CN115509087A - Photosensitive composition - Google Patents

Photosensitive composition Download PDF

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Publication number
CN115509087A
CN115509087A CN202210701455.0A CN202210701455A CN115509087A CN 115509087 A CN115509087 A CN 115509087A CN 202210701455 A CN202210701455 A CN 202210701455A CN 115509087 A CN115509087 A CN 115509087A
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group
photosensitive composition
lens
formula
light
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佐藤梓实
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/061—Polyesters; Polycarbonates
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/12—Optical coatings produced by application to, or surface treatment of, optical elements by surface treatment, e.g. by irradiation
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G02B3/0006—Arrays
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • 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
    • G03F7/16—Coating processes; 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
    • G03F7/20—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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

The present invention relates to a photosensitive composition. The invention provides a photosensitive composition for forming a light shielding layer at the periphery of a lens, a method for manufacturing an optical element using the photosensitive composition, and an optical element, wherein the photosensitive composition can form the light shielding layer by coating the lens and exposing and developing the formed coating film in a position selective manner, and can inhibit the reduction of the transmittance of the lens at an unexposed part. The photosensitive composition comprises an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light-shielding agent (D), wherein the light-shielding agent (D) comprises an organic black pigment (D1), and the ratio of the mass of the organic black pigment (D1) to the mass of the solid component of the photosensitive composition is 5-30 mass%.

Description

Photosensitive composition
Technical Field
The present invention relates to a photosensitive composition for forming a light shielding layer around a lens, a method for manufacturing an optical element, and an optical element.
Background
Lenses are used as optical elements in optical devices such as cameras, microscopes, semiconductor exposure apparatuses, and binoculars.
In such a lens, in order to suppress flare (flare), ghost (ghost), and the like caused by reflection of incident light, the following techniques are disclosed: a technique of providing a matte film on the peripheral edge of a lens by plating and coating processes (see patent document 1); a technique of providing a light shielding layer on the peripheral edge of a lens by exposing and developing a coating film formed by coating a black colored photosensitive resin composition on the lens in a position-selective manner (see patent document 2).
Documents of the prior art
Patent literature
Patent document 1: japanese patent laid-open No. 2020-109510
Patent document 2: japanese patent laid-open publication No. 2011-107588
Disclosure of Invention
Problems to be solved by the invention
As optical devices have been miniaturized, lenses have also been miniaturized, and therefore, a finer light-shielding layer and the like have been desired. As in patent document 2, a light-shielding layer having a fine pattern shape can be provided by exposing and developing a coating film formed by coating a negative black colored photosensitive resin composition on a lens in a position-selective manner.
However, when the light shielding layer is provided by performing position-selective exposure and development on a coating film formed by coating a negative-type black colored photosensitive resin composition on a lens as in patent document 2, the following problems occur in the lens: the transmittance of the unexposed portion (i.e., the region through which incident light passes) that is not the peripheral portion of the light-shielding layer is low. Therefore, it is desirable to suppress a decrease in transmittance of the lens in the unexposed portion.
The present invention has been made in view of the above-described problems, and an object thereof is to provide a photosensitive composition for forming a light shielding layer on the periphery of a lens, which is capable of forming a light shielding layer by applying the photosensitive composition to a lens and exposing and developing the formed coating film in a position-selective manner, and which is capable of suppressing a decrease in the transmittance of the lens in an unexposed portion, a method for manufacturing an optical element using the photosensitive composition, and an optical element.
Means for solving the problems
The inventors of the present invention have found that the above problems can be solved by preparing a photosensitive composition which comprises an alkali-soluble resin (a), a photopolymerizable monomer (B), a photopolymerization initiator (C) and a light-shielding agent (D) for forming a light-shielding layer at the periphery of a lens, and in which the light-shielding agent (D) comprises an organic black pigment (D1) and the ratio of the mass of the organic black pigment (D1) to the mass of the solid components of the photosensitive composition is 5 to 30 mass%, and have completed the present invention. Specifically, the present invention provides the following means.
The invention of the 1 st mode for photosensitive composition, it is used in the lens peripheral edge formation light shield layer photosensitive composition,
the photosensitive composition comprises an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light-shading agent (D),
the light-shading agent (D) contains an organic black pigment (D1), and the ratio of the mass of the organic black pigment (D1) to the mass of the solid component of the photosensitive composition is 5-30 mass%.
A2 nd aspect of the present invention is a method for manufacturing an optical element including a lens and a light shielding layer located at a peripheral edge of the lens, the method including the steps of:
a coating film forming step of applying the photosensitive composition according to claim 1 to the lens to form a coating film;
an exposure step of exposing a position of the coating film where the light shielding layer is to be formed in a position selective manner;
a developing step of developing the exposed coating film; and
and a heat curing step of heating and curing the developed coating film.
The invention according to claim 3 is an optical element comprising a lens and a light shielding layer located at a peripheral edge of the lens,
the light-shielding layer is formed from a cured product of the photosensitive composition according to claim 1.
Effects of the invention
According to the present invention, there can be provided a photosensitive composition which can form a light shielding layer at the periphery of a lens by applying the photosensitive composition to the lens and exposing and developing the formed coating film in a position-selective manner, and can suppress a decrease in the transmittance of the lens in an unexposed portion, a method for manufacturing an optical element using the photosensitive composition, and an optical element.
Drawings
FIG. 1 is a schematic view of an optical element formed using a photosensitive composition.
FIG. 2 is a schematic cross-sectional view for explaining a method of manufacturing an optical element.
Description of the reference numerals
1. Lens and lens assembly
2. Light shielding layer
3. Position for forming light shielding layer
4. Negative mask
5. Unexposed part
10. Optical element
Detailed Description
The present invention will be described below based on preferred embodiments. In the present specification, the range represented by the term "to" is defined as a range including both numerical values and ratios.
Photosensitive composition
The photosensitive composition (black photosensitive composition) of the present invention is used for forming a light shielding layer around the periphery of a lens. The peripheral edge of the lens forming the light-shielding layer is a peripheral edge when the thickness direction of the lens (the direction in which light is incident) is the axis.
The lens may be a resin lens. Examples of the resin constituting the lens include polycarbonate, cycloolefin polymer, epoxy resin, and acrylic resin.
The thickness of the lens is not particularly limited, but is, for example, 1cm or less, preferably 100 μm or more and 2000 μm or less. Note that the thickness of the lens is the thickness of the thickest part. The diameter of the lens is not particularly limited, but is, for example, 40mm or less, preferably 1mm or more and 10mm or less, and more preferably 1mm or more and 5mm or less.
The photosensitive composition comprises an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light-shading agent (D). The light-shading agent (D) contains an organic black pigment (D1). The ratio of the mass of the organic black pigment (D1) to the mass of the solid component of the photosensitive composition is 5 mass% or more and 30 mass% or less.
By using such a photosensitive composition, an optical element 10 including a lens 1 and a light shielding layer 2 located at the periphery of the lens 1 as shown in fig. 1 can be manufactured. Fig. 1 is a schematic view of an optical element 10 formed using a photosensitive composition, in which fig. 1 (a) is a cross-sectional view and fig. 1 (b) is a plan view. The shape of the lens 1 and the light shielding layer 2 in fig. 1 is an example, and may be a shape corresponding to the desired optical element 10.
For example, by using such a photosensitive composition as a material for forming a coating film, a method including the steps of:
a step of forming a coating film by coating the lens with the coating film;
a step of exposing a position of the coating film where the light shielding layer is to be formed in a position selective manner;
a step of developing the exposed coating film; and
and a thermosetting step of heating and curing the developed coating film.
For example, the OD value (optical density) per 1 μm thickness of the light shielding layer 2 (patterned cured product) formed around the lens 1 by such a photosensitive composition is, for example, 0.2 or more, preferably 0.6 or more, more preferably 0.8 or more, and further preferably 1.0 or more. The upper limit is not particularly limited, and is, for example, 4.0 or less.
The transmittance in the thickness direction of the lens 1 in the unexposed area may be changed by less than 2% or less than 1% as determined by the following equation.
Transmittance change (%) = (T) 1 /T 0 )×100
T 0 : before applying the photosensitive compositionTransmittance of lens
T 1 : transmittance of unexposed part of lens formed with light-shielding layer
It is considered that the decrease in transmittance is caused by the generation of development residues from the light-screening agent contained in the photosensitive composition in the unexposed portion. It is presumed that the use of the organic black pigment (D1) can suppress the generation of the development residue, and as a result, suppress the decrease in transmittance.
The light-shielding layer 2 formed around the lens 1 by the photosensitive composition contains the organic black pigment (D1), and therefore has light-shielding properties. Therefore, flare, ghost, and the like caused by reflection of incident light are suppressed. In addition, since the generation of development residue in unexposed portions (i.e., regions through which incident light passes) is suppressed, it is possible to maintain a high transmittance of the lens 1 with respect to incident light (visible light). Therefore, the optical element 10 having the light shielding layer 2 formed on the periphery of the lens 1 can be preferably used for optical devices such as cameras, microscopes, and semiconductor exposure apparatuses.
On the other hand, when the photosensitive composition does not contain the organic black pigment (D1), or when the ratio of the mass of the organic black pigment (D1) to the mass of the solid components of the photosensitive composition is out of the range of 5 mass% to 30 mass%, it is difficult to simultaneously form the light-shielding layer and suppress the decrease in transmittance of the lens in the unexposed portion.
Hereinafter, essential components or optional components of the photosensitive composition will be described.
< alkali-soluble resin (A) >)
The photosensitive composition contains an alkali-soluble resin (a) (hereinafter, also referred to as a component (a)). The photosensitive composition can be imparted with alkali developability by blending an alkali-soluble resin (a) with the photosensitive composition.
Here, the alkali-soluble resin in the present specification means a resin having a functional group (for example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, or the like) in the molecule to make it alkali-soluble.
The alkali-soluble resin (a) preferably contains a resin having a photopolymerizable group such as an ethylenically unsaturated double bond in the molecule. In this case, when a cured product (light shielding layer) is formed using the photosensitive composition, crosslinking occurs between the alkali-soluble resin (a) and the photopolymerizable monomer (B). Therefore, even if the baking temperature at the time of forming a cured product is low, for example, 120 ℃ or lower, further 100 ℃ or lower, or 95 ℃ or lower, a cured product having high solvent resistance is easily formed.
Typical examples of the photopolymerizable group include functional groups having an unsaturated double bond such as a vinyl group, an allyl group, and a (meth) acryloyl group.
The alkali-soluble resin (A) preferably contains a resin (a-1) having a Cardo structure in the molecule. The Cardo structure will be described in detail later.
When a resin having a Cardo structure in a molecule is used, a photosensitive composition having excellent resolution can be easily obtained, and a cured product having good adhesion to a lens can be easily formed using the photosensitive composition.
[ resin (a-1) having Cardo Structure ]
As the resin (a-1) having a Cardo structure (hereinafter also referred to as Cardo resin (a-1)), a resin having a Cardo structure in a molecule and having a predetermined alkali solubility can be used. The Cardo structure is a skeleton in which the 2 nd and 3 rd cyclic structures are bonded to 1 ring carbon atom constituting the 1 st cyclic structure. The 2 nd cyclic structure and the 3 rd cyclic structure may be the same or different.
As a typical example of the Cardo structure, a skeleton in which 2 aromatic rings (for example, benzene rings) are bonded to the carbon atom at the 9-position of the fluorene ring is given.
The Cardo resin (a-1) is not particularly limited, and conventionally known resins can be used. Among them, a resin represented by the following formula (a-1) is preferable. As shown in the following formula (a-2), the resin represented by the following formula (a-1) has a (meth) acryloyl group in the molecule. Therefore, the resin represented by the following formula (a-1) belongs to a resin containing a photopolymerizable group in the molecule.
[ chemical formula 1]
Figure BDA0003703480590000061
In the formula (a-1), X a Represents a group represented by the following formula (a-2). m1 represents an integer of 0 to 20 inclusive.
[ chemical formula 2]
Figure BDA0003703480590000071
In the above formula (a-2), R a1 Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R a2 Each independently represents a hydrogen atom or a methyl group, R a3 Each independently represents a linear or branched alkylene group, m2 represents 0 or 1 a Represents a group represented by the following formula (a-3).
[ chemical formula 3]
Figure BDA0003703480590000072
In the formula (a-2), as R a3 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, a propane-1, 2-diyl group, and a propane-1, 3-diyl group.
The ring A in the formula (a-3) represents an aliphatic ring which may be fused with an aromatic ring or may have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring.
Examples of the alicyclic ring include monocycloalkane, bicycloalkane, tricycloalkane and tetracycloalkane.
Specific examples thereof include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane.
The aromatic ring which may be condensed with the aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and is preferably an aromatic hydrocarbon ring. Specifically, benzene ring and naphthalene ring are preferable.
Preferred examples of the 2-valent group represented by the formula (a-3) include the following groups.
[ chemical formula 4]
Figure BDA0003703480590000081
The 2-valent group X in the formula (a-1) a By providing a residue Z a The tetracarboxylic dianhydride (b) is introduced into the Cardo resin (a-1) by reacting with a diol compound represented by the following formula (a-2 a).
[ chemical formula 5]
Figure BDA0003703480590000082
In the formula (a-2 a), R a1 、R a2 、R a3 And m2 is as described for formula (a-2). The ring A in the formula (a-2 a) is as described for the formula (a-3).
The diol compound represented by the formula (a-2 a) can be produced, for example, by the following method.
