a bonded.
Specifically, when a plurality of structural units (A1 A1)) represented by the above formula (A-3) are contained in one main chain constituting the polymer (A1), R in each structural unit (A1 A1) b1 And R is b2 The structural units (A1) may be the same or different from each other.
When a plurality of structural units (A1 a 2)) represented by the above formula (A-4) are contained in one main chain constituting the polymer (A1), R in each structural unit (A1 a 2) b1 And R is b2 The structural units (A1 a 2) may be the same or different from each other.
In addition, when the structural unit (A1 A1)) represented by the above formula (A-3) and the structural unit (A1 a 2)) represented by the above formula (A-4) are contained in one main chain constituting the polymer (A1), R in each structural unit (A1 A1) b1 And R is b2 R in each structural unit (A1 a 2) b1 And R is b2 May be the same or different.
The structural unit (A1 A1)) represented by the above formula (A-3) may be a part of a repeating unit (hereinafter, also referred to as "repeating unit (ar 1)") represented by the following formula (A-5). The structural unit (A1 a 2)) represented by the above formula (a-4) may be a part of a repeating unit (hereinafter, also referred to as "repeating unit (ar 2)") represented by the following formula (a-6).
[ chemical formula 52]
(in the formula (A-5) and the formula (A-6), R b1 And R is b2 Each independently is the same as described above. )
Examples of the monomer providing each repeating unit represented by the above formulae (A-5) and (A-6) include 1, 6-dienes represented by the following formulae.
[ chemical formula 53]
(in the above formula, R b3 Each independently is the same as described above. )
In the monomer composition of the polymer (A1)) having the structural unit (A1 a)) represented by the above formula (a-1) in the main chain, the content of the monomer (A1 ma) having the repeating unit (which may include the structural unit (A1) and the structural unit (A1 a 2)) of the structural unit (A1 a) is preferably 1% by mass or more and 60% by mass or less, more preferably 5% by mass or more and 50% by mass or less, and particularly preferably 10% by mass or more and 40% by mass or less, with respect to the total amount of the monomers in the monomer composition.
The polymer (A1) preferably has a repeating unit (A1 b) having an acid group in a side chain. When the polymer (A1) has a repeating unit (A1 b) having an acid group in a side chain, a photosensitive composition excellent in alkali developability can be obtained. Examples of the monomer (A1 mb) constituting the repeating unit (A1 b) having an acid group in a side chain include monomers having a carboxyl group such as (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, itaconic acid, and ω -carboxyl-polycaprolactone monoacrylate; monomers having carboxylic anhydride groups such as maleic anhydride and itaconic anhydride. Among them, (meth) acrylic acid is preferable.
In the monomer composition for providing the polymer (A1), the content of the monomer (A1 mb) constituting the repeating unit (A1 b) having an acid group in a side chain is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, still more preferably 10% by mass or more and 35% by mass or less, relative to the total amount of the monomers in the monomer composition.
Preferably, the polymer (A1) has a repeating unit (A1 c) having a carbon double bond in a side chain. The repeating unit (A1 c) having a carbon double bond in the side chain can be obtained by adding a compound having a carbon double bond to a reaction site of a part or all (preferably a part) of the acid groups of the repeating unit (A1 b) having an acid group in the side chain.
When the acid group of the repeating unit (A1 b) having an acid group in a side chain is a carboxyl group, a compound having an epoxy group and a double bond, a compound having an isocyanate group and a double bond, or the like can be used as the compound having a carbon double bond. Examples of the compound having an epoxy group and a double bond include glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and 4-hydroxybutyl acrylate glycidyl ether. Examples of the compound having an isocyanate group and a double bond include 2-isocyanatoethyl (meth) acrylate and the like. When the acid group of the repeating unit (A1 b) having an acid group in the side chain is a carboxylic acid anhydride group, a compound having a hydroxyl group and a double bond can be used as the compound having a carbon double bond. Examples of the compound having a hydroxyl group and a double bond include 2-hydroxyethyl (meth) acrylate and the like.
The polymer (A1) may further have another repeating unit (A1 e) derived from another monomer (A1 me) copolymerizable with the monomer (A1 ma), the monomer (A1 mb) and/or the monomer (A1 mc).
The other monomer (A1 me) may further have a repeating unit having 2 or more oxyalkylene groups (oxyalkylene group) in a side chain, for example. Examples of the repeating unit having 2 or more oxyalkylene groups in the side chain include repeating units represented by the following formula.
[ chemical formula 54]
In the above formula, R b7 、R b8 And R is b9 Each independently is a hydrogen atom or a methyl groupPreferably a hydrogen atom. R is R b10 The aromatic hydrocarbon group is preferably a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably a linear alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a linear alkyl group having 6 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a linear alkyl group having 1 to 5 carbon atoms, a phenyl group, or a biphenyl group, and particularly preferably a methyl group, a phenyl group, or a biphenyl group. The alkyl group, the alkenyl group, and the aromatic hydrocarbon group may have a substituent. AO represents an oxyalkylene group. The number of carbon atoms of the oxyalkylene group represented by AO is 2 or more and 20 or less, preferably 2 or more and 10 or less, more preferably 2 or more and 5 or less, and still more preferably 2. The repeating unit having 2 or more oxyalkylene groups in the side chain may contain 1 or 2 or more oxyalkylene groups. x represents an integer of 0 to 2. y represents 0 or 1.z represents an average molar number of addition of the oxyalkylene groups, and is preferably 2 or more and 100 or less, more preferably 2 or more and 50 or less, and still more preferably 2 or more and 15 or less.
The repeating unit having 2 or more oxyalkylene groups in the side chain is constituted of a monomer having 2 or more oxyalkylene groups in the side chain. Examples of the monomer include monomers represented by the following formula.