First, if necessary, the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2 b) is replaced with-R a3 A group represented by-OH, followed by glycidylation using epichlorohydrin or the like to obtain an epoxy compound represented by the following formula (a-2 c).
Subsequently, the epoxy compound represented by the formula (a-2 c) is reacted with acrylic acid or methacrylic acid to obtain a diol compound represented by the formula (a-2 a).
In the formulae (a-2 b) and (a-2 c), R a1 、R a3 And m2 is as described for formula (a-2). The ring A in the formulae (a-2 b) and (a-2 c) is as described for the formula (a-3).
The method for producing the diol compound represented by the formula (a-2 a) is not limited to the above-described method.
[ chemical formula 6]
Figure BDA0003703480590000091
Preferable examples of the diol compound represented by the formula (a-2 b) include the following diol compounds.
[ chemical formula 7]
Figure BDA0003703480590000092
In the above formula (a-1), R a0 Is a hydrogen atom or-CO-Y a -COOH, or a group represented by the formula. Here, Y a The residue is obtained by removing an acid anhydride group (-CO-O-CO-) from a dicarboxylic anhydride. Examples of the dicarboxylic anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, and the like.
In the above formula (a-1), Z a The residue is obtained by removing 2 acid anhydride groups from a tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include tetracarboxylic dianhydrides represented by the following formula (a-4), pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, and the like.
In the formula (a-1), m1 represents an integer of 0 to 20 inclusive.
[ chemical formula 8]
Figure BDA0003703480590000101
(in the formula (a-4), R a4 、R a5 And R a6 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 m3 represents an integer of 0 to 12. )
Can be selected as R in the formula (a-4) a4 The alkyl group of (2) is an alkyl group having 1 to 10 carbon atoms. By setting the number of carbon atoms of the alkyl group within this range, the heat resistance of the obtained carboxylic ester can be further improved. R a4 In the case of an alkyl group, the number of carbon atoms is preferably 1 to 6, more preferably 1 to 5, even more preferably 1 to 4, and particularly preferably 1 to 3, from the viewpoint of easily obtaining a Cardo resin having excellent heat resistance.
R a4 In the case of an alkyl group, the alkyl group may be linear or branched.
As R in the formula (a-4) a4 Each of these groups is more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, independently, from the viewpoint of facilitating the production of a Cardo resin having excellent heat resistance. R in the formula (a-4) a4 More preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and particularly preferably a hydrogen atom or a methyl group.
The plurality of R in the formula (a-4) is preferred in view of easy preparation of a tetracarboxylic dianhydride with high purity a4 Preferably the same groups.
M3 in the formula (a-4) represents an integer of 0 to 12 inclusive. When the value of m3 is 12 or less, the tetracarboxylic dianhydride can be easily purified.
The upper limit of m3 is preferably 5, more preferably 3, from the viewpoint of ease of purification of the tetracarboxylic dianhydride.
From the viewpoint of chemical stability of the tetracarboxylic dianhydride, the lower limit of m3 is preferably 1, and more preferably 2.
M3 in formula (a-4) is particularly preferably 2 or 3.
Can be selected as R in the formula (a-4) a5 And R a6 And an alkyl group having 1 to 10 carbon atoms and optionally R a4 The same applies to the alkyl group having 1 to 10 carbon atoms.
R is easy to purify the tetracarboxylic dianhydride a5 And R a6 Preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (preferably 1 to 6, more preferably 1 to 5, further 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 (a-4) include norbornane-2-spiro- α -cyclopentanone- α '-spiro-2 ″ -norbornane-5, 5 ″,6 ″ -tetracarboxylic dianhydride (the alias "norbornane-2-spiro-2' -cyclopentanone-5 '-spiro-2 ″ -norbornane-5, 5 ″,6 ″ -tetracarboxylic dianhydride"), methylnorbornane-2-spiro- α -cyclopentanone- α' -spiro-2 ″ - (methylnorbornane) -5,5 ″,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro- α -cyclohexanone- α '-spiro-2 ″ -norbornane-5, 5 ″,5",6,6" -tetracarboxylic dianhydride (the alias "norbornane-2-spiro-2' -cyclohexanone-6 '-spiro-2" -norbornane-5, 5", 6" -tetracarboxylic dianhydride "), methylnorbornane-2-spiro- α -cyclohexanone- α' -spiro-2" - (methylnorbornane) -5,5", 6" -tetracarboxylic dianhydride, norbornane-2-spiro- α -cyclopropanone- α '-spiro-2 "-norbornane-5, 5",6 "-tetracarboxylic dianhydride, norbornane-2-spiro- α -cyclobutanone- α' -spiro-2" -norbornane-5, 5", <xnotran> 6,6"- , -2- - α - - α ' - -2" - -5,5",6,6" - , -2- - α - - α ' - -2"- -5,5",6,6"- , -2- - α - - α ' - -2" - -5,5",6,6" - , -2- - α - - α ' - -2"- -5,5",6,6"- , -2- - α - - α ' - -2" - -5,5",6,6" - , -2- - α - - α ' - -2"- -5,5",6,6"- , -2- - α - - α ' - -2" - -5,5",6,6" - , -2- - α - - α ' - -2"- -5,5",6,6"- , -2- - α - - α ' - -2" - </xnotran> 5,5', 6' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha- (methylcyclopentanone) -alpha '-spiro-2' -norbornane-5, 5', 6, 6' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha- (methylcyclohexanone) -alpha '-spiro-2' -norbornane-5, 5', 6' -tetracarboxylic dianhydride, and the like.
The alkali-soluble resin (a) may also contain an alkali-soluble resin other than the resin (a-1) having a Cardo structure.
The content of the resin (a-1) having a Cardo structure in the alkali-soluble resin (a) is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more.
The mass average molecular weight of the alkali-soluble resin (a) is preferably 10000 or less, more preferably 4000, and further preferably 2500 or less. When the mass average molecular weight of the alkali-soluble resin (a) is 2500 or less, the decrease in the transmittance of the lens in the unexposed portion can be further suppressed. The lower limit of the mass average molecular weight of the alkali-soluble resin (a) is preferably 1000 or more, more preferably 1500 or more, and further preferably 2000 or more.
In the present specification, the mass average molecular weight Mw is a measured value in terms of polystyrene by Gel Permeation Chromatography (GPC).
The content of the alkali-soluble resin (a) in the entire solid content of the photosensitive composition is preferably 5 mass% or more and 75 mass% or less, more preferably 10 mass% or more and 71 mass% or less, and still more preferably 15 mass% or more and 65 mass% or less. If the content of the alkali-soluble resin (a) in the entire solid components of the photosensitive composition is within the above range, the solid components of the photosensitive composition are well dissolved in the developer in the unexposed portion, whereas the solid components of the cured photosensitive composition are not easily dissolved in the developer in the exposed portion, and the photosensitive composition having excellent developability and resolution is easily obtained.
In the present specification, the solid component is a component other than the organic solvent (S).
< photopolymerizable monomer (B) >)
The photosensitive composition contains a photopolymerizable monomer (B). The photopolymerizable monomer (B) is preferably a compound having an ethylenically unsaturated group. The compound having an ethylenically unsaturated group includes a monofunctional compound and a polyfunctional compound.
As the monofunctional compound, there may be mentioned, there may be mentioned (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-butylacrylamide 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, dimethylaminoethyl (meth) acrylate, glycerol (meth) acrylate, 2-trifluoroethyl (meth) acrylate, 2-trifluoromethyl (2-2, 2, 3-tetrafluoropropyl (meth) acrylate, a half ester of (meth) acrylate of a phthalic acid derivative, and the like. These monofunctional compounds may be used alone or in combination of 2 or more.
On the other hand, examples of the polyfunctional compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethyleneglycol di (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, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2-bis (4- (meth) acryloyloxypolyethoxy phenyl) propane, (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, glycerol polyglycidyl ether poly (meth) acrylate, glycerol tri (meth) acrylate, urethane (meth) acrylate, i.e., a reactant of 2-hydroxyethyl (meth) acrylate such as tolylene diisocyanate, trimethylhexamethylene diisocyanate, or hexamethylene diisocyanate), a polyfunctional compound such as methylenebis (meth) acrylamide, (meth) acrylamidomethylene ether, or a condensate of a polyol and N-methylol (meth) acrylamide, 1,3, 5-triacryloylhexahydro-1, 3, 5-triazine (triacrylformal), and the like. These polyfunctional compounds may be used alone or in combination of 2 or more.
In the polyfunctional compound, the photopolymerizable monomer (B) preferably contains a polyfunctional (meth) acrylate having a hydroxyl group. By including a polyfunctional (meth) acrylate having a hydroxyl group in the photosensitive composition, the generation of development residue can be further suppressed, and the decrease in transmittance can be further suppressed. In addition, although development residue is likely to be generated when the content of the light-shielding agent (D) is large, the generation of development residue can be very suppressed by including a polyfunctional (meth) acrylate having a hydroxyl group in the photosensitive composition, even when the content of the light-shielding agent (D) in the entire solid components of the photosensitive composition is 25 mass% or more, for example. This enables a light-shielding layer having a higher OD value of, for example, 0.8 or more, particularly 1.0 or more, to be formed satisfactorily.
The polyfunctional (meth) acrylate having a hydroxyl group may be a compound having 1 or more hydroxyl groups and 2 or more (meth) acryloyl groups in the molecule, and conventionally known compounds can be used. The number of (meth) acryloyl groups in the molecule is preferably 6 or less.
The polyfunctional (meth) acrylate having a hydroxyl group may be used alone or in combination of 2 or more.
Examples of the hydroxyl group-containing polyfunctional (meth) acrylate include a hydroxyl group-containing glycerol poly (meth) acrylate, a hydroxyl group-containing polyglycerol poly (meth) acrylate, a hydroxyl group-containing pentaerythritol poly (meth) acrylate, a hydroxyl group-containing trimethylolpropane poly (meth) acrylate, and the like.
Examples of the hydroxyl group-containing glycerol poly (meth) acrylate include glycerol di (meth) acrylate, glycerol mono (meth) acrylate, and glycerol di (meth) acrylate.
Examples of the hydroxyl group-containing polyglycerol poly (meth) acrylate include diglycerol di (meth) acrylate, diglycerol tri (meth) acrylate, triglycerol di (meth) acrylate, triglycerol tri (meth) acrylate, and triglycerol tetra (meth) acrylate.
Examples of the hydroxyl group-containing pentaerythritol poly (meth) acrylate include pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, and pentaerythritol tri (meth) acrylate.
Examples of the hydroxyl group-containing polypentaerythritol poly (meth) acrylate include dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol di (meth) acrylate, tripentaerythritol tri (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, and tripentaerythritol hepta (meth) acrylate.
Examples of the hydroxyl group-containing trimethylolpropane poly (meth) acrylate include trimethylolpropane di (meth) acrylate and the like.
Examples of the hydroxyl group-containing polytrimethylolpropane poly (meth) acrylate include ditrimethylolpropane di (meth) acrylate, ditrimethylolpropane tri (meth) acrylate and the like.
The photopolymerizable monomer (B) may include a polyfunctional (meth) acrylate having no hydroxyl group and a polyfunctional (meth) acrylate having a hydroxyl group.
In the present specification, "(meth) acrylate" means both "acrylate" and "methacrylate", "meth) acrylic-" means both "acrylic-" and "methacrylic-", "(meth) acryloyl" means both "acryloyl" and "methacryloyl", and "(meth) acryloyloxy" means both "acryloyloxy" and "methacryloyloxy".
The content of the photopolymerizable monomer (B) in the entire solid content of the photosensitive composition is preferably 1 mass% or more and 30 mass% or less, and more preferably 5 mass% or more and 20 mass% or less.
< photopolymerization initiator (C) >
The photopolymerization initiator (C) is not particularly limited, and conventionally known photopolymerization initiators can be used.
Examples of the photopolymerization initiator (C) include oxime ester compounds.
The oxime ester compound is preferably a compound having a partial structure represented by the following formula (c 1).
[ chemical formula 9]
Figure BDA0003703480590000161
(in the formula (c 1),
n1 is 0 or 1, and n is a linear alkyl group,
R c2 is a monovalent organic group, and is a monovalent organic group,
R c3 is a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted aryl group,
is a chemical bond. )
The compound having a partial structure represented by the formula (c 1) preferably has a carbazole skeleton, a fluorene skeleton, a diphenyl ether skeleton, or a phenylene sulfide skeleton.
The compound having a partial structure represented by the formula (c 1) preferably has 1 or 2 partial structures represented by the formula (c 1).
Examples of the compound having a partial structure represented by the formula (c 1) include compounds represented by the following formula (c 2).
[ chemical formula 10]
Figure BDA0003703480590000162
(in the formula (c 2), R c1 Is a group represented by the following formula (c 3), (c 4) or (c 5),
n1 is 0 or 1, and n is a linear alkyl group,
R c2 is a monovalent organic group, and is a monovalent organic group,
R c3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. )
[ chemical formula 11]
Figure BDA0003703480590000171
(in the formula (c 3), R c4 And R c5 Each independently is a 1-valent organic group,
n2 is an integer of 0 to 3 inclusive,
when n2 is 2 or 3, a plurality of R c5 A plurality of R's, which may be the same or different, are c5 May be bonded to each other to form a ring.
Is a chemical bond. )
[ chemical formula 12]
Figure BDA0003703480590000172
(in the formula (c 4), R c6 And R c7 Each independently 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 c6 and R c7 May be bonded to each other to form a ring,
R c7 and benzene rings in the fluorene skeleton may be bonded to each other to form a ring,
R c8 is a nitro group or a 1-valent organic group,
n3 is an integer of 0 to 4 inclusive,
it is a chemical bond. )
[ chemical formula 13]
Figure BDA0003703480590000181
(in the formula (c 5), R c9 Is a 1-valent organic group, a halogen atom, a nitro group or a cyano group,
a is S or O, and the content of A is,
n4 is an integer of 0 to 4 inclusive,
is a chemical bond. )
In the formula (c 3), R c4 Is a 1-valent organic group. R c4 May be selected from various organic groups within a range not interfering with the object of the present invention. The organic group is preferably a group containing a carbon atom, and more preferably a group containing 1 or more carbon atoms and 1 or more atoms selected from the group consisting of H, O, S, se, N, B, P, si, and a halogen atom. The number of carbon atoms of the group containing a carbon atom is not particularly limited, but is preferably 1 to 50, and more preferably 1 to 20.
As R c4 Preferable examples of (3) include an alkyl group which may have a substituent(s) having 1 to 20 carbon atoms, a cycloalkyl group which may have a substituent(s) having 3 to 20 carbon atoms, a saturated aliphatic acyl group which may have a substituent(s) having 2 to 20 carbon atoms, an alkoxycarbonyl group which may have a substituent(s) having 2 to 20 carbon atoms, a phenyl group which may have a substituent(s), a benzoyl group which may have a substituent(s), a phenoxycarbonyl group which may have a substituent(s), a phenylalkyl group which may have a substituent(s) having 7 to 20 carbon atoms, a naphthyl group which may have a substituent(s), a naphthoyl group which may have a substituent(s), a naphthyloxycarbonyl group which may have a substituent(s), a naphthylalkyl group which may have a substituent(s) having 11 to 20 carbon atoms, a heterocyclic group which may have a substituent(s), a heterocyclic carbonyl group which may have a substituent(s), and the like.
R c4 Of these, preferred isAn alkyl group having 1 to 20 carbon atoms. The alkyl group may be linear or branched. R is a compound represented by the formula (c 3) in view of its good solubility in the photosensitive composition c4 The number of carbon atoms of the alkyl group (2) 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 (c 3) in the photosensitive composition, because the compatibility with other components is good c4 The number of carbon atoms of the alkyl group (2) is preferably 15 or less, more preferably 10 or less.
R c4 When the compound has a substituent, preferable examples of the substituent include a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aliphatic acyl group having 2 to 20 carbon atoms, an aliphatic acyloxy group having 2 to 20 carbon atoms, a phenoxy group, a benzoyl group, a benzoyloxy group, -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.
R c4 In the case of a heterocyclic group, the heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. R c4 In the case of the heterocyclic group, the heterocyclic group is a 5-or 6-membered monocyclic ring containing 1 or more of N, S and O, or a heterocyclic group in which the monocyclic rings are fused with each other or with a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is 3 or less. Examples of the heterocyclic ring 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 c4 In the case of a heterocyclic group, examples of the substituent which the heterocyclic group may have include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, and a nitro groupAnd the like.
R as described above c4 Specific preferred examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, pentane-3-yl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and 2-ethylhexyl group.
In addition, from the viewpoint of good solubility of the compound represented by the formula (c 3) in the photosensitive composition, n-octyl group and 2-ethylhexyl group are preferable, and 2-ethylhexyl group is more preferable.
In the formula (c 3), R c5 Is a 1-valent organic group. R c5 May be selected from various organic groups within a range not interfering with the object of the present invention. The organic group is preferably a group containing a carbon atom, and more preferably a group containing 1 or more carbon atoms and 1 or more atoms selected from the group consisting of H, O, S, se, N, B, P, si, and a halogen atom. The number of carbon atoms of the group containing a carbon atom is not particularly limited, but is preferably 1 to 50, and more preferably 1 to 20.
With respect to as R c5 Examples of the preferable 1-valent organic group 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 naphthyloxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthyloxycarbonyl 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 by 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, a cyano group, a group containing HX 2 C-or H 2 And a substituent of a group represented by XC- (wherein X is each independently a halogen atom), and the like.
R c5 Is an alkaneIn the case of the alkyl group, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 6. In addition, R c5 In the case of an alkyl group, the alkyl group may be linear or branched. As R c5 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 groups. In addition, R c5 In the case of an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.
R c5 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 c5 When the alkoxy group is used, the alkoxy group may be linear or branched. As R c5 Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, an n-pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, a tert-pentyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an isooctyloxy group, a sec-octyloxy group, a tert-octyloxy group, an n-nonyloxy group, an isononyloxy group, an n-decyloxy group, and an isodecyloxy group. In addition, R c5 In the case of an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxyethoxy, and methoxypropyloxy groups.
R c5 In the case of a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 to 10, more preferably 3 to 6. As R c5 Is a cycloalkaneSpecific examples of the group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. As R c5 Specific examples of the cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.
R c5 In the case of a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, more preferably 2 to 7. As R c5 Specific examples of the saturated aliphatic acyl group include acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentanoyl, 2-dimethylpropanoyl, 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 c5 Specific examples of the saturated aliphatic acyloxy group include an acetyloxy group, a propionyloxy group, an n-butyryloxy group, a 2-methylpropionyloxy group, an n-pentanoyloxy group, a2, 2-dimethylpropionyloxy group, an n-hexanoyloxy group, an n-heptanoyloxy group, an n-octanoyloxy group, an n-nonanoyloxy group, an n-decanoyloxy group, an n-undecanoyloxy group, an n-dodecanoyloxy group, an n-tridecanoyloxy group, an n-tetradecanoyloxy group, an n-pentadecanoyloxy group, and an n-hexadecanoyloxy group.
R c5 In the case of an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 20, more preferably 2 to 7. As R c5 Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, a sec-butyloxycarbonyl group, a tert-butyloxycarbonyl group, an n-pentyloxycarbonyl group, an isopentyloxycarbonyl group, a sec-pentyloxycarbonyl group, a tert-pentyloxycarbonyl group, an n-hexyloxycarbonyl group, an n-heptyloxycarbonyl group, an n-octyloxycarbonyl group, an isooctyloxycarbonyl group, a sec-octyloxycarbonyl groupAlkylcarbonyl, tert-octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, isodecyloxycarbonyl and the like.
R c5 In the case of a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 to 20, more preferably 7 to 10. In addition, R c5 In the case of a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 to 20, more preferably 11 to 14. As R c5 Specific examples of phenylalkyl groups include benzyl, 2-phenylethyl, 3-phenylpropyl and 4-phenylbutyl. As R c5 Specific examples of the naphthylalkyl group include α -naphthylmethyl group, β -naphthylmethyl group, 2- (. Alpha. -naphthyl) ethyl group, and 2- (. Beta. -naphthyl) ethyl group. R is c5 In the case of phenylalkyl or naphthylalkyl, R c5 May further have a substituent on the phenyl group or the naphthyl group.
R c5 In the case of a heterocyclic group, the heterocyclic group is bonded to R in the formula (c 3) c4 In the case of a heterocyclic group, the heterocyclic group may further have a substituent.
R c5 In the case of heterocyclylcarbonyl, the heterocyclyl group contained in the heterocyclylcarbonyl and R c5 The same applies to heterocyclic groups.
R c5 In the case of an amino group substituted with 1 or 2 organic groups, preferable examples of the organic group 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 which may have a substituent, 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 which may have a substituent, a heterocyclic group and the like. Specific examples of these preferred organic groups and R c5 The same is true. Specific examples of the amino group substituted with 1 or 2 organic groups include a methylamino group, an ethylamino group, a diethylamino group, an n-propylamino group, a di-n-propylamino group, an isopropylamino group, an n-butylamino group, a di-n-butylamino group, an n-pentylamino groupPhenylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, phenylamino, naphthylamino, acetylamino, propionylamino, n-butyrylamino, n-valerylamino, n-hexanoylamino, n-heptanoylamino, n-octanoylamino, n-decanoylamino, benzoylamino, alpha-naphthoylamino, beta-naphthoylamino and the like.
As R c5 The substituent in the case where the phenyl group, naphthyl group and heterocyclic group contained in (1) further have a substituent includes HX 2 C-or H 2 Substituent of group represented by XC- (e.g., containing HX) 2 C-or H 2 Haloalkoxy of the group represented by XC-, comprising HX 2 C-or H 2 XC-) 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, a morpholin-1-yl group, a piperazin-1-yl group, a benzoyl group, a halogen, a nitro group, a cyano group, or the like. R c5 When the phenyl group, naphthyl group and heterocyclic group contained in (1) further have a substituent, the number of the substituent is not limited within the range not interfering with the object of the present invention, and is preferably 1 to 4. R c5 When the phenyl group, naphthyl group and heterocyclic group included in (1) have a plurality of substituents, the plurality of substituents may be the same or different.
As R c5 The substituent in the case where the benzoyl group contained in (1) further has a substituent includes an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a 2-thenoyl (thien-2-ylcarbonyl) group, a furan-3-ylcarbonyl group, a phenyl group and the like.
Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom and the like, and a fluorine atom is preferable.
As containing HX 2 C-or H 2 Group represented by XC-As the substituent(s) of (3), there may be mentioned those containing HX 2 C-or H 2 Haloalkoxy of a group represented by XC-, having a structure comprising HX 2 C-or H 2 Group of haloalkoxy groups of the group represented by XC-, comprising HX 2 C-or H 2 Haloalkyl group of group represented by XC-, having a structure containing HX 2 C-or H 2 A haloalkyl group of the group represented by XC-, etc., more preferably HX 2 C-or H 2 Haloalkoxy of a group represented by XC-, or having a structure containing HX 2 C-or H 2 A group of haloalkoxy groups of the group represented by XC-.
As having HX contained 2 C-or H 2 Examples of the haloalkyl group of the group represented by XC-include HX 2 C-or H 2 An aromatic group substituted with a haloalkyl group of the group represented by XC- (e.g., phenyl, naphthyl, etc.), containing HX 2 C-or H 2 Cycloalkyl substituted with haloalkyl of the group represented by XC- (e.g., cyclopentyl, cyclohexyl, etc.), etc., preferably by inclusion of HX 2 C-or H 2 A haloalkyl-substituted aromatic radical of the group represented by XC-.
As having HX contained 2 C-or H 2 Examples of the group of haloalkoxy of the group represented by XC-include those containing HX 2 C-or H 2 Haloalkoxy-substituted aromatic group of group represented by XC- (e.g., phenyl, naphthyl, etc.), substituted with a halogen atom containing HX 2 C-or H 2 Alkyl substituted with haloalkoxy of the group represented by XC- (e.g., methyl, ethyl, n-propyl, isopropyl, etc.), by inclusion of HX 2 C-or H 2 A cycloalkyl group substituted with a haloalkoxy group of the group represented by XC- (e.g., cyclopentyl, cyclohexyl, etc.), etc., preferably a cycloalkyl group substituted with a haloalkoxy group of the group represented by XC-, and the like, preferably contains HX 2 C-or H 2 A haloalkoxy-substituted aromatic group of the group represented by XC-.
In addition, as R c5 Cycloalkylalkyl, phenoxyalkyl which may have a substituent on the aromatic ring, phenylthioalkyl which may have a substituent on the aromatic ring are also preferable. Phenoxyalkyl group, and phenylthioalkyl group-optionally-substituted group and R c5 The phenyl group contained in (A) may haveThe same applies to the substituents.
In the 1-valent organic radical, as R c5 Preferably, the alkyl group, the cycloalkyl group, the phenyl group which may have a substituent, or the cycloalkylalkyl group, the phenylthioalkyl group which may have a substituent on the aromatic ring are used. 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 the phenyl groups which may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, 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 to 8, more preferably 1 to 4, and particularly preferably 2. Among the phenylsulfanylalkyl groups which may have a substituent on the aromatic ring, 2- (4-chlorophenylthio) ethyl is preferable.
In the group represented by the formula (c 3), R c5 There are a plurality of, a plurality of R c5 When the ring is bonded to each other to form a ring, examples of the ring to be formed include a hydrocarbon ring and a heterocyclic ring. Examples of the hetero atom contained in the hetero ring include N, O, and S. As a plurality of R c5 The rings formed by bonding to each other are particularly preferably aromatic rings. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The aromatic ring is preferably an aromatic hydrocarbon ring. A plurality of R in the following formula (c 3) c5 Specific examples of the case where benzene rings are formed by bonding to each other.
[ chemical formula 14]
Figure BDA0003703480590000251
In the group represented by the formula (c 4), R c8 Is nitro or a 1-valent organic group. R c8 Condensed in formula (c 4)Bonded on the ring to- (CO) n1 The group represented by (A) is bonded to a 6-membered aromatic ring different from the aromatic ring to which the group represented by (B) is bonded. In the formula (c 4), R c8 The bonding position (2) is not particularly limited. The group represented by the formula (c 4) has 1 or more R c8 In the case (2), from the viewpoint of ease of synthesis of the compound represented by the formula (c 4), it is preferable that R is 1 or more c8 1 in (2) is bonded to the position of 7-position of the fluorene skeleton. That is, the group represented by the formula (c 4) has 1 or more R c8 In the case of (b), the group represented by the formula (c 4) is preferably represented by the following formula (c 6). R c8 In the case of plural, plural R c8 May be the same or different.