[ chemical formula 55]
(in the above formula, R b7 、R b8 、R b9 、R b10 The AO, x, y, and z are the same as described above. )
Examples of the monomer having 2 or more alkylene oxide groups in the side chain include ethoxylated o-phenylphenol (meth) acrylate (EO 2 mol), phenoxydiglycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate (EO 4 mol), methoxypolyethylene glycol (meth) acrylate (EO 9 mol), methoxypolyethylene glycol (meth) acrylate (EO 13 mol), methoxytriethylene glycol (meth) acrylate, ethoxydiglycol (meth) acrylate, butoxydiglycol (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate (EO 4-17 mol), nonylphenoxy polypropylene glycol (meth) acrylate (PO 5 mol), EO modified cresol (meth) acrylate (EO 2 mol), and the like. These monomers may be used alone or in combination of 2 or more. Among them, preferable are ethoxylated ortho-phenylphenol (meth) acrylate (EO 2 mol), methoxypolyethylene glycol (meth) acrylate (EO 9 mol), methoxypolyethylene glycol (meth) acrylate (EO 13 mol). Further preferable examples thereof include ethoxylated ortho-phenylphenol acrylate (EO 2 mol), methoxypolyethylene glycol acrylate (EO 9 mol), and methoxypolyethylene glycol acrylate (EO 13 mol). In the present specification, for example, "EO2 mol", "PO5 mol", and the like are described as representing the average addition mole number of the oxyalkylene group.
Examples of the other monomer (A1 me) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, biphenyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethylene glycol (meth) acrylate, 2-ethylhexyl ethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, biphenoxyethyl (meth) acrylate, dicyclopentyl (dicyclopentanyl (meth) acrylate), tricyclodecyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate (dicyclopentanyl oxyethyl (meth) acrylate), tricyclodecyloxyethyl (meth) acrylate, nonylphenoxy (meth) acrylate, and (meth) acrylate (2-hydroxy ethyl (meth) acrylate (meth) acrylates such as ethoxylated ortho-phenylphenol (meth) acrylate; (meth) acrylamides such as morpholinyl (meth) acrylate, (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, N-t-butyl (meth) acrylamide, N-t-octyl (meth) acrylamide, acetylacetone (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, N-triphenylmethyl (meth) acrylamide, N-dimethyl (meth) acrylamide; aromatic vinyl compounds such as styrene, vinyl toluene, and α -methylstyrene; butadiene or substituted butadiene compounds such as butadiene and isoprene; ethylene or substituted ethylene compounds such as ethylene, propylene, vinyl chloride, and acrylonitrile; vinyl esters such as vinyl acetate, and the like. These monomers may be used alone or in combination of 2 or more.
In the monomer composition for providing the polymer (A1), the content of the monomer (A1 me) for providing the other repeating unit (A1 e) is preferably 0 mass% or more and 55 mass% or less, more preferably 5 mass% or more and 50 mass% or less, and still more preferably 10 mass% or more and 45 mass% or less, relative to the total amount of the monomers in the monomer composition.
The polymer (A1) may be a random copolymer or a block copolymer. The polymer (A1) may be used alone or in combination of 2 or more.
The weight average molecular weight of the polymer (A1) is preferably 3,000 or more and 200,000 or less, more preferably 3,500 or more and 100,000 or less, still more preferably 4,000 or more and 50,000 or less, as measured by Gel Permeation Chromatography (GPC) using a Tetrahydrofuran (THF) solvent. When the amount is within the above range, heat resistance can be ensured, and a photosensitive composition having a viscosity suitable for forming a coating film can be obtained.
The polymer (A1) can be obtained by polymerizing a monomer composition providing the polymer (A1) by any suitable method. The polymerization method includes, for example, a solution polymerization method.
The monomer composition providing the polymer (A1) may comprise any suitable solvent. Examples of the solvent include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and propylene glycol monomethyl ether; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; alcohols such as methanol and ethanol; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform; dimethyl sulfoxide, and the like. These solvents may be used alone or in combination of 2 or more. The polymerization concentration in polymerizing the monomer composition is preferably 5% by mass or more and 90% by mass or less, more preferably 5% by mass or more and 50% by mass or less, and still more preferably 10% by mass or more and 50% by mass or less.
The monomer composition providing the polymer (A1) may contain any suitable polymerization initiator. Examples of the polymerization initiator include organic peroxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate (tert-butylperoxy isopropyl carbonate), t-amyl peroxy-2-ethylhexanoate, and t-butyl peroxy-2-ethylhexanoate; azo compounds such as 2,2 '-azobis (isobutyronitrile), 1' -azobis (cyclohexane carbonitrile), 2 '-azobis (2, 4-dimethylvaleronitrile), and dimethyl 2,2' -azobis (2-methylpropionate). The content ratio of the polymerization initiator is preferably 0.1 part by mass or more and 15 parts by mass or less, more preferably 0.5 part by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the total monomers in the monomer composition.
The polymerization temperature in the case of polymerizing the polymer (A1) by the solution polymerization method is preferably 40℃or more and 150℃or less, more preferably 60℃or more and 130℃or less.
In the case of obtaining the polymer (A1) having the repeating unit (A1 c) having a carbon double bond in a side chain, the compound having a carbon double bond is added to the obtained polymer after the polymerization. As a method for adding a compound having a carbon double bond, any suitable method can be employed. For example, a compound having a carbon double bond is reacted with part or all (preferably part) of the acid groups of the repeating unit (A1 b) having an acid group in a side chain in the presence of a polymerization inhibitor and a catalyst to perform addition, whereby the repeating unit (A1 c) having a carbon double bond in a side chain can be formed.
The addition amount of the compound having a carbon double bond is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more, based on 100 parts by mass of the polymer after polymerization (i.e., the polymer before addition of the compound having a carbon double bond). When the amount is within the above range, a photosensitive composition excellent in exposure sensitivity can be obtained. When such a photosensitive composition is used, the following tends to be present: a dense cured coating film is easily formed, and a pattern excellent in substrate adhesion can be obtained. When the addition amount of the compound having a carbon double bond is within the above range, hydroxyl groups are sufficiently formed by the addition of the compound having a carbon double bond, and a photosensitive composition excellent in solubility in an alkali developer can be obtained. The upper limit of the addition amount of the compound having a carbon double bond is preferably 170 parts by mass or less, more preferably 150 parts by mass or less, and still more preferably 140 parts by mass or less, per 100 parts by mass of the polymer after polymerization (i.e., the polymer before addition of the compound having a carbon double bond). When the addition amount of the compound having a carbon double bond is within the above range, the storage stability and solubility of the photosensitive composition can be maintained.
Examples of the polymerization inhibitor include alkylphenol compounds such as 6-tert-butyl-2, 4-xylenol. Examples of the catalyst include tertiary amines such as dimethylbenzylamine and triethylamine.
The content of the resin (B2) described above is preferably 1% by mass or more and 95% by mass or less, more preferably 3% by mass or more and 85% by mass or less, particularly preferably 5% by mass or more and 70% by mass or less, with respect to the solid content of the photosensitive composition.