[ chemical formula 15]
Figure BDA0003703480590000252
(in the formula (c 6), R c6 、R c7 、R c8 N3 is independently the same as R in the formula (c 4) c6 、R c7 、R c8 And n3 are the same. )
R c8 In the case of a 1-valent organic radical, R c8 The present invention is not particularly limited insofar as it does not interfere with the object of the present invention. The organic group is preferably a group containing carbon atoms, and more preferably a group containing 1 or more carbon atoms and 1 or more atoms selected from the group consisting of H, O, S, se, N, B, P, si, and halogen atoms. The number of carbon atoms of the group containing a carbon atom is not particularly limited, but is preferably 1 to 50, and more preferably 1 to 20.
As R c8 Preferred examples of the 1-valent organic group include c5 The same groups are preferred as the 1-valent organic group in (1).
In the formula (c 4), R c6 And R c7 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 c6 And R c7 May be bonded to each other to form a ring. Of these groups, as R c6 And R c7 Preferably, the alkyl group is a chain alkyl group which may have a substituent. R c6 And R c7 When the alkyl group is a linear alkyl group which may have a substituent, the linear alkyl group may be a linear alkyl group or a branched alkyl group.
R c6 And R c7 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, and particularly preferably 1 to 6. As R c6 And R c7 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 groups. In addition, R c6 And R c7 In the case of an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.
R c6 And R c7 In the case of a chain alkyl group having a substituent, the number of carbon atoms in the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably straight.
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. Preferred examples of the substituent include an alkoxy group, a cyano group, a halogen atom, a haloalkyl group, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, fluorine atom, chlorine atom and bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclic group. As specific examples of cycloalkyl, with R c8 The same applies to the preferred case of cycloalkyl. As the aromatic hydrocarbon groupSpecific examples thereof include phenyl, naphthyl, biphenyl, anthryl, phenanthryl and the like. As specific examples of heterocyclic groups, with R c8 The same applies to the preferred examples in the case of heterocyclic groups. R c8 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 contained 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 preferable substituents varies depending on the number of carbon atoms of the chain alkyl group. Typically, the number of substituents is 1 to 20, preferably 1 to 10, more preferably 1 to 6.
R c6 And R c7 In the case of a chain alkoxy group having no substituent, the number of carbon atoms of the chain alkoxy group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. As R c6 And R c7 Specific examples of the chain alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. In addition, R c6 And R c7 In the case of an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxyethoxy, and methoxypropyloxy groups.
R c6 And R c7 In the case of a chain alkoxy group having a substituent, the substituent which the alkoxy group may have and R c6 And R c7 The same applies to the case of a chain alkyl group.
R c6 And R c7 In the case of a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group. R c6 And R c7 In the case of a cyclic organic group, the substituent which the cyclic organic group may have and R c6 And R c7 The same applies to the case of a chain alkyl group.
R c6 And R c7 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 via a carbon-carbon bond, or a group in which a plurality of benzene rings are condensed. 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 benzene rings included in the aromatic hydrocarbon group is not particularly limited, but is preferably 3 or less, more preferably 2 or less, and particularly preferably 1. Preferred specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, and the like.
R c6 And R c7 In the case of an alicyclic cyclic hydrocarbon group, the alicyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 to 20, and more preferably 3 to 10. Examples of the monocyclic cyclic hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, tetracyclododecyl (tetracyclodocecyl), adamantyl, and the like.
R c6 And R c7 In the case of a heterocyclic group, R in the formula (c 3) is preferably a group c5 The heterocyclic group of (3) is the same as the above group.
R c6 And R c7 May be bonded to each other to form a ring. Comprising R c6 And R c7 The radical of the ring formed is preferably a cycloalkylidene group. R c6 And R c7 When the cyclic alkylidene group is formed by bonding, the ring constituting the cyclic alkylidene group is preferably a 5-to 6-membered ring, more preferably a 5-membered ring.
R c7 When a ring is formed with the benzene ring of the fluorene skeleton, the ring may be an aromatic ring or an aliphatic ring.
R c6 And R c7 When the group to which the bond is formed is a cycloalkylidene group, the cycloalkylidene group may be fused with 1 or more other rings. Examples of the ring which may be condensed with a cycloalkylidene 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, a pyrimidine ring and the like.
R in the above description c6 And R c7 Among them, preferred examples of the group include groups represented by the formula-A1-A2. In the formula, the following may be mentioned: a1 is a straight-chain alkylene group, and A2 is an alkoxy group, a cyano group, a halogen atom, a haloalkyl group, a cyclic organic group, or an alkoxycarbonyl group.
The number of carbon atoms of the linear alkylene group of A1 is preferably 1 to 10, more preferably 1 to 6. When A2 is an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. The carbon number of the alkoxy group is preferably 1 to 10, more preferably 1 to 6. When A2 is a halogen atom, it is preferably a fluorine atom, chlorine atom, bromine atom or iodine atom, and more preferably a fluorine atom, chlorine atom or bromine atom. When A2 is 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, and more preferably a fluorine atom, a chlorine atom, or a bromine atom. The haloalkyl group may be linear or branched, and is preferably linear. When A2 is a cyclic organic group, examples of the cyclic organic group are the same as R c6 And R c7 The same applies to the cyclic organic group contained as a substituent. In the case where A2 is alkoxycarbonyl, examples of alkoxycarbonyl are given with R c6 And R c7 The same applies to alkoxycarbonyl groups that may be present as substituents.
As R c6 And R c7 Preferable specific examples of the (C) include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-firstAlkoxyalkyl groups such as an oxyethyl group, a 3-methoxy-n-propyl group, a 4-methoxy-n-butyl group, a 5-methoxy-n-pentyl group, a 6-methoxy-n-hexyl group, a 7-methoxy-n-heptyl group, an 8-methoxy-n-octyl group, a 2-ethoxyethyl group, a 3-ethoxy-n-propyl group, a 4-ethoxy-n-butyl group, a 5-ethoxy-n-pentyl group, a 6-ethoxy-n-hexyl group, a 7-ethoxy-n-heptyl group, and an 8-ethoxy-n-octyl group; cyanoalkyl groups such as 2-cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl, 5-cyano-n-pentyl, 6-cyano-n-hexyl, 7-cyano-n-heptyl, and 8-cyano-n-octyl; 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, 3-cyclohexyl-n-propyl, 4-cyclohexyl-n-butyl, 5-cyclohexyl-n-pentyl, 6-cyclohexyl-n-hexyl, 7-cyclohexyl-n-heptyl, 8-cyclohexyl-n-octyl, 2-cyclopentylethyl, 3-cyclopentyl-n-propyl, 4-cyclopentyl-n-butyl, 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-n-octyl; an alkoxycarbonylalkyl group such as a 2-methoxycarbonylethyl group, a 3-methoxycarbonyl-n-propyl group, a 4-methoxycarbonyl-n-butyl group, a 5-methoxycarbonyl-n-pentyl group, a 6-methoxycarbonyl-n-hexyl group, a 7-methoxycarbonyl-n-heptyl group, an 8-methoxycarbonyl-n-octyl group, a 2-ethoxycarbonylethyl group, a 3-ethoxycarbonyl-n-propyl group, a 4-ethoxycarbonyl-n-butyl group, a 5-ethoxycarbonyl-n-pentyl group, a 6-ethoxycarbonyl-n-hexyl group, a 7-ethoxycarbonyl-n-heptyl group, and an 8-ethoxycarbonyl-n-octyl group; 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, n-pentyl, hexyl, and heptyl 4-bromo-n-butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl, 7-bromo-n-heptyl, 8-bromo-n-octyl 3,3, 3-trifluoropropyl, and 3,3,4, 5-heptafluoro-n-pentyl.
As R c6 And R c7 <xnotran>, , , , ,2- ,2- ,2- ,2- ,2- ,2- ,2- ,3,3,3- , 3,3,4,4,5,5,5- . </xnotran>
In the formula (c 5), a is particularly preferably S, because a photopolymerization initiator having excellent sensitivity can be easily obtained.
In the formula (c 5), R c9 Is a 1-valent organic group, a halogen atom, a nitro group, or a cyano group.
R in the formula (c 5) c9 In the case of a 1-valent organic group, it may be selected from various organic groups within a range not interfering with the object of the present invention. The organic group is preferably a group containing a carbon atom, and more preferably a group containing 1 or more carbon atoms and 1 or more atoms selected from the group consisting of H, O, S, se, N, B, P, si, and a halogen atom. The number of carbon atoms of the group containing a carbon atom is not particularly limited, but is preferably 1 to 50, and more preferably 1 to 20.
As R in formula (c 5) c9 Preferable examples of the organic group include R in the formula (c 3) c5 The 1-valent organic group of (1) is the same group.
R c9 Among them, benzoyl is preferred; a naphthoyl group; a benzoyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; a nitro group; a benzofuranylcarbonyl group which may have a substituent, more preferably a benzoyl group; a naphthoyl group; 2-methylphenylcarbonyl; 4- (piperazin-1-yl) phenylcarbonyl; 4- (phenyl) phenylcarbonyl.
In the formula (c 5), n4 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. When n4 is 1, R c9 Is preferably relative to R c9 The chemical bond bonding the bonded phenyl group to the oxygen atom or the sulfur atom is para.
In the formulae (c 1) and (c 2), R is c2 The 1-valent organic group in (1) is not particularly limited insofar as it does not interfere with the object of the present invention. The organic group is preferably a group containing carbon atoms, and more preferably a group containing 1 or more carbon atoms and 1 or more atoms selected from the group consisting of H, O, S, se, N, B, P, si, and halogen atoms. Containing carbonThe number of carbon atoms in the atomic group is not particularly limited, but is preferably 1 to 50, and more preferably 1 to 20.
As to R c2 Preferable examples of the 1-valent organic group in (c 3) include c5 The 1-valent organic group of (1) is the same group. Specific examples of these groups are those for R in the formula (c 3) c5 The same applies to the groups described.
In addition, as R c2 Cycloalkylalkyl, phenoxyalkyl which may have a substituent on the aromatic ring, and phenylthioalkyl which may have a substituent on the aromatic ring are also preferable. A substituent which the phenoxyalkyl group and the phenylthioalkyl group may have with R in the formula (c 3) c5 The same applies to the substituents when the phenyl group, naphthyl group and heterocyclic group contained in (1) further have a substituent.
In the organic radical, as R c2 Preferably, the above-mentioned monomer composition contains HX 2 C-or H 2 A substituent of the group represented by XC-, 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 the aromatic ring. With respect to the alkyl group, the phenyl group which may have a substituent, the carbon number of the cycloalkyl group contained in the cycloalkylalkyl group, the carbon number of the alkylene group contained in the cycloalkylalkyl group, the carbon number of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring, or the phenylthioalkyl group which may have a substituent on the aromatic ring, and R of the formula (c 3) c5 The same is true.
In addition, as R c2 Also preferred are groups represented by-A3-CO-O-A4. A3 is a 2-valent organic group, preferably a 2-valent hydrocarbon group, preferably an alkylene group. A4 is a 1-valent organic group, preferably a 1-valent hydrocarbon group.
When A3 is an alkylene group, the alkylene group may be linear or branched, and is preferably linear. When A3 is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.
Preferred examples of A4 include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Preferable specific examples of A4 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, phenyl, naphthyl, benzyl, phenethyl, α -naphthylmethyl, β -naphthylmethyl and the like.
Preferred examples of the group represented by-A3-CO-O-A4 include a 2-methoxycarbonylethyl group, a 2-ethoxycarbonylethyl group, a 2-n-propyloxycarbonylethyl group, a 2-n-butyloxycarbonylethyl group, a 2-n-pentyloxycarbonylethyl group, a 2-n-hexyloxycarbonylethyl group, a 2-benzyloxycarbonylethyl group, a 2-phenoxycarbonylethyl group, A3-methoxycarbonyl-n-propyl group, A3-ethoxycarbonyl-n-propyl group, A3-n-propyloxycarbonyl-n-propyl group, A3-n-butyloxycarbonyl-n-propyl group, A3-n-pentyloxycarbonyl-propyl group, A3-n-hexyloxycarbonyl-propyl group, A3-benzyloxycarbonyl-n-propyl group, and A3-phenoxycarbonyl-n-propyl group.
In addition, as R c2 Also, a group represented by the following formula (c 7) or (c 8) is preferable.
[ chemical formula 16]
Figure BDA0003703480590000321
(in the formulae (c 7) and (c 8), R c10 And R c11 Each independently is a 1-valent organic group,
n5 is an integer of 0 to 4 inclusive,
R c10 and R c11 In the case of presence in adjacent positions on the benzene ring, R c10 And R c11 May be bonded to each other to form a ring,
R c12 is a 1-valent organic group, and is a divalent organic group,
n6 is an integer of 1 to 8 inclusive,
n7 is an integer of 1 to 5 inclusive,
n8 is an integer of 0 to (n 7+ 3). )
As R in formula (c 7) c10 And R c11 Organic group of (2) andr in the formula (c 4) c8 The same applies. As R c10 Preferably containing HX 2 C-or H 2 Haloalkoxy of the group represented by XC-, comprising HX 2 C-or H 2 A haloalkyl group, an alkyl group or a phenyl group of the group represented by XC-. R is c10 And R c11 When a ring is bonded to form a bond, the ring may be an aromatic ring or an aliphatic ring. With respect to R as a group represented by the formula (c 7) c10 And R c11 Preferred examples of the group having a ring formed thereon include naphthalen-1-yl group, 1,2,3, 4-tetrahydronaphthalen-5-yl group and the like.