When the photosensitive composition contains the resin (B2) in the above-mentioned amount, the film forming property of the photosensitive composition is good, and a cured film having good mechanical properties and shape is easily formed.
In addition, when the resin (B2) is alkali-soluble, good alkali developability is easily achieved.
< colorant (C) >)
The photosensitive composition may contain a colorant (C) according to the purpose of a cured film formed using the photosensitive composition. The colorant (C) is preferably a pigment from the viewpoints of good light resistance and weather resistance, and less tendency to bleed out (bleeding).
As the Pigment, for example, a compound classified as Pigment (Pigment) in the dye index (c.i.; issued by The Society of Dyers and Colourists company) may be used, and specifically, such a Pigment with a dye index (c.i.) number as described below may be used.
Examples of yellow pigments that can be preferably used include c.i. pigment yellow 1 (hereinafter, also referred to as "c.i. pigment yellow", only numbers are described therein), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73,74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185.
Examples of orange pigments that can be preferably used include c.i. pigment orange 1 (hereinafter, also referred to as "c.i. pigment orange", only numbered are described), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, and 73.
Examples of violet pigments that can be preferably used include c.i. pigment violet 1 (hereinafter, also referred to as "c.i. pigment violet", only numbered herein), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50.
Examples of the red pigment that can be preferably used include c.i. pigment red 1 (hereinafter, also referred to as "c.i. pigment red", only numbered.) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 220, 226, 223, 240, 245, 240, and 245.
Examples of blue pigments that can be preferably used include c.i. pigment blue 1 (hereinafter, also referred to as "c.i. pigment blue", only reference numerals are given), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64, and 66.
Examples of pigments having hues other than the above-mentioned ones that can be preferably used include green pigments such as c.i. pigment green 7, c.i. pigment green 36, c.i. pigment green 37, brown pigments such as c.i. pigment brown 23, c.i. pigment brown 25, c.i. pigment brown 26, c.i. pigment brown 28, and black pigments such as c.i. pigment black 1 and c.i. pigment black 7.
In addition, when light-shielding properties are imparted to the photosensitive composition, the photosensitive composition preferably contains a black pigment as the colorant (C). The photosensitive composition containing the black pigment can be suitably used for formation of a black matrix or a black column spacer in a liquid crystal display panel, formation of a bank for dividing a light-emitting layer in an organic EL element.
Examples of the black pigment include carbon black, perylene pigments, lactam pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, and other metal oxides, composite oxides, metal sulfides, metal sulfates, metal carbonates, and other various pigments (both organic and inorganic). Among these black pigments, carbon black is preferred in terms of easy availability and easy formation of a cured film excellent in light shielding properties and high in electrical resistance.
The hue of the black pigment is not limited to black which is achromatic in colorimetry, and may be violet black, blue black, or red black.
As the carbon black, known carbon blacks such as channel black (channel black), furnace black (thermal black), thermal black (thermal black) and lamp black (lamp black) can be used. In addition, carbon black coated with a resin may be used.
Carbon black to which a treatment for introducing an acidic group is applied is also preferable as carbon black. The acidic group introduced into the carbon black is a functional group exhibiting acidity based on the definition of bronsted. Specific examples of the acidic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The acidic groups introduced into the carbon black may form salts. The cation forming a salt with an acidic group is not particularly limited insofar as it does not interfere with the object of the present invention. Examples of the cations include various metal ions, cations of nitrogen-containing compounds, and ammonium ions, and alkali metal ions such as sodium ions, potassium ions, and lithium ions, and ammonium ions are preferable.
Among the carbon blacks subjected to the acidic group-introduced treatment described above, carbon blacks having 1 or more functional groups selected from the group consisting of carboxylic acid groups, carboxylate groups, sulfonic acid groups, and sulfonate groups are preferable from the viewpoint of achieving high resistance of a light-shielding cured film formed using the photosensitive composition.
The method of introducing the acidic group into the carbon black is not particularly limited. Examples of the method for introducing the acidic group include the following methods.
Method 1), a sulfonic acid group is introduced into carbon black by a direct substitution method (which uses concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or the like), or an indirect substitution method (which uses sulfite, bisulfite, or the like).
Method 2) diazo coupling an organic compound having an amino group and an acidic group with carbon black.
Method 3) reacting an organic compound having a halogen atom and an acidic group with carbon black having a hydroxyl group by the Williamson etherification method.
Method 4) reacting an organic compound having a halocarbonyl group and an acidic group protected by a protecting group with carbon black having a hydroxyl group.
Method 5) Friedel-Crafts reaction and deprotection of carbon black using an organic compound having a halocarbonyl group and an acidic group protected by a protecting group.
Among these methods, method 2) is preferred in view of easiness of the treatment of introducing an acidic group and safety. As the organic compound having an amino group and an acidic group used in method 2), a compound in which an amino group and an acidic group are bonded to an aromatic group is preferable. Examples of such a compound include aminobenzenesulfonic acid such as p-aminobenzenesulfonic acid and aminobenzoic acid such as 4-aminobenzoic acid.
The number of moles of the acidic groups to be introduced into the carbon black is not particularly limited within a range that does not hinder the object of the present invention. The number of moles of the acidic groups introduced into the carbon black is preferably 1mmol or more and 200mmol or less, more preferably 5mmol or more and 100mmol or less, per 100g of the carbon black.
For carbon black having an acid group introduced thereinto, a coating treatment with a resin may be performed.
When a photosensitive composition containing a resin-coated carbon black is used, a light-shielding cured film excellent in light shielding and insulation properties and having low surface reflectance can be easily formed. The coating treatment with the resin does not adversely affect the dielectric constant of the light-shielding cured film formed using the photosensitive composition. Examples of the resin that can be used for the carbon black coating include thermoplastic resins such as phenol resins, melamine resins, xylene resins, diallyl phthalate resins, thermosetting resins such as glycerin (glyptal) resins, epoxy resins, and alkylbenzene resins, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polysulfone, poly (paraphenylene terephthalamide), polyamide imide, polyimide, polyaminobismaleimide, polyethersulfone polyphenylene sulfone, polyarylate, and polyetheretherketone. The coating amount of the resin on the carbon black is preferably 1 mass% or more and 30 mass% or less with respect to the total of the mass of the carbon black and the mass of the resin.