In the formula (c 7), n7 is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.
In the above formula (c 8), R c12 Is an organic group. Examples of the organic group include those related to R in the formula (c 4) c8 And the organic groups illustrated are the same. Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. As R c12 Examples thereof include preferably methyl, ethyl, propyl, isopropyl, butyl and the like, and among them, methyl is more preferred.
In the formula (c 8), n7 is an integer of 1 to 5, preferably 1 to 3, and more preferably 1 or 2. In the formula (c 8), n8 is an integer of 0 to (n 7+ 3), preferably 0 to 3, more preferably 0 to 2, and particularly preferably 0.
In the formula (c 8), n8 is an integer of 1 to 8, preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2.
In the formula (c 2), R c3 Is a hydrogen atom, 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 c3 Examples of the substituent which may be contained in the aliphatic hydrocarbon group include a phenyl group and a naphthyl group.
In the formulae (c 1) and (c 2), R is c3 Preferable examples thereof include a hydrogen atom, a methyl group ethyl, n-propyl, isopropyl,N-butyl, 2-cyclopentylethyl, 2-cyclobutylethyl, cyclohexylmethyl, phenyl, benzyl, methylphenyl, naphthyl and the like, among them, methyl or phenyl is more preferable.
As R, a group represented by the formula (c 2) and having the formula (c 3) c1 Preferable specific examples of the compound (b) include the following compounds.
[ chemical formula 17]
Figure BDA0003703480590000331
[ chemical formula 18]
Figure BDA0003703480590000341
[ chemical formula 19]
Figure BDA0003703480590000351
[ chemical formula 20]
Figure BDA0003703480590000352
As R, a group represented by the formula (c 2) and having the formula (c 4) c1 Preferable specific examples of the compound (b) include the following compounds.
[ chemical formula 21]
Figure BDA0003703480590000361
[ chemical formula 22]
Figure BDA0003703480590000371
[ chemical formula 23]
Figure BDA0003703480590000381
[ chemical formula 24]
Figure BDA0003703480590000391
[ chemical formula 25]
Figure BDA0003703480590000401
As R, a group represented by the formula (c 2) and having the formula (c 5) c1 Specific preferred examples of the compound (b) include the following compounds.
[ chemical formula 26]
Figure BDA0003703480590000402
Examples of the photopolymerization initiator (C) other than the oxime ester compound include α -aminoketone compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-dimethylaminophenyl) butan-1-one, 2- (4-methylbenzyl) -2-diethylamino-1- (4-morpholinophenyl) butan-1-one, 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1- [4- (hexyl) phenyl ] -2-morpholinopropan-1-one, and 2-ethyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one; α -hydroxyketone photopolymerization initiators such as 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, and 1-hydroxycyclohexyl phenyl ketone; benzoin-based photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzil dimethyl acetal; benzophenone-based photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl 4 '-methyldiphenyl sulfide, and 4,4' -bisdiethylaminobenzophenone; thioxanthone-based photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone and 2, 4-diisopropylthioxanthone; triazine-based photopolymerization initiators such as 2,4, 6-trichloro-s-triazine, 2-phenyl-4, 6-bis (trichloromethyl) s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (p-tolyl) -4, 6-bis (trichloromethyl) s-triazine, 2-piperonyl-4, 6-bis (trichloromethyl) s-triazine, 2, 4-bis (trichloromethyl) -6-styryl s-triazine, 2- (naphthalen-1-yl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-methoxy-naphthalen-1-yl) -4, 6-bis (trichloromethyl) s-triazine, 2, 4-trichloromethyl- (piperonyl) -6-triazine, 2, 4-trichloromethyl- (4' -methoxystyryl) -6-triazine, and 2- [4- (4-methoxystyryl) phenyl ] -4, 6-bis (trichloromethyl) -1,3, 5-triazine; a carbazole-based photopolymerization initiator; <xnotran> 2,2' - (2- ) -4,4',5,5' - (4- ) -1,2' - ,2,2 ' - (2- ) -4,4',5,5' - (4- ) -1,2' - ,2,2 ' - (2- ) -4,4',5,5' - -1,2' - ,2,2 ' - (2,4- ) -4,4',5,5' - -1,2' - ,2,2 ' - (2,4,6- ) -4,4',5,5' - -1,2' - ,2,2 ' - (2- ) -4,4,5,5' - -1,2' - ,2,2 ' - (2,4- ) -4,4',5,5' - -1,2' - ,2,2 ' - (2,4,6- ) -4,4',5,5' - -1,2' - ; </xnotran> And a benzimidazoline photopolymerization initiator represented by the following formula.
[ chemical formula 27]
Figure BDA0003703480590000411
The photopolymerization initiator may be used alone or in combination of 2 or more. By using 2 or more types in combination, light having a wide range of wavelengths included in exposure light can be effectively used, and the sensitivity of the photosensitive composition can be easily adjusted to an appropriate range.
The content of the photopolymerization initiator (C) in the entire solid content of the photosensitive composition is preferably 0.5 mass% to 15 mass%, more preferably 1 mass% to 10 mass%.
When a photopolymerization initiator other than the oxime ester compound is used in combination, the ratio of the mass of the oxime ester compound to the mass of the photopolymerization initiator (C) is preferably 50 mass% or more, more preferably 50 mass% or more and 99 mass% or less, particularly preferably 70 mass% or more and 97 mass% or less, and most preferably 80 mass% or more and 95 mass% or less.
When the oxime ester compound is contained in the photopolymerization initiator (C) in an amount within the above range, it is particularly difficult to form a patterned cured product having a width larger than a desired width.
< opacifier (D) >
The photosensitive composition contains a light-shading agent (D). Further, the light-shading agent (D) contains an organic black pigment (D1).
The ratio of the mass of the organic black pigment (D1) to the mass of the solid component of the photosensitive composition is 5 mass% to 30 mass%. If the mass ratio of the organic black pigment (D1) is more than 30 mass%, it is difficult to suppress the decrease in the transmittance of the lens in the unexposed portion. When the mass ratio of the organic black pigment (D1) is less than 5 mass%, it is difficult to form the light-shielding layer.
[ organic Black pigment (D1) ]
The sunscreen agent (D) may contain 1 or more than 2 organic black pigments (D1).
Examples of the organic black pigment (D1) include lactam pigments and perylene pigments.
< lactam-based pigments >
The lactam-based pigment is a compound represented by the following formula (d 1).
[ chemical formula 28]
Figure BDA0003703480590000431
In the formula (d 1), X d Represents a double bond, as a geometric isomer, each independently is an E or Z isomer, R d1 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 d2 Each independently represents a hydrogen atom, a methyl group, or a phenyl group. R d3 Each independently represents a hydrogen atom, a methyl group, or a chlorine atom.
The compound represented by the formula (d 1) may be used alone or in combination of 2 or more.
R is R from the viewpoint of easiness of production of the compound represented by the formula (d 1) d1 Preferably bonded to the 6-position, R of the indolinone ring d3 Preferably to the 4-position of the indolinone ring. From the same viewpoint, R d1 、R d2 And R d3 Preferably a hydrogen atom.
The compound represented by the formula (d 1) may have EE, ZZ, and EZ isomers as geometric isomers, and may be a single compound of any of these or a mixture of these geometric isomers.
The compound represented by formula (d 1) can be produced, for example, by the methods described in international publication nos. 2000/24736 and 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 or more and 1000nm or less.
< perylene pigments >
The perylene pigment is not particularly limited as long as it is a black pigment, and is a compound having a perylene skeleton.
Specific examples of the perylene pigment include a perylene pigment represented by the following formula (d 2), a perylene pigment represented by the following formula (d 3), and a perylene pigment represented by the following formula (d 4). Among commercially available products, perylene pigments such as product names K0084 and K0086, pigment black (Pigment black) 21, 30, 31, 32, 33, and 34 manufactured by BASF corporation can be preferably used.
[ chemical formula 29]
Figure BDA0003703480590000441
In the formula (d 2), R d11 And R d12 Each independently represents an alkylene group having 1 to 3 carbon atoms, R d13 And R d14 Each independently represents a hydrogen atom, a hydroxyl group, a methoxy group, or an acetyl group.
[ chemical formula 30]
Figure BDA0003703480590000442
In the formula (d 3), R d15 And R d16 Each independently represents an alkylene group having 1 to 7 carbon atoms.
[ chemical formula 31]
Figure BDA0003703480590000443
In the formula (d 4), R d17 And R d18 Each independently represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or a hetero atom of N, O, S, or P. R is d17 And R d18 In the case of an alkyl group, the alkyl group may be linear or branched.
The compound represented by the above formula (d 2), the compound represented by the above formula (d 3) and the compound represented by the above formula (d 4) can be synthesized, for example, by the methods described in Japanese patent application laid-open Nos. Sho 62-1753 and Sho 63-26784. Namely, perylene-3, 5,9, 10-tetracarboxylic acid or dianhydride thereof and amines are used as raw materials, and are subjected to a heating reaction 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, thereby obtaining the target product.
In order to disperse the perylene pigment well in the photosensitive composition and form a cured product having a low transmittance with respect to light in a wide wavelength range, the volume average particle diameter of the perylene pigment is preferably 10nm or more and 1000nm or less, more preferably 10nm or more and 500nm or less, and particularly preferably 10nm or more and 200nm or less.
When the volume particle diameter of the perylene pigment is within the above range, a cured product having a smooth surface with a low arithmetic average roughness Ra can be easily and stably formed.
[ Black pigment (D2) ]
The sunscreen (D) may contain a black pigment (D2). The black pigment (D2) is a black pigment (inorganic black pigment) other than the organic black pigment (D1). The black pigment (D2) is preferably carbon black subjected to treatment for introducing an acidic group.
The photosensitive composition preferably contains substantially no inorganic black pigment other than the carbon black subjected to the treatment of introducing an acidic group, for example, carbon black not subjected to the treatment of introducing an acidic group, titanium oxynitride, titanium nitride, fine particles mainly composed of a silver-tin (AgSn) alloy, metal oxides, complex oxides, metal sulfides, metal sulfates, or metal carbonates of copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, or the like.
Here, the photosensitive composition containing substantially no inorganic black pigment other than the carbon black subjected to the treatment of introducing an acidic group means that: the content of the inorganic black pigment other than the carbon black subjected to the treatment of introducing an acid group is small enough not to impair the desired effect. Typically, the content of the inorganic black pigment other than the acidic group-introducing carbon black in the photosensitive composition is preferably 1% by mass or less, more preferably 0.5% by mass or less, further preferably 0.1% by mass or less, and particularly preferably 0% by mass, based on the total mass of the organic black pigment (D1) and the acidic group-introducing carbon black. That is, it is particularly preferable that the photosensitive composition does not contain an inorganic black pigment other than carbon black subjected to treatment for introducing an acidic group.
< carbon Black having been subjected to treatment for introducing acidic group >
The carbon black subjected to the treatment of introducing an acidic group is carbon black having an acidic group introduced therein.
The acidic group introduced into the carbon black is a functional group showing 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 also 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 cation include various metal ions, cations of nitrogen-containing compounds, ammonium ions, and the like, and alkali metal ions such as sodium ions, potassium ions, and lithium ions, and ammonium ions are preferable.
The number of the acid groups introduced into the carbon black may be 1, or 2 or more.
As the carbon black, known carbon blacks such as channel black, furnace black, thermal black and lamp black can be used.
The method for introducing an acidic group into carbon black is not particularly limited. Examples of the method for introducing an acidic group include the following methods.
Method 1), a sulfonic acid group is introduced into carbon black by a direct substitution method using concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or the like, or an indirect substitution method using 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) of reacting an organic compound having a halogen atom and an acidic group with carbon black having a hydroxyl group by the etherification method of Williamson.
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), a Friedel-crafts reaction is performed on carbon black using an organic compound having a halocarbonyl group and an acid group protected by a protecting group, and then deprotection is performed.
Among these methods, method 2) is preferable in terms of ease and safety of introduction treatment of an acid group. The organic compound having an amino group and an acidic group used in the method 2) is preferably a compound in which an amino group and an acidic group are bonded to an aromatic group. Examples of such a compound include aminobenzenesulfonic acid such as sulfanilic acid, and aminobenzoic acid such as 4-aminobenzoic acid.
The number of moles of the acidic group introduced into the carbon black is not particularly limited within a range not interfering with the object of the present invention. The number of moles of the acidic group introduced into the carbon black is preferably 1mmol to 200mmol, more preferably 5mmol to 100mmol, per 100g of the carbon black.
[ other pigments ]
The light-shading agent (D) may contain other pigments besides the organic black pigment (D1) and the black pigment (D2). Sunscreen (D) may contain 1 or more than 2 other pigments.
The form of the light-shading agent (D) (organic black pigment (D1), black pigment (D2) and the like) used for producing the photosensitive composition is not particularly limited. The light-shading agent (D) may be used in the form of a powder or a dispersion. The light-shading agent (D) is preferably used in the form of a dispersion for producing a photosensitive composition.
As the dispersion liquid, a dispersion liquid containing 2 or more kinds of light-shading agents (D) can be used. Further, a dispersion of 2 or more kinds each containing a different kind of light-shading agent may be used.
As the dispersion medium, for example, an organic solvent such as propylene glycol monomethyl ether acetate, cellosolve acetate, 3-methoxybutyl acetate, methoxypropyl acetate, 2-methoxyethyl acetate, ethyl 3-ethoxypropionate, and propylene glycol monomethyl ether propionate can be used.