Furthermore, perylene pigments can be preferably used as the black pigment. Specific examples of the perylene pigment include perylene pigments represented by the following formula (d-1), perylene pigments represented by the following formula (d-2), and perylene pigments represented by the following formula (d-3). Among commercial products, product names K0084 and K0086 manufactured by BASF corporation, pigment black 21, 30, 31, 32, 33, 34, and the like can be preferably used as the perylene pigment.
[ chemical formula 56]
In the formula (c-1), R c1 And R is c2 Each independently represents an alkylene group having 1 to 3 carbon atoms, R c3 And R is c4 Each independently represents a hydrogen atom, a hydroxyl group, a methoxy group, or an acetyl group.
[ chemical formula 57]
In the formula (c-2), R c5 And R is c6 Each independently represents an alkylene group having 1 to 7 carbon atoms.
[ chemical formula 58]
/>
In the formula (c-3), R c7 And R is c8 Each independently of the otherThe alkyl group having 1 to 22 carbon atoms may contain a heteroatom N, O, S or P. R is R c7 And R is c8 In the case of an alkyl group, the alkyl group may be linear or branched.
The compound represented by the above formula (c-1), the compound represented by the formula (c-2) and the compound represented by the formula (c-3) can be synthesized by the methods described in, for example, japanese patent application laid-open No. 62-1753 and Japanese patent application laid-open No. 63-26784. Namely, perylene-3,5,9,10-tetracarboxylic acid or dianhydride thereof and amines are used as raw materials, and the raw materials are heated and reacted in water or an organic solvent. Then, the obtained crude product is reprecipitated in sulfuric acid or recrystallized in water, an organic solvent or a mixed solvent thereof, whereby the objective product can be obtained.
In order to disperse the perylene pigment in the photosensitive composition well, the average particle diameter of the perylene pigment is preferably 10nm or more and 1000nm or less.
Further, as the light-shielding agent, a lactam-based pigment may be contained. Examples of the lactam-based pigment include compounds represented by the following formula (c-4).
[ chemical formula 59]
In the formula (c-4), X c Represents a double bond, each of which is independently E or Z, R c9 Each independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine atom, a chlorine atom, a fluorine atom, a carboxyl group, or a sulfo group, R c10 Each independently represents a hydrogen atom, a methyl group, or a phenyl group, R c11 Each independently represents a hydrogen atom, a methyl group, or a chlorine atom.
The compounds represented by the formula (c-4) may be used alone or in combination of 2 or more.
R is a group represented by the formula (c-4) in view of easy production of the compound c9 Preferably bonded to the 6-position of the indolinone ring, R c11 Preferably bonded to the 4-position of the indolinone ring. From the same point of view, R c9 、R c10 And R is c11 Preferably a hydrogen atom.
The compound represented by the formula (c-4) has EE, ZZ and EZ as geometric isomers, and may be a single compound of any one of them or may be a mixture of these geometric isomers.
The compound represented by the formula (c-4) can be produced, for example, by the method described in International publication No. 2000/24736 and International publication No. 2010/081624.
In order to disperse the lactam-based pigment in the photosensitive composition well, the average particle diameter of the lactam-based pigment is preferably 10nm to 1000 nm.
Further, fine particles containing silver-tin (AgSn) alloy as a main component (hereinafter, referred to as "AgSn alloy fine particles") are also preferably used as the black pigment. The fine particles of the AgSn alloy may contain, for example, ni, pd, au, or the like as other metal components as long as the AgSn alloy is the main component.
The average particle diameter of the AgSn alloy fine particles is preferably 1nm to 300 nm.
When AgSn alloy is represented by chemical formula AgxSn, the range of x capable of obtaining AgSn alloy with stable chemical property is not less than 1 and not more than 10, and the range of x capable of simultaneously obtaining chemical stability and blackness is not less than 3 and not more than 4.
Here, in the above range of x, the mass ratio of Ag in the AgSn alloy was obtained, and as a result,
when x=1, ag/agsn= 0.4762
When x=3, 3·ag/ag3sn= 0.7317
When x=4, 4·ag/ag4sn= 0.7843
When x=10, 10·ag/ag10sn= 0.9008.
Therefore, the chemical stability and blackness can be effectively obtained according to the amount of Ag when the AgSn alloy contains 47.6 mass% or more and 90 mass% or less, and when the AgSn alloy contains 73.17 mass% or more and 78.43 mass% or less.
The AgSn alloy fine particles can be produced by a conventional fine particle synthesis method. Examples of the microparticle synthesis method include an air phase reaction method, a spray pyrolysis method, a spray dispersion method, a liquid phase reaction method, a freeze drying method, and a hydrothermal synthesis method.
Although the AgSn alloy fine particles have high insulation properties, the surface may be coated with an insulating film to further improve the insulation properties depending on the application of the photosensitive composition. As a material of such an insulating film, a metal oxide or an organic polymer compound is preferable.
As the metal oxide, a metal oxide having insulating properties, such as silicon oxide (silica), aluminum oxide (alumina), zirconium oxide (zirconia), yttrium oxide (yttria), titanium oxide (titania), or the like, can be suitably used.
As the organic polymer compound, a resin having insulating properties, such as polyimide, polyether, polyacrylate, polyamine compound, or the like, can be suitably used.
The thickness of the insulating film is preferably 1nm to 100nm, more preferably 5nm to 50nm, in order to sufficiently improve the insulation properties of the surface of the fine particles of the AgSn alloy.
The insulating film can be easily formed using a surface modification technique or a surface coating technique. In particular, when an alkoxide such as tetraethoxysilane or aluminum triethoxide is used, an insulating film having a uniform film thickness can be formed at a relatively low temperature, which is preferable.
The perylene pigment, the lactam pigment, and the AgSn alloy fine particles may be used alone or in combination.
Further, for the purpose of adjusting the hue and the like, the black pigment may contain pigments of hues of red, blue, green, yellow and the like. Pigments having hues other than black pigments can be appropriately selected from known pigments. For example, as pigments having hues other than black pigments, the above-described various pigments can be used. The amount of the coloring matter used in the hues other than the black pigment is preferably 15% by mass or less, more preferably 10% by mass or less, based on the total mass of the black pigment.
In order to uniformly disperse the pigment described above in the photosensitive composition, a dispersing agent may be further used. As such a dispersant, a polymer dispersant of polyethyleneimine type, polyurethane resin type, or acrylic resin type is preferably used. In particular, when carbon black is used as the pigment, an acrylic resin-based dispersant is preferably used as the dispersant.