A dispersant may be used to stabilize the dispersion of the light-shielding agent (D) in the dispersion and to improve the dispersibility of the light-shielding agent (D) in the photosensitive composition.
As the dispersant, a polymer dispersant such as a polyethyleneimine-based, urethane resin-based, or acrylic resin-based dispersant is preferably used.
Among them, a polyurethane resin-based dispersant is preferable because it has good solubility in a developer and is less likely to cause adhesion of residues to a substrate, a developing device, a pipe, and the like after development.
When dispersion is used, the content of the dispersant in the photosensitive composition is, for example, 5 mass% to 50 mass%, preferably 10 mass% to 40 mass%, with respect to the content of the light-shielding agent (D).
In some cases, corrosive gas due to the dispersant is generated from the cured product. Therefore, a method of dispersing the light-shading agent (D) without using a dispersant is also a preferable example.
The viscosity of the dispersion of the light-shading agent (D) is not particularly limited. The viscosity of the dispersion is preferably 3 mPas to 200 mPas as measured with a cone-plate viscometer at 25 ℃.
The particle diameter of the light-shading agent (D) in the dispersion is preferably 80nm to 300nm in terms of the dispersion average particle diameter. The dispersion average particle diameter can be measured using a laser diffraction particle size distribution meter.
The content of the light-shading agent (D) in the entire solid content of the photosensitive composition is preferably 5 mass% or more and 60 mass% or less, more preferably 10 mass% or more and 50 mass% or less, and still more preferably 20 mass% or more and 40 mass% or less.
When the light-shading agent (D) contains the black pigment (D2), the proportion of the black pigment (D2) to the light-shading agent (D) is preferably 20 to 80 mass%, more preferably 30 to 75 mass%, and still more preferably 40 to 70 mass%.
< multifunctional epoxy Compound (F) >)
The photosensitive composition may contain a polyfunctional epoxy compound (F). By further including the polyfunctional epoxy compound (F) in the photosensitive composition, the photosensitive composition can be easily cured at a low temperature.
In the present specification, the polyfunctional epoxy compound (F) is an epoxy compound having 2 or more epoxy groups in 1 molecule.
As the polyfunctional epoxy compound (F), various polyfunctional epoxy compounds conventionally blended in photosensitive compositions can be used. Further, the multifunctional epoxy compound (F) and a curing agent corresponding to the kind of the multifunctional epoxy compound (F) may be contained as necessary. In the case of using a curing agent, it is preferable to use a curing agent which generates latency in the action as a curing agent by baking in view of long-term stability of the photosensitive composition.
The polyfunctional epoxy compound (F) has a molecular weight (Mw) of 2000 or less, preferably 1500 or less. The polyfunctional epoxy compound is preferably a monomeric compound or a compound having no repeating unit of 2 or more, and is not a polymer or an oligomer.
Examples of the polyfunctional epoxy compound (F) include: 2-functional epoxy compounds such as bisphenol a type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, bisphenol AD type epoxy compounds, naphthalene type epoxy compounds, and biphenyl type epoxy compounds; epoxy group-containing fluorene compounds such as 9,9-bis [4- (glycidyloxy) phenyl ] -9H-fluorene, 9,9-bis [4- [2- (glycidyloxy) ethoxy ] phenyl ] -9H-fluorene, 9,9-bis [4- [2- (glycidyloxy) ethyl ] phenyl ] -9H-fluorene, 9,9-bis [4- (glycidyloxy) -3-methylphenyl ] -9H-fluorene, 9,9-bis [4- (glycidyloxy) -3, 5-dimethylphenyl ] -9H-fluorene, and 9,9-bis (6-glycidyloxynaphthalen-2-yl) -9H-fluorene; glycidyl amine type epoxy compounds such as tetraglycidyl aminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidyl-m-xylylenediamine, and tetraglycidyl bisaminomethylcyclohexane; 3-functional oxygen compounds such as phloroglucinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, 2- [4- (2, 3-epoxypropoxy) phenyl ] -2- [4- [1, 1-bis [4- (2, 3-epoxypropoxy) phenyl ] ethyl ] phenyl ] propane, and 1, 3-bis [4- [1- [4- (2, 3-epoxypropoxy) phenyl ] -1-methylethyl ] phenyl ] ethyl ] phenoxy ] -2-propanol; 4-functional epoxy compounds such as tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether and tetraglycidoxybiphenyl.
Other examples of the polyfunctional epoxy compound (F) include polyfunctional alicyclic epoxy compounds having an alicyclic epoxy group. Specific examples of the alicyclic epoxy compound include 2- (3, 4-epoxycyclohexyl-5, 5-spiro-3, 4-epoxy) cyclohexane-m-dioxane, bis (3, 4-epoxycyclohexylmethyl) adipate, bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexyl 3',4' -epoxy-6 ' -methylcyclohexanecarboxylate, epsilon-caprolactone-modified 3',4' -epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate, trimethylcaprolactone-modified 3',4' -epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate, beta-methyl-delta-valerolactone-modified 3',4' -epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate, methylenebis (3, 4-epoxycyclohexane), bis (3, 4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis (3, 4-epoxycyclohexanecarboxylate) ethylene, and polyfunctional epoxy compounds having an oxidocyclodecenyl group, and compounds represented by the following formulae (F1-1) to (F5).
These alicyclic epoxy compounds may be used alone or in combination of 2 or more.
[ chemical formula 32]
Figure BDA0003703480590000501
(in the formula (F1-1), Z represents a single bond or a linking group (a divalent group having 1 or more atoms) F1 ～R F18 Each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. )
As the linking group Z, for example, examples thereof include those selected from the group consisting of 2-valent hydrocarbon groups, -O-,) -O-CO-, -S-, -SO 2 -、-CBr 2 -、-C(CBr 3 ) 2 -、-C(CF 3 ) 2 -, and-R F19 And 2-valent groups in the group consisting of-O-CO-, and groups in which a plurality of these groups are bonded to each other.
Examples of the divalent hydrocarbon group as the linking group Z include a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group, and the like. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene (dimethylene group), trimethylene (trimethylene group), and the like. Examples of the divalent alicyclic hydrocarbon group include cycloalkylene groups (including cycloalkylidene groups) such as 1, 2-cyclopentylene group, 1, 3-cyclopentylene group, cyclopentylidene group, 1, 2-cyclohexylene group, 1, 3-cyclohexylene group, 1, 4-cyclohexylene group, cyclohexylidene group, etc.
R F19 An alkylene group having 1 to 8 carbon atoms, preferably a methylene group or an ethylene group.
[ chemical formula 33]
Figure BDA0003703480590000502
(in the formula (F1-2), R F1 ～R F12 Is a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. )
[ chemical formula 34]
Figure BDA0003703480590000511
(in the formula (F1-3), R F1 ～R F10 Is a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R is F2 And R F8 May be bonded to each other. )
[ chemical formula 35]
Figure BDA0003703480590000512
(in the formula (F1-4), R F1 ～R F12 Is a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R is F2 And R F10 Can be bonded with each other。)
[ chemical formula 36]
Figure BDA0003703480590000513
(in the formula (F1-5), R F1 ～R F12 Is a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. )
In the formulae (F1-1) to (F1-5), R F1 ～R F18 In the case of an organic group, the organic group is not particularly limited insofar as it does not interfere with the object of the present invention, and may be a hydrocarbon group, a group formed of a carbon atom and a halogen atom, or a group containing a carbon atom, a hydrogen atom, a heteroatom such as a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, a fluorine atom and the like.
As the organic group, preferred are: a hydrocarbyl group; a group formed of a carbon atom, a hydrogen atom and an oxygen atom; a halogenated hydrocarbon group; a group formed of a carbon atom, an oxygen atom and a halogen atom; and a group formed of a carbon atom, a hydrogen atom, an oxygen atom and a halogen atom. When the organic group is a hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group containing an aromatic skeleton and an aliphatic skeleton. The number of carbon atoms of the organic group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5.
Specific examples of the hydrocarbon group include linear alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-eicosyl; chain alkenyl groups such as vinyl, 1-propenyl, 2-n-propenyl (allyl), 1-n-butenyl, 2-n-butenyl, and 3-n-butenyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl; aryl groups such as phenyl, o-tolyl, m-tolyl, p-tolyl, α -naphthyl, β -naphthyl, biphenyl-4-yl, biphenyl-3-yl, biphenyl-2-yl, anthryl, and phenanthryl; aralkyl groups such as benzyl, phenethyl, α -naphthylmethyl, β -naphthylmethyl, α -naphthylethyl, and β -naphthylethyl.
Specific examples of the halogenated hydrocarbon group include halogenated chain alkyl groups such as chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl and perfluorodecyl; halocycloalkyl groups such as 2-chlorocyclohexyl, 3-chlorocyclohexyl, 4-chlorocyclohexyl, 2, 4-dichlorocyclohexyl, 2-bromocyclohexyl, 3-bromocyclohexyl and 4-bromocyclohexyl; halogenated aryl groups such as 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2, 3-dichlorophenyl, 2, 4-dichlorophenyl, 2, 5-dichlorophenyl, 2, 6-dichlorophenyl, 3, 4-dichlorophenyl, 3, 5-dichlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-fluorophenyl, 3-fluorophenyl, and 4-fluorophenyl; and halogenated aralkyl groups such as 2-chlorophenylmethyl, 3-chlorophenylmethyl, 4-chlorophenylmethyl, 2-bromophenylmethyl, 3-bromophenylmethyl, 4-bromophenylmethyl, 2-fluorophenylmethyl, 3-fluorophenylmethyl, and 4-fluorophenylmethyl.
Specific examples of the group composed of a carbon atom, a hydrogen atom and an oxygen atom include a hydroxy chain alkyl group such as a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group and a 4-hydroxy-n-butyl group; halocycloalkyl groups such as 2-hydroxycyclohexyl, 3-hydroxycyclohexyl, and 4-hydroxycyclohexyl; hydroxyaryl groups such as 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2, 3-dihydroxyphenyl, 2, 4-dihydroxyphenyl, 2, 5-dihydroxyphenyl, 2, 6-dihydroxyphenyl, 3, 4-dihydroxyphenyl and 3, 5-dihydroxyphenyl; a hydroxyaralkyl group such as a 2-hydroxyphenylmethyl group, a 3-hydroxyphenylmethyl group, or a 4-hydroxyphenylmethyl group; chain alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecyloxy, and n-eicosyloxy groups; chain alkenyloxy groups such as vinyloxy, 1-propenyloxy, 2-n-propenyloxy (allyloxy), 1-n-butenyloxy, 2-n-butenyloxy and 3-n-butenyloxy; aryloxy groups such as phenoxy, o-tolyloxy, m-tolyloxy, p-tolyloxy, α -naphthyloxy, β -naphthyloxy, biphenyl-4-yloxy, biphenyl-3-yloxy, biphenyl-2-yloxy, anthracenyloxy, and phenanthrenyloxy; aralkyloxy groups such as benzyloxy, phenethyloxy, α -naphthylmethyloxy, β -naphthylmethyloxy, α -naphthylethyloxy, and β -naphthylethyloxy; alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, n-propoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl, 3-methoxy-n-propyl, 3-ethoxy-n-propyl, 3-n-propoxy-n-propyl, 4-methoxy-n-butyl, 4-ethoxy-n-butyl, and 4-n-propoxy-n-butyl; alkoxyalkoxy groups such as methoxymethoxy, ethoxymethoxy, n-propoxymethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 2-n-propoxyethoxy, 3-methoxy-n-propoxy, 3-ethoxy-n-propoxy, 3-n-propoxy, 4-methoxy-n-butyloxy, 4-ethoxy-n-butyloxy, and 4-n-propoxy-n-butyloxy; alkoxyaryl groups such as 2-methoxyphenyl, 3-methoxyphenyl, and 4-methoxyphenyl; alkoxyaryloxy groups such as 2-methoxyphenoxy group, 3-methoxyphenoxy group and 4-methoxyphenoxy group; aliphatic acyl groups such as formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, and decanoyl; aromatic acyl groups such as benzoyl, α -naphthoyl and β -naphthoyl; chain alkyloxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butyloxycarbonyl, n-pentyloxycarbonyl, n-hexylcarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, n-nonyloxycarbonyl, and n-decyloxycarbonyl; an aryloxycarbonyl group such as a phenoxycarbonyl group, an α -naphthyloxycarbonyl group, and a β -naphthyloxycarbonyl group; aliphatic acyloxy groups such as formyloxy, acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, and decanoyloxy; aromatic acyloxy groups such as benzoyloxy group, α -naphthoyloxy group, and β -naphthoyloxy group.
R F1 ～R F18 Each independently is preferably a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms, and particularly R is more preferably from the viewpoint of easiness of forming a cured product having excellent mechanical properties F1 ～R F18 All are hydrogen atoms.
In the formulae (F1-2) to (F1-5), R F1 ～R F12 And R in the formula (F1-1) F1 ～R F12 The same is true. In the formulae (F1-2) and (F1-4), R is F2 And R F10 The 2-valent group formed when bonded to each other includes, for example, -CH 2 -、-C(CH 3 ) 2 -. In the formula (F1-3), as R F2 And R F8 The 2-valent group formed when bonded to each other includes, for example, -CH 2 -、-C(CH 3 ) 2 -。
Among the alicyclic epoxy compounds represented by the formula (F1-1), preferable examples of the compounds include alicyclic epoxy compounds represented by the following formula (F1-1 a), formula (F1-1 b), and formula (F1-1 c), 2-bis (3, 4-epoxycyclohexan-1-yl) propane [ =2, 2-bis (3, 4-epoxycyclohexyl) propane ], and the like.
[ chemical formula 37]
Figure BDA0003703480590000551
Among the alicyclic epoxy compounds represented by the formula (F1-2), preferred examples of the compounds include a bicyclonodiene diepoxide represented by the following formula (F1-2 a), a bicyclonodiene diepoxide, and the like.
[ chemical formula 38]
Figure BDA0003703480590000552
Among the alicyclic epoxy compounds represented by the formula (F1-3), preferable specific examples of the compounds include S-spiro [ 3-oxatricyclo [3.2.1.0 ] 2,4 ]Octane-6, 2' -oxetanes]And so on.
Among the alicyclic epoxy compounds represented by the formula (F1-4), preferred examples of the compound include 4-vinylcyclohexene diepoxide (4-vinylcyclohexene dioxide), dipentene dioxide, limonene dioxide, 1-methyl-4- (3-methyloxetan-2-yl) -7-oxabicyclo [4.1.0] heptane and the like.
Among the alicyclic epoxy compounds represented by the formula (F1-5), preferable examples of the compound include 1,2,5, 6-diepoxycyclooctane and the like.
Further, a compound represented by the following formula (F-1) can be preferably used as the polyfunctional epoxy compound (F).
[ chemical formula 39]
Figure BDA0003703480590000561
(in the formula (F-1), X f1 、X f2 And X f3 Each independently a hydrogen atom, or an organic group which may contain an epoxy group, X f1 、X f2 And X f3 The total number of epoxy groups is 2 or more. ),
the compound represented by the formula (F-1) is preferably a compound represented by the following formula (F1-6).
[ chemical formula 40]
Figure BDA0003703480590000562
(in the formula (F1-6), R f20 ～R f22 Is a linear, branched or cyclic alkylene group, arylene group, -O-,; -C (= O) -, -NH-and groups formed from combinations thereof, each may be the same or different. E 1 ～E 3 Is at least 1 substituent selected from the group consisting of an epoxy group, an oxetanyl group, an ethylenically unsaturated group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, a thiol group, a carboxyl group, a hydroxyl group and a succinic anhydride group, or a hydrogen atom. Wherein, E 1 ～E 3 At least 2 of which are groups having epoxy groups. )
In the formula (F1-6), for R f20 And E 1 、R f21 And E 2 And R f22 And E 3 As the group(s) represented, for example, it is preferable that at least 2 groups are each a group represented by the following formula (F1-6 a), and it is more preferable that all groups are each a group represented by the following formula (F1-6 a). The plurality of groups represented by the formula (F1-6 a) bonded in 1 compound are preferably the same group.
-L-C a (F1-6a)
<xnotran> ( (F1-6 a) , L , , , -O-, -C (= O) -, -NH- , C </xnotran> a Is an epoxy group. In the formula (F1-6 a), L and C a May be bonded to form a ring structure. )
In the formula (F1-6 a), the linear, branched or cyclic alkylene group as L is preferably an alkylene group having 1 to 10 carbon atoms, and the arylene group as L is preferably an arylene group having 5 to 10 carbon atoms. In the formula (F1-6 a), L is preferably a linear alkylene group having 1 to 3 carbon atoms, a phenylene group, -O-, -C (= O) -, -NH-, or a group formed of a combination thereof, and is preferably at least 1 of a linear alkylene group having 1 to 3 carbon atoms and a phenylene group such as a methylene group, or a group formed of a combination thereof and at least 1 of-O-, -C (= O) -and NH-.
In the formula (F1-6 a), as L and C a When a cyclic structure is formed by bonding, for example, a branched alkylene group is bonded to an epoxy group to form a cyclic structure (an epoxy having an alicyclic structure)The structure of the group) includes organic groups represented by the following formulae (F1-6 b) or (F1-6 c).
[ chemical formula 41]
Figure BDA0003703480590000571
(in the formula (F1-6 b), R f23 Is a hydrogen atom or a methyl group. )
Examples of the compound represented by the formula (F1-6) include, but are not limited to, epoxy compounds having an oxetanyl group or an alicyclic epoxy group.
[ chemical formula 42]
Figure BDA0003703480590000581
Examples of the compound that can be preferably used as the polyfunctional epoxy compound (F) include silicone compounds having 2 or more epoxy groups in the molecule (hereinafter, also simply referred to as "silicone compounds").
The siloxane compound has a siloxane skeleton composed of siloxane bonds (Si-O-Si) and 2 or more glycidyl groups or alicyclic epoxy groups in the molecule. The alicyclic epoxy group is an alicyclic group in which 2 carbon atoms, which are adjacent ring-constituting atoms in the alicyclic group, are bonded to each other through an oxygen atom. That is, the alicyclic epoxy group has an epoxy group containing a 3-membered ring formed of 2 carbon atoms and 1 oxygen atom on an aliphatic ring.
Examples of the siloxane skeleton in the siloxane compound include a cyclic siloxane skeleton, a cage-type polysilsesquioxane skeleton, and a ladder (ladder) -type polysilsesquioxane skeleton.
Among them, preferred as the siloxane compound is a compound having a cyclic siloxane skeleton represented by the following formula (F1-7) (hereinafter, may be referred to as "cyclic siloxane").
[ chemical formula 43]
Figure BDA0003703480590000591
In the formula (F1-7), R f24 And R f25 Represents an epoxy group-containing 1-valent group or an alkyl group. Wherein x 1R in the compound represented by the formula (F1-7) f24 And x 1R f25 At least 2 of which are epoxy-containing 1-valent groups. In addition, x1 in the formula (F1-7) represents an integer of 3 or more. R in the compound represented by the formula (F1-7) f24 、R f25 May be the same or different. In addition, a plurality of R f24 May be the same or different. Plural R f25 They may be the same or different.
The epoxy group-containing monovalent group is preferably-D-O-R f26 The glycidyl ether group [ D represents an alkylene group, R f26 Represents a glycidyl group]. Examples of the D (alkylene) group include a linear or branched alkylene group having 1 to 18 carbon atoms such as a methylene group, a methylmethylene group, a dimethylmethylene group, and a trimethylene group.
Additionally, -D-R f27 The alicyclic epoxy group-containing group shown is also preferable. R f27 Is an epoxycycloalkyl group. As previously described, D is alkylene. Preferred examples of the alkylene group as D are also as described above. With respect to as R f27 The epoxycycloalkyl group of (A) is preferably a2, 3-epoxycyclopentyl group, a3, 4-epoxycyclohexyl group, and a2, 3-epoxycyclohexyl group. as-D-R f27 The group represented is preferably a 2- (3, 4-epoxycyclohexyl) ethyl group.
With respect to as R f24 And R f25 Preferable examples of the alkyl group of (2) include a linear or branched alkyl group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms) such as a methyl group, an ethyl group, a propyl group, and an isopropyl group.
In the formula (F1-7), x1 represents an integer of 3 or more, and among them, an integer of 3 or more and 6 or less is preferable from the viewpoint of excellent crosslinking reactivity when a cured product is formed.
The siloxane compound has 2 or more epoxy groups in the molecule, and is preferably 2 or more and 6 or less, and particularly preferably 2 or more and 4 or less, from the viewpoint of excellent crosslinking reactivity when a cured product is formed.
The photosensitive composition may contain, in addition to the siloxane compound represented by the formula (F1-7), compounds having a siloxane skeleton, such as alicyclic epoxy group-containing cyclic siloxane, alicyclic epoxy group-containing silicone resin described in japanese patent application laid-open No. 2008-248169, and organic polysilsesquioxane resin having at least 2 epoxy functional groups in 1 molecule described in japanese patent application laid-open No. 2008-19422.
More specifically, the siloxane compound includes a cyclic siloxane represented by the following formula and having 2 or more epoxy groups in the molecule. Further, as the silicone compound, commercially available products such as "X-40-2670", "X-40-2701", "X-40-2728", "X-40-2738" and "X-40-2740" (manufactured by shin-Etsu chemical industries, ltd.) can be used.
[ chemical formula 44]
Figure BDA0003703480590000611
[ chemical formula 45]
Figure BDA0003703480590000621
The content of the polyfunctional epoxy compound (F) in the photosensitive composition is preferably 0.1 mass% or more and 20 mass% or less, more preferably 0.5 mass% or more and 10 mass% or less, and particularly preferably 1 mass% or more and 5 mass% or less in the entire solid content of the photosensitive composition.
< organic solvent (S) >)
The photosensitive composition preferably contains an organic solvent (S) for dilution. Examples of the organic solvent (S) include (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol n-propyl ether, diethylene glycol 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, etc.; (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, butyl 3-methoxyacetate, butyl 3-methyl-3-methoxypropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
Among them, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, the above-mentioned other ethers, alkyl lactate esters, and the above-mentioned other esters are preferable, and alkylene glycol monoalkyl ether acetates, the above-mentioned other ethers, and the above-mentioned other esters are more preferable. These solvents may be used alone or in combination of 2 or more.
The content of the organic solvent (S) is preferably an amount that the solid content concentration of the photosensitive composition becomes 1 mass% or more and 50 mass% or less, and more preferably an amount that the solid content concentration of the photosensitive composition becomes 5 mass% or more and 40 mass% or less.
< other ingredients >
The photosensitive composition may contain various additives as necessary. Examples of the additives include a sensitizer, a curing accelerator, a filler, a dispersant, an adhesion promoter such as a silane coupling agent, an antioxidant, a deflocculant, a thermal polymerization inhibitor, a defoaming agent, and a surfactant.
< method for producing photosensitive composition >
The photosensitive composition can be prepared by mixing the above-mentioned components with a stirrer. In order to homogenize the photosensitive composition prepared, filtration may be carried out using a filter or the like through which the content such as the light-shading agent (D) can pass.
Method for manufacturing optical element and optical element
By using the photosensitive composition described above, an optical element 10 including the lens 1 and the light shielding layer 2 located at the periphery of the lens 1 as shown in fig. 1 can be manufactured.
Typically, the optical element 10 including the lens 1 and the light shielding layer 2 located at the periphery of the lens 1 can be manufactured by a method including the following steps:
a coating film forming step of forming a coating film 2a by applying the photosensitive composition to the lens 1;
an exposure step of exposing a position 3 of the coating film 2a where the light shielding layer 2 is to be formed in a position selective manner;
a developing step of developing the exposed coating film 2a; and
and a heat curing step of heating and curing the developed coating film 2a.
Hereinafter, each step will be described with reference to fig. 2. Fig. 2 is a schematic cross-sectional view illustrating a method of manufacturing the optical element 10.
< coating film formation Process >
In the coating film forming step, as shown in fig. 2 (a) and 2 (b), the photosensitive composition is coated on the lens 1 using a non-contact coating apparatus such as a spray coater or a dip coater.
The lens 1 is as described in the above-mentioned "photosensitive composition".
After the photosensitive composition is applied, the solvent is removed by drying as necessary, thereby forming a coating film 2a.
The drying (heating) is preferably performed at a low temperature, for example, 100 ℃ or lower, preferably 80 ℃ or lower, so that the thermal curing of the photosensitive composition does not excessively proceed. The drying may be carried out in a reduced pressure atmosphere as required.
< Exposure Process >
In the exposure step, as shown in fig. 2 (c), the position 3 where the light shielding layer 2 is to be formed in the coating film 2a formed in the coating film forming step is exposed in a position-selective manner. In the exposure step, the coating film 2a is exposed by irradiating it with an active energy ray such as i-ray (365 nm) or excimer laser light in a position-selective manner in accordance with the desired shape (pattern shape) of the light-shielding layer 2. The position-selective exposure is performed, for example, through a negative mask 4 having a shape corresponding to the shape of the light-shielding layer 2.
In the exposure, a light source emitting ultraviolet rays such as a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, or a carbon arc lamp may be used. The exposure amount varies depending on the composition of the photosensitive composition, and is preferably 10mJ/cm, for example 2 Above 600mJ/cm 2 About the following.
< developing Process >
In the developing step, the unexposed portions 5 of the coating film 2a exposed in the exposing step are developed with a developing solution such as an alkaline developing solution.
The developing method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Specific examples of the developer include organic solutions such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.
By using the photosensitive composition, the generation of development residue in the unexposed portion 5 can be suppressed. Therefore, in the obtained optical element 10, a decrease in transmittance of the unexposed portion 5 of the lens 1 can be suppressed.
< Heat curing Process >
In the thermosetting step, the developed coating film is heated (baked). As a result, as shown in fig. 2d, the developed coating film is cured by heating, and the light shielding layer 2 (cured product of the pattern) can be formed.
The baking temperature may be set to, for example, 120 ℃ or lower, 100 ℃ or lower, or further 95 ℃ or lower. The lower limit of the baking temperature is not particularly limited as long as the curing of the coating film proceeds well, and is preferably 80 ℃ or higher.
As described above, by using the photosensitive composition, baking can be performed at a low temperature, and therefore, even when a lens formed of a material having low heat resistance is used as the lens 1, it is possible to simultaneously achieve light-shielding properties of the light-shielding layer 2 and suppression of a decrease in transmittance of the lens 1 in the unexposed portion 5.
The baking time is not particularly limited, and the curing of the coating film can be sufficiently performed. Typically, the baking time is preferably 15 to 60 minutes.