In some cases, corrosive gas may be generated from the cured film due to the dispersant. Therefore, it is also an example of a preferable embodiment to disperse the pigment without using a dispersant.
In addition, the inorganic pigment and the organic pigment may be used singly or in combination of 2 or more, and in the case of using them in combination, the organic pigment is preferably used in a range of 10 parts by mass or more and 80 parts by mass or less, more preferably 20 parts by mass or more and 40 parts by mass or less, relative to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment.
The pigment and the dye may be used in combination in the photosensitive composition. The dye may be selected appropriately from known materials.
Examples of the dye that can be used in the photosensitive composition include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinone imine dyes, methine (methine) dyes, and phthalocyanine dyes.
Further, these dyes can be used as the colorant (C) by being dispersed in an organic solvent or the like by performing laking (salification).
In addition to these dyes, for example, dyes described in Japanese patent application laid-open No. 2013-225132, japanese patent application laid-open No. 2014-178477, japanese patent application laid-open No. 2013-137543, japanese patent application laid-open No. 2011-38085, japanese patent application laid-open No. 2014-197206, and the like can be preferably used.
The amount of the colorant (C) used in the photosensitive composition can be appropriately selected within a range that does not hinder the object of the present invention, and is typically preferably 2% by mass or more and 75% by mass or less, more preferably 3% by mass or more and 70% by mass or less, relative to the mass of the entire solid content of the photosensitive composition.
When a pigment is used as the colorant (C), it is preferable that the pigment is dispersed in a proper concentration in the presence or absence of a dispersant to prepare a dispersion liquid, and then added to the photosensitive composition.
In the present specification, the amount of the pigment used may be defined as a value including the dispersant present as described above.
< other Components >)
The photosensitive composition may contain various additives as needed. Specifically, the solvent, the surface conditioner, the sensitizer, the curing accelerator, the photocrosslinker, the photosensitizing agent, the dispersing aid, the filler, the adhesion accelerator, the antioxidant, the ultraviolet absorber, the deflocculant, the thermal polymerization inhibitor, the antifoaming agent, the surfactant, the chain transfer agent, and the like can be exemplified. All additives can be used as known in the art. Examples of the surfactant include anionic compounds, cationic compounds, and nonionic compounds. As the adhesion improving agent, a known silane coupling agent is known. Examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether. Examples of the defoaming agent include silicone compounds and fluorine compounds.
Examples of the chain transfer agent include thiol compounds, halogen compounds, quinone compounds, and α -methylstyrene dimers. By containing the chain transfer agent, the pattern shape (particularly, CD variation of hole pattern, exposure margin) can be well controlled. Among them, 2, 4-diphenyl-4-methyl-1-pentene (α -methylstyrene dimer) is preferable in view of reducing sublimates, coloring and odor in addition to the above effects.
When a solvent is used in the photosensitive composition, examples of usable solvents include (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, and the like; (poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; alkyl lactate esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; other esters such as ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide. These solvents may be used alone or in combination of 2 or more.
Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (GPMEA), propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether (megg), cyclohexanone, 3-methoxybutyl acetate (MBA) exhibit excellent solubility for the above-mentioned component (A1) and component (A2) and optionally component (B), and propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are particularly preferably used. The content of the solvent may be appropriately determined depending on the application of the photosensitive composition, and may be, for example, about 50 parts by mass or more and 900 parts by mass or less based on 100 parts by mass of the total solid content of the photosensitive composition.
Process for producing photosensitive composition
The photosensitive composition according to the present invention can be prepared by: the above components were uniformly stirred and mixed to be uniformly dissolved and dispersed, and then, if necessary, filtered with a filter such as a 0.2 μm membrane filter.
Method for Forming cured Material and cured Material
The method for forming a cured product is similar to the conventional method for forming a cured product using a photosensitive composition, except that the photosensitive composition is used.
The method for forming a cured product using the photosensitive composition is not particularly limited, and may be appropriately selected from conventionally employed methods. The cured product can be formed into a molded article having a desired shape by a combination of control of the shape of the coating film, position-selective exposure and development at the time of coating the photosensitive composition. A preferable method for forming a cured product includes a coating film forming step of forming a coating film using the photosensitive composition and an exposure step of exposing the coating film. In the case of positionally selective exposure, the exposed coating film may be developed with a developer, thereby obtaining a patterned cured product.
First, in a coating film forming step, for example, a photosensitive composition according to the present invention is applied to a substrate on which a cured product is to be formed by using a contact transfer type coating apparatus such as a roll coater, a reverse coater, a bar coater, etc., a non-contact type coating apparatus such as a spin coater (spin coater), a curtain flow coater (curtain flow coater), etc., and if necessary, a solvent is removed by drying (prebaking) to form a coating film.
For convenience, the droplets contained on the substrate, the photosensitive composition filled in the concave portion of the substrate having the irregularities, the photosensitive composition filled in the concave portion of the mold, and the like are also referred to as "coating film".
Next, the formed coating film is subjected to an exposure process. In the exposure step, the coating film is irradiated with ArF excimer laser, krF excimer laser, F 2 The coating film is exposed to radiation or electromagnetic waves such as excimer laser, extreme Ultraviolet (EUV), vacuum Ultraviolet (VUV), electron beam, X-ray, soft X-ray, g-ray, i-ray, and h-ray. The exposure of the coating film can be performed position-selectively through a negative mask. The exposure amount varies depending on the composition of the photosensitive composition, and is preferably 10mJ/cm 2 Above and 600mJ/cm 2 The following is left and right.
The exposed coating film is developed as needed.
The photosensitive composition is not easily dissolved excessively in an alkali developer after exposure. Therefore, by using the photosensitive composition, a patterned cured product having a good shape in which the exposed portion is a convex portion and the unexposed portion is a concave portion can be easily formed.
In the developing step, the exposed coating film is developed with a developing solution, whereby a cured product patterned in a desired shape is formed. The developing method is not particularly limited, and dipping, spraying, and the like can be used. Specific examples of the developer include organic developer such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.
Then, if necessary, the cured product after exposure or the patterned cured product after development may be subjected to post baking and further heat curing. The post-baking temperature is preferably 150 ℃ to 270 ℃.