The thickness of the light-shielding layer 2 to be formed is not particularly limited. The thickness of the light-shielding layer 2 is preferably 0.05 μm or more, and more preferably 1 μm or more. The upper limit of the thickness of the light-shielding layer 2 is not particularly limited, and may be, for example, 50 μm or less or 20 μm or less. The thickness of the light-shielding layer 2 is preferably 10 μm or less.
The light-shielding layer 2 formed around the periphery of the lens 1 by the method for manufacturing the optical element 10 using the photosensitive composition has light-shielding properties. In addition, the unexposed portion 5 of the lens 1 is inhibited from developing residues, and has a high transmittance to visible light. Therefore, the optical element 10 suppresses flare, ghost, and the like generated by reflection of incident light, and suppresses a decrease in transmittance of the unexposed portion (i.e., the region through which the incident light passes) 5, and thus can be preferably used for optical apparatuses such as cameras, microscopes, and semiconductor exposure devices.
Examples
The present invention will be described more specifically with reference to the following examples, but the scope of the present invention is not limited to these examples.
In examples and comparative examples, as the alkali-soluble resin (a), resin a-1 and resin a-2, which are alkali-soluble Cardo resins, were used. Resin A-1 was the resin obtained in preparation example 1 below, and resin A-2 was the resin obtained in preparation example 2 below.
Preparation example 1
First, 235g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110mg of tetramethylammonium chloride, 100mg of 2, 6-di-t-butyl-4-methylphenol and 72.0g of acrylic acid were put into a 500ml four-necked flask, and dissolved by heating at 90 to 100 ℃ while blowing air at a rate of 25 ml/min. Then, the temperature of the solution was gradually increased while the solution was kept cloudy, and the solution was heated to 120 ℃ to be completely dissolved. At this time, the solution gradually became transparent and viscous, and stirring was continued in this state. During this time, the acid value was measured, and heating and stirring were continued until the acid value became less than 1.0mgKOH/g. It took 12 hours until the acid value reached the target value. Then, the mixture was cooled to room temperature to obtain a bisphenol fluorene type epoxy acrylate represented by the following formula which was colorless and transparent and was solid.
[ chemical formula 46]
Figure BDA0003703480590000671
Then, 600g of 3-methoxybutyl acetate was added to 307.0g of the bisphenol fluorene type epoxy acrylate obtained as described above, and dissolved, and then 80.5g of 3,3', 4' -biphenyltetracarboxylic dianhydride and 1g of tetraethylammonium bromide were mixed and the temperature was gradually increased. The reaction is carried out for 4 hours at 110 to 115 ℃. After confirming the disappearance of the acid anhydride groups, 38.0g of 1,2,3, 6-tetrahydrophthalic anhydride was mixed and reacted at 90 ℃ for 6 hours to obtain resin A-1. The disappearance of the acid anhydride group was confirmed by IR spectroscopy. The mass average molecular weight of the resin A-1 in terms of polystyrene as measured by gel permeation chromatography was 3100.
(preparation example 2)
Resin A-2 was obtained in the same manner as in preparation example 1 except that 3,3', 4' -biphenyltetracarboxylic dianhydride was changed to 40.3g of 3,3', 4' -biphenyltetracarboxylic dianhydride and 20.5g of 1,2,3, 6-tetrahydrophthalic dianhydride. The mass average molecular weight of the resin A-2 in terms of polystyrene as measured by gel permeation chromatography was 2300.
In examples and comparative examples, the following B-1 and B-2 were used as the photopolymerizable monomer (B).
B-1: dipentaerythritol hexaacrylate (DPHA)
B-2: mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (product name ARONIX M-933, manufactured by Toyo chemical Co., ltd.)
In examples and comparative examples, the following C-1 was used as the photopolymerization initiator (C).
[ chemical formula 47]
Figure BDA0003703480590000681
In examples and comparative examples, the following D1-1 (lactam-based pigment) and D1-2 (perylene-based pigment) as the organic black pigment (D1) and the following D2-1 and D2-2 as the black pigment (D2) other than the organic black pigment (D1) were used as the light-shading agent (D). The black pigment (D2) is used in the form of a black pigment dispersion liquid (carbon black dispersion liquid). The method for producing the carbon black dispersion is described below as production example 4. The organic black pigment (D1) is used in the form of an organic black pigment dispersion liquid. The method for preparing the organic black pigment dispersion is described below as preparation example 5.
[ chemical formula 48]
Figure BDA0003703480590000682
D2-1: carbon Black having benzenesulfonyl group introduced thereinto obtained in preparation example 3 below
D2-2: carbon Black not subjected to acid group introduction treatment (Regal 250R, manufactured by Cabot corporation)
(preparation example 3
550g of carbon black (Regal 250R, cabot corporation), 31.5g of sulfanilic acid, and 1000g of ion-exchanged water were charged into a reaction vessel equipped with a jacket and a stirrer (the jacket temperature was set at 60 ℃). A solution prepared by dissolving 12.6g of sodium nitrite in 100g of deionized water was charged into a Brownmixer (Brown mixer), and the mixture in the mixer was stirred at 60 ℃ for 2 hours at 50 rpm to conduct a diazo coupling reaction. After stirring, the contents of the mixer were cooled to room temperature. Next, the carbon black contained in the contents of the mixer was purified by percolation using deionized water. It was found that benzenesulfonic acids derived from sulfanilic acid were not detected in the washing water, and that benzenesulfonic acid groups were introduced into carbon black by the diazo coupling reaction. The purified carbon black was dried at 75 ℃ overnight and then pulverized to obtain a carbon black (D2-1) having a benzenesulfonic acid group introduced therein.
Preparation example 4 preparation of carbon Black Dispersion
A carbon black dispersion was prepared according to the following formulation using the above D2-1 and D2-2 as carbon black.
Carbon black (15 g), a dispersant (BYK-167, manufactured by BYK Chemie Japan K.K.) (4.5 g), and butyl 3-methoxyacetate (50 g) were mixed and stirred by a bead mill to disperse the carbon black in the butyl 3-methoxyacetate. Thereafter, the mixture was diluted with butyl 3-methoxyacetate so that the solid content concentration became 30 mass%, thereby obtaining a carbon black dispersion.
Preparation example 5 preparation of organic Black pigment Dispersion
An organic black pigment dispersion was obtained in the same manner as in preparation example 4, except that D1-1 or D1-2 as the organic black pigment (D1) was used instead of carbon black.
In examples and comparative examples, the following F-1 was used as the polyfunctional epoxy compound (F).
[ chemical formula 49]
Figure BDA0003703480590000691
[ examples 1 to 8 and comparative examples 1 to 3]
Photosensitive compositions of examples 1 to 8 and comparative examples 1 to 3 were prepared by uniformly dissolving and dispersing an alkali-soluble resin (a), a photopolymerizable monomer (B), a photopolymerization initiator (C), a light-shielding agent (D), and a polyfunctional epoxy compound (F) in the kind and parts by mass described in table 1 in a solvent (S) so that the solid content concentration became 25 mass%. The solvent (S) was a mixed solvent of 20 mass% of butyl 3-methoxyacetate and 80 mass% of Propylene Glycol Monomethyl Ether Acetate (PGMEA). The light-shading agent (D) was blended using a dispersion so that the light-shading agent (D) was in the type and amount shown in table 1. The amount of dispersant is also reported in table 1.
Using the photosensitive compositions of the respective examples and comparative examples obtained, the OD value and the transmittance (development residue) of the lens were evaluated in the following manner. The results are shown in Table 1.
[ evaluation of OD value ]
At 10cm 2 The photosensitive composition was applied to the glass substrate (glass XG, corning), and then heated (dried) at 80 ℃ for 120 seconds to form a coating film. Next, a broadband (broad band) light including an i-line (365 nm) was irradiated to the coating film by using a proximity exposure apparatus (product name: TME-150RTO, manufactured by TOPCON CORPORATION). The exposure amount was set to 100mJ/cm 2 . Then, it was heated (baked) on a hot plate at 90 ℃ for 30 minutes. The thickness of the light-shielding film (cured product) was 1.0. Mu.m. The OD value of the light-shielding film (cured product) was measured using D200-II (manufactured by Macbeth).
[ evaluation of transmittance of lens (development residue) ]
Using the photosensitive composition, a light-shielding layer 2 was formed around the periphery of the lens 1 by the method shown in fig. 2.
Specifically, first, the photosensitive composition was applied to the entire surface of a lenticular substrate (made of polycarbonate) having a diameter of 3cm and a thickness of 3mm by a spray coater, and heated (dried) at 80 ℃ for 120 seconds to form a coating film. Next, the center of the lens was masked with a light-shielding material having a diameter of 2cm, and broadband light including i-rays (365 nm) was irradiated with the light using a double-sided printer "HMW-532D manufactured by ORC corporation". The exposure amount was set to 100mJ/cm 2 . The coating film after exposure was developed in a 0.04 mass% KOH aqueous solution at 26 ℃ for 50 seconds, and then heated (baked) at 90 ℃ for 30 minutes, thereby forming a light-shielding layer 2 having a thickness of 1.0 μm at the periphery of the lens 1.
The transmittance in the thickness direction at a wavelength of 380nm to 780nm was measured using an MCPD-3000 (manufactured by luka electronics corporation) for the lens 1 before the application of the photosensitive composition and the lens on which the light shielding layer 2 was formed, and the average values were obtained as the transmittance of the lens before the application of the photosensitive composition and the transmittance of the unexposed portion of the lens on which the light shielding layer was formed. The unexposed portion of the lens formed with the light-shielding layer was measured, and the same portion of the lens before the application of the photosensitive composition as that of the lens formed with the light-shielding layer was measured. The case where the transmittance change obtained by the following formula was less than 1% was evaluated as "excellent", the case where the transmittance change was 1% or more and less than 2% was evaluated as "good", and the case where the transmittance change was 2% or more was evaluated as "x".
Transmittance change (%) = (T) 1 /T 0 )×100
T 0 : transmittance of lens before application of photosensitive composition
T 1 : transmittance of unexposed part of lens formed with light-shielding layer
[ Table 1]
Figure BDA0003703480590000711
From examples 1 to 8, it is understood that, in the photosensitive composition which comprises the alkali-soluble resin (a), the photopolymerizable monomer (B), the photopolymerization initiator (C) and the light-shielding agent (D), and in which the light-shielding agent (D) comprises the organic black pigment (D1) and the ratio of the mass of the organic black pigment (D1) to the mass of the solid component of the photosensitive composition is 5 mass% or more and 30 mass% or less, the light-shielding layer can be formed by applying the coating film to the lens and exposing and developing the coating film formed in a position-selective manner, and the decrease in the transmittance of the lens in the unexposed portion can be suppressed. Among them, in example 4 in which the mass average molecular weight of the alkali-soluble resin (a) was 2500 or less, the transmittance of the lens in the unexposed portion was particularly high.
On the other hand, according to comparative examples 1 to 3, when a photosensitive composition not containing the organic black pigment (D1) was used, and a photosensitive composition in which the ratio of the mass of the organic black pigment (D1) to the mass of the solid component was out of the range of 5 mass% to 30 mass%, development residue was generated, and the transmittance of the lens in the unexposed portion was low.

Claims (13)

1. A photosensitive composition for forming a light shielding layer around a lens,
the photosensitive composition comprises an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C) and a light-shading agent (D),
the light-shading agent (D) contains an organic black pigment (D1), and the ratio of the mass of the organic black pigment (D1) to the mass of the solid component of the photosensitive composition is 5-30 mass%.
2. The photosensitive composition according to claim 1, wherein the alkali-soluble resin (a) comprises a resin having a Cardo structure with a mass average molecular weight of 2500 or less.
3. The photosensitive composition according to claim 1, wherein the photopolymerizable monomer (B) comprises a polyfunctional (meth) acrylate having a hydroxyl group.
4. The photosensitive composition according to claim 1, which comprises a polyfunctional epoxy compound (F).
5. The photosensitive composition according to claim 1, wherein the organic black pigment (D1) comprises at least one selected from a lactam-based pigment and a perylene-based pigment.
6. The photosensitive composition according to claim 1, wherein the light-shading agent (D) comprises a black pigment (D2) other than the organic black pigment (D1).
7. The photosensitive composition according to any one of claims 1 to 6, wherein the lens is formed of a resin.
8. The photosensitive composition according to claim 7, wherein the resin is polycarbonate, a cycloolefin polymer, an epoxy resin, or an acrylic resin.
9. A method for manufacturing an optical element including a lens and a light-shielding layer located at a peripheral edge of the lens, the method comprising:
a coating film forming step of forming a coating film by applying the photosensitive composition according to any one of claims 1 to 8 to the lens;
an exposure step of exposing a position of the coating film where the light shielding layer is to be formed in a position selective manner;
a developing step of developing the exposed coating film; and
and a heat curing step of heating and curing the developed coating film.
10. The method for manufacturing an optical element according to claim 9, wherein the heat curing step is performed at a temperature of 100 ℃ or lower.
11. The method of manufacturing an optical element according to claim 9, wherein the lens is formed of a resin.
12. The method of manufacturing an optical element according to claim 11, wherein the resin is polycarbonate, a cycloolefin polymer, an epoxy resin, or an acrylic resin.
13. An optical element including a lens and a light-shielding layer located on a peripheral edge of the lens,
the light-shielding layer is formed from a cured product of the photosensitive composition according to any one of claims 1 to 8.
CN202210701455.0A 2021-06-23 2022-06-20 Photosensitive composition Pending CN115509087A (en)

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