The cured product is formed using the photosensitive composition described above. The cured product is preferably an insulating film or a protective film laminated on a photoresist film. When the photosensitive composition is transparent without containing the colorant (C), the transmittance of the cured product is usually 90% or more, preferably 93% or more, and more preferably 95% or more, as an average value of the transmittance of light rays having a wavelength in the range of 400nm to 650nm when a sample having a thickness of 3.5 μm (optical path length of 3.5 μm) is produced. As described above, the cured product is excellent In transmittance, and therefore, can be suitably used as an insulating film for a display device requiring an insulating film excellent In transparency, such as an In-cell touch panel (In-cell touch panel) type liquid crystal display device and a UHA (Ultra High Aperture) panel.
In addition, when a patterned cured film is formed by exposing the photosensitive composition to light through a halftone mask, a sufficient level difference can be formed between the full-tone exposure portion and the halftone exposure portion in the patterned cured product formed, and a sufficient level of the halftone exposure portion can be ensured. Accordingly, a cured film formed using the photosensitive composition can be suitably used as a spacer, particularly a black columnar spacer, used for a display panel such as a liquid crystal display panel.
Photosensitive adhesive and bonding method
The photosensitive composition can be suitably used as a photosensitive adhesive. When the photosensitive composition is used as a photosensitive adhesive, the photosensitive composition may or may not contain the colorant (C) for the purpose of imparting visibility and light shielding properties.
As described above, the photosensitive composition used as the photosensitive adhesive is excellent in light transmittance. Therefore, when the photosensitive composition is used as a photosensitive adhesive, exposure light is likely to reach the entire adhesive, and the adhesive is rapidly cured by exposure.
In particular, when an adhesive layer having a film thickness of 1 μm or more and 500 μm or less is formed and bonded, the photosensitive adhesive described above can be suitably used.
In particular, when welding, screwing, and other joining operations in the production of various products by industrial robots in the production of automobiles, motorcycles, bicycles, railway vehicles, airplanes, ships, various building members, and the like are changed to bonding by the photosensitive adhesive, there are various advantages as follows: the weight of the final product obtained by the bonding is reduced; the screw and the cutting of the screw caused by metal fatigue and the like when the joint based on the screw fixation and the screw fixation is carried out are avoided; corrosion caused by solidification of the battery when the dissimilar metals are combined does not occur; etc.
The bonding method using the photosensitive adhesive is not particularly limited. The photosensitive adhesive described above can be used for a method of bonding the surfaces to be bonded of various articles.
Typical bonding methods include the following steps:
forming an adhesive layer formed of a photosensitive adhesive on one or both of the opposed adherend surfaces; and
the adhesive layer is cured by exposure to light.
The method for forming the adhesive layer formed of the photosensitive adhesive is not particularly limited. Typically, the adhesive layer may be formed by applying a photosensitive adhesive to one or both of the opposed surfaces to be bonded.
The photosensitive adhesive may be injected into the gap with a gap of a desired width formed between the surfaces to be bonded.
The number of articles to be bonded may be 1 or 2 or more. When the material of the object to be bonded has flexibility and softness, the number of the object to be bonded may be 1. When the number of articles to be bonded is 1, for example, the following may be mentioned: the 1 rectangular plastic plate is rolled into a cylinder shape, and the joint portions of the plastic plates are bonded.
The exposure was performed in the same manner as the formation of the cured film described above. When the object to be bonded is transparent, the method of irradiating the adhesive layer with exposure light is not particularly limited. In this case, the exposure light may be irradiated to the adhesive layer through the object to be adhered, or may be irradiated so that the exposure light is incident from the end face of the adhesive layer.
When the object to be bonded is made of an opaque material such as metal, exposure is performed such that exposure light is incident from the end face of the adhesive layer.
Other uses
The photosensitive composition can be used for various applications such as formation of etching masks in semiconductor processing, glass processing, and the like, in which the photosensitive composition has been used conventionally.
The photosensitive composition described above can also be applied to formation of a photosensitive composition layer in a stereolithography method by so-called 3D printing, which includes a step of forming the photosensitive composition layer.
Lamination of layers cured by exposure in 3D printing is so-called self-adhesion of layers of a cured product formed using a photosensitive composition. Therefore, a stereolithography method using a photosensitive adhesive containing the photosensitive composition and based on 3D printing is also included as one embodiment in the above-described adhesion method using a photosensitive adhesive.
Since the photosensitive composition has excellent light transmittance, the photosensitive composition layer can be cured well in a short time by exposure even if the film thickness of the photosensitive composition layer is increased. Therefore, when the photosensitive composition is applied to three-dimensional modeling by 3D printing, the film thickness of the photosensitive composition layer can be increased, and thus the number of layers of the photosensitive composition and the number of exposure can be reduced, and a three-dimensional modeling object having a desired shape can be produced in a short time.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
[ example 1 and comparative examples 1 to 4 ]
3 parts by mass of a photopolymerization initiator (a), 38 parts by mass of a photopolymerizable compound (B1), and 62 parts by mass of a resin (B2) were dissolved in an organic solvent so that the solid content concentration was 24% by mass, to prepare a photosensitive composition.
As the photopolymerization initiator (A), PI-1, PI-2, and PI-3 described below were used. The light absorption characteristics of these photopolymerization initiators are shown in table 1 below. The gram absorbance of PI-3 in Table 1 is at 400 nm.
[ chemical formula 60]
TABLE 1
The types and amounts of photopolymerization initiators used in example 1 and comparative examples 1 to 4 are shown in table 2 below.
Dipentaerythritol hexaacrylate is used as the photopolymerizable compound (B1).
As the resin (B2), an acrylic resin (Mw: 10000) composed of the following structural units was used. The lower right numerical value of the bracket in the following formula is the content (mass%) of each structural unit in the resin.
[ chemical formula 61]
As the organic solvent, a mixed solvent of diethylene glycol methyl ethyl ether (megg), propylene Glycol Monomethyl Ether Acetate (PGMEA), and 3-methoxybutyl acetate (MBA) (mixing ratio (mass ratio): megg: PGMEA: mba=85:10:5) was used.
Using the photosensitive compositions of example 1 and comparative examples 1 to 4 obtained, halftone characteristics and transmittance of cured films were evaluated in the following manner. The evaluation results of the halftone characteristics are shown in table 2.
< halftone characteristic evaluation >)
The photosensitive compositions obtained in each of examples and comparative examples were applied to a glass substrate using a spin coater, and then the coating film was dried at 80 ℃ for 10 minutes to obtain a coating film having the following film thickness: when full-tone exposure is performed, a cured film having a film thickness of about 3.5 μm is formed.
Next, an exposure apparatus (manufactured by Canon, MPA600 FA) was used at 40mJ/cm 2 The coating film was exposed to an open-frame (open-frame) light through a halftone mask.
After exposure, spin-on immersion (puddle) development was performed at 23 ℃ for 60 seconds using an aqueous solution of tetramethylammonium hydroxide having a concentration of 0.5 mass% as a developer.
Post-baking was performed on the developed exposed coating film at 100℃for 100 minutes, and further at 220℃for 40 minutes, to obtain a patterned cured film.
In the post-baking, the film thickness T1 of the coating film before the post-baking and the film thickness T2 of the cured film after the post-baking were measured using a stylus surface shape measuring instrument (manufactured by ULVAC, dektak 3 st). From the measured T1 and T2, the residual film ratio (%) was calculated according to the following formula:
residual film ratio (%) =t2/t1×100
Using the calculated film residue (%), whether the film residue at the time of post baking of the halftone exposure portion was good or not was evaluated according to the following criteria.
O: the residual film rate is more than 65 percent
X: the residual film rate is less than 65 percent
In addition, a patterned cured film was obtained in the same manner as described above, except that a full tone mask (full tone mask) was used. The film thickness T3 of the patterned cured film after post baking, which was obtained by exposure using a full tone mask, was measured using a stylus surface shape measuring instrument (manufactured by ULVAC, dektak 3 st).
From the value of T2 and the value of T3, Δh (=t3—t2) which is the difference between the height of the pattern at the time of full-tone exposure and the height of the pattern at the time of halftone exposure is calculated.
From the result of the determinationThe difference between the film thickness of the cured film by full-tone exposure and the film thickness of the cured film by halftone exposure was evaluated according to the following criteria.
O: the value of DeltaH isAbove mentioned
Delta: the value of DeltaH isAbove and less than->
X: the value of delta H is less than
The halftone characteristics were evaluated from the residual film ratio and Δh values described above according to the following criteria.
O: the residual film rate is 65% or more, and the value of DeltaH isAbove mentioned
Delta: the residual film rate is 65% or more, and the value of DeltaH isAbove and less than->
X: the residual film rate is less than 65%, or the residual film rate is more than 65%, and the value of delta H is less than
The average value of light transmittance in the wavelength region of 400nm to 650nm was measured for a cured film having a thickness of 3.5 μm formed by full-tone exposure using the photosensitive composition of example 1, and as a result, the value was 95%. That is, the cured film formed using the photosensitive composition of example 1 was excellent in light transmittance.
TABLE 2
As is clear from table 2, only the photosensitive composition of example 1, which contains 2 kinds of oxime ester compounds having peaks in a wavelength region of 320nm or more and less than 400nm in an absorption spectrum as a photopolymerization initiator (a), does not contain a compound showing a gram absorbance coefficient of 10 or more at any wavelength in a wavelength region of 400nm or more as a photopolymerization initiator (a), and the maximum wavelengths of the peaks of the 2 oxime ester compounds are different from each other, shows good halftone characteristics.
[ example 2 and comparative example 5 ]
A photosensitive composition was prepared by dissolving and dispersing 5 parts by mass of a photopolymerization initiator (A), 10 parts by mass of a photopolymerizable compound (B1), 32 parts by mass of a resin (B2), 8 parts by mass of carbon black, 34 parts by mass of a perylene pigment, and 6 parts by mass of a dispersant in an organic solvent so that the solid content concentration was 25% by mass.
As photopolymerization initiator (A), the above-mentioned PI-1 and PI-2 were used. The types and amounts of photopolymerization initiators are shown in Table 3. As the photopolymerizable compound (B1), 3 parts by mass of tetraethyleneglycol dimethacrylate and 7 parts by mass of dipentaerythritol hexaacrylate were used.
As the resin (B2), cardo resin synthesized by the following method was used.
First, 235g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110mg of tetramethyl ammonium chloride, 100mg of 2, 6-di-t-butyl-4-methylphenol and 72.0g of acrylic acid were placed in a 500mL four-necked flask, and air was blown thereinto at a rate of 25 mL/min, followed by heating and dissolution at 90 to 100 ℃. Then, the temperature was gradually raised while keeping the solution cloudy, and the solution was heated to 120℃to be completely dissolved. At this time, the solution became transparent and viscous, but the stirring was continued while maintaining this state. The acid value was measured during this period, and stirring was continued with heating to an acid value of less than 1.0mgKOH/g. Until the acid value reached the target value, it took 12 hours. Then, the mixture was cooled to room temperature to obtain a colorless transparent bisphenol fluorene type epoxy acrylate represented by the following formula as a solid.
[ chemical formula 62]
Then, 600g of 3-methoxybutyl acetate was added to 307.0g of the bisphenol fluorene type epoxy acrylate obtained in the above manner, and dissolved, followed by mixing 80.5g of benzophenone tetracarboxylic dianhydride and 1g of tetraethylammonium bromide, and then gradually heating the mixture, and carrying out a reaction at 110 to 115℃for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0g of 1,2,3, 6-tetrahydrophthalic anhydride was mixed and reacted at 90℃for 6 hours to obtain Cardo resin. The disappearance of the acid anhydride group was confirmed by IR spectroscopy.
As the organic solvent, a mixed solvent of 3-methoxybutyl acetate (MBA) and Propylene Glycol Monomethyl Ether Acetate (PGMEA) (mixing ratio (mass ratio): MBA pgmea=5:95) was used.
Using the photosensitive compositions of example 2 and comparative example 5 obtained, halftone characteristics and residues after development were evaluated in the following manner. The evaluation results of the halftone characteristics are shown in table 3.
< halftone characteristic evaluation >)
The photosensitive compositions obtained in each of examples and comparative examples were applied to a glass substrate using a spin coater, and then the coating film was dried at 100 ℃ for 120 seconds to obtain a coating film having the following film thickness: when full-tone exposure is performed, a cured film having a film thickness of about 3.5 μm is formed.
Next, an exposure apparatus (manufactured by TOPCON CORPORATION, TME150 RTO) was used at 50mJ/cm 2 The coating film is subjected to open frame exposure through a halftone mask.
After exposure, an aqueous solution of potassium hydroxide having a concentration of 0.05 mass% was used as a developer, and spray development was performed at 25℃for 60 seconds.
Post-baking was performed on the developed exposed coating film at 230℃for 20 minutes to obtain a patterned cured film.
In the post-baking, the film thickness T1 of the coating film before the post-baking and the film thickness T2 of the cured film after the post-baking were measured using a stylus surface shape measuring instrument (manufactured by ULVAC, dektak 3 st). From the measured T1 and T2, the residual film ratio (%) was calculated according to the following formula:
residual film ratio (%) =t2/t1×100
Using the calculated film residue (%), whether the film residue at the time of post baking of the halftone exposure portion was good or not was evaluated according to the following criteria.
O: the residual film rate is more than 80 percent
X: the residual film rate is less than 80 percent
In addition, a patterned cured film was obtained in the same manner as described above, except that a full-tone mask was used. The film thickness T3 of the patterned cured film after post baking, which was obtained by exposure using a full tone mask, was measured using a stylus surface shape measuring instrument (manufactured by ULVAC, dektak 3 st).
From the value of T2 and the value of T3, Δh (=t3—t2) which is the difference between the height of the pattern at the time of full-tone exposure and the height of the pattern at the time of halftone exposure is calculated.
From the result of the determinationThe difference between the film thickness of the cured film by full-tone exposure and the film thickness of the cured film by halftone exposure was evaluated according to the following criteria.
O: the value of DeltaH isAbove mentioned
X: the value of delta H is less than
The halftone characteristics were evaluated from the residual film ratio and Δh values described above according to the following criteria.
O: the residual film rate is 80% or more, and the value of DeltaH isAbove mentioned
X: the residual film rate is less than 80%, or the residual film rate is more than 80%, and the value of delta H is less than
The cured film having a thickness of 3.5 μm formed by full-tone exposure using the photosensitive composition of example 2 was observed under a microscope to confirm the presence or absence of residues in the pattern, but no residues were confirmed.
TABLE 3
As is clear from table 3, also for the photosensitive composition containing the colorant (C), only the photosensitive composition of example 2, which contains 2 kinds of oxime ester compounds having peaks in a wavelength region of 320nm or more and less than 400nm in the absorption spectrum as the photopolymerization initiator (a), contains no compound showing a gram absorption coefficient of 10 or more at any wavelength in a wavelength region of 400nm or more as the photopolymerization initiator (a), and the maximum wavelengths of the peaks of the 2 kinds of oxime ester compounds are different from each other, shows good halftone characteristics.

Claims (10)

1. The use of a photosensitive composition containing a photopolymerization initiator (A) for halftone exposure through a halftone mask,
the photosensitive composition comprises 2 or more oxime ester compounds having peaks in a wavelength region of 320nm or more and less than 400nm in an absorption spectrum,
the photopolymerization initiator (A) does not contain a compound exhibiting a gram absorbance coefficient of 10 or more at any wavelength in a wavelength region of 400nm or more,
the maximum wavelengths of the peaks of 2 or more of the above oxime ester compounds are different from each other,
the photopolymerization initiator (A) comprises an oxime ester compound (A1) represented by the following formula (A1) and satisfying at least 1 condition in the following formulas (1) to (3), and an oxime ester compound (A2) represented by the following formula (A2),
[ chemical formula 1]
In the formula (a 1), R 1 Is a monovalent organic group, R 2 Is a hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent, R 3 Is a monovalent organic group, R 4 Is a monovalent organic group, R 5 And R is 6 Each independently is a benzene ring which may have a substituent, or a naphthalene ring which may have a substituent, and each of m1, m2, and m3 is 0 or 1;
(1)R 1 comprising-OR 7 A group represented by R 7 Is a halogen alkyl group, and is a halogen alkyl group,
(2) m2 is 1, R 4 comprising-OR 7 A group represented by R 7 Is a halogen alkyl group, and is a halogen alkyl group,
(3)R 3 a branched alkyl group which may have a substituent;
[ chemical formula 2]
In the formula (a 2), CR is a group represented by the following formula (a 2 a) or the following formula (a 2 b), R a4 Is phenyl which may have a substituent, or phenylthioalkyl which may have a substituent on the aromatic ring, R a5 An aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, n2 is 0 or 1,
[ chemical formula 3]
R a1 Is a hydrogen atom, a nitro group or a monovalent organic group, R a2 And R is a3 Each is a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, R a2 And R is R a3 Can be bonded to each other to form a ring, and n1 is an integer of 0 to 4 inclusive.
2. The use according to claim 1, wherein R a4 Is a group represented by the following formula (c 2-a),
in the formula (c 2-a), R a7 And R is a8 Each is an organic group, n3 is an integer of 0 to 4, R a7 And R is a8 When present at adjacent positions on the benzene ring, R a7 And R is R a8 Can be bonded to each other to form a ring.
3. The use according to claim 1, wherein the maximum wavelength on the longest wavelength side among the maximum wavelengths of the peaks of 2 or more kinds of the oxime ester compounds is denoted as lambda max-r The maximum wavelength at the shortest wavelength side is denoted as lambda max-b When the lambda is max-r With said lambda max-b The difference is 20nm or more.
4. The use according to claim 1, wherein in the formula (a 2), the CR is a group represented by the formula (a 2 a).
5. The use according to any one of claims 1 to 4, wherein the photosensitive composition comprises a polymerizable base material component (B) comprising a photopolymerizable compound (B1) or a photopolymerizable compound (B1) and a resin (B2).
6. A method of forming a cured product comprising the steps of:
a coating film formed using the photosensitive composition for use according to any one of claims 1 to 5, and
the coating film is subjected to exposure to light,
the exposure is a halftone exposure via a halftone mask.
7. The method for forming a cured product according to claim 6, comprising the steps of:
exposing the coating film positionally selectively,
the exposed coating film is developed.
8. A cured product of a photosensitive composition which has been subjected to halftone exposure through a halftone mask for use according to any one of claims 1 to 5.
9. A photosensitive adhesive comprising a photosensitive composition which is subjected to halftone exposure through a halftone mask for use according to any one of claims 1 to 5.
10. A method of bonding bonded surfaces, the method comprising the steps of:
an adhesive layer formed of the photosensitive adhesive according to claim 9 is formed on one or both of the opposed surfaces to be adhered, and
the adhesive layer is cured by exposure to light.
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