Photocurable composition, film, optical filter, solid-state imaging element, and image display device
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- FUJIFILM CORP
- Filing Date
- 2026-01-07
- Publication Date
- 2026-07-30
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Figure JPOXMLDOC01-APPB-C000001 
Figure JPOXMLDOC01-APPB-C000002 
Figure JPOXMLDOC01-APPB-C000003
Abstract
Description
Photocurable compositions, films, optical filters, solid-state image sensors, and image display devices.
[0001] This invention relates to a photocurable composition comprising a photopolymerization initiator and a polymerizable monomer. Furthermore, this invention relates to films, optical filters, solid-state image sensors, and image display devices using the photocurable composition.
[0002] Photocurable compositions containing a photopolymerization initiator and a polymerizable monomer can be polymerized and cured by irradiation with light, and are therefore used in optical filters, photocurable inks, photosensitive printing plates, various photoresists, and the like.
[0003] Patent Document 1 discloses a method of forming pixels by creating a pattern using a photocurable composition containing a photopolymerization initiator and a polymerizable monomer, via photolithography.
[0004] Japanese Patent Publication No. 2022-063556
[0005] Further improvements are needed in the sensitivity of photocurable compositions containing photopolymerization initiators and polymerizable monomers to exposure light.
[0006] According to the inventors' research, it was found that there is room for further improvement in these properties of the photocurable composition disclosed in Patent Document 1.
[0007] Therefore, an object of the present invention is to provide a photocurable composition with excellent sensitivity. Another object of the present invention is to provide a film, optical filter, solid-state image sensor, and image display device using the photocurable composition.
[0008] The present invention provides the following:
[0009] <1> A photocurable composition comprising a polymerizable monomer and a photopolymerization initiator, wherein the polymerizable monomer comprises polymerizable monomer a having an amino group, an alkylene oxy group, and an ethylenically unsaturated bond-containing group, and the photopolymerization initiator comprises an oxime compound. <2> The photocurable composition according to <1>, wherein the alkylene oxy group of polymerizable monomer a is an ethylene oxy group. <3> The photocurable composition according to <1> or <2>, wherein the hydroxyl value of polymerizable monomer a is 100 mg KOH / g or less. <4> The photocurable composition according to any one of <1> to <3>, wherein the amine value of polymerizable monomer a is 80 mg KOH / g or less. <5> The photocurable composition according to any one of <1> to <4>, wherein the ethylenically unsaturated bond-containing value of polymerizable monomer a is 1.5 mmol / g or more. <6> The photocurable composition according to any one of <1> to <5>, wherein the polymerizable monomer a comprises polymerizable monomer a1 having an amino group, an alkylene oxy group, and six or more ethylenically unsaturated bond-containing groups. <7> The photocurable composition according to <6>, wherein the polymerizable monomer a further comprises polymerizable monomer a2 having an amino group, an alkylene oxy group, and one to five ethylenically unsaturated bond-containing groups. <8> The photocurable composition according to any one of <1> to <5>, wherein the polymerizable monomer further comprises polymerizable monomer b other than polymerizable monomer a, and either polymerizable monomer a or polymerizable monomer b comprises a compound having six or more ethylenically unsaturated bond-containing groups, while the other comprises a compound having one to five ethylenically unsaturated bond-containing groups. <9> The photocurable composition according to any one of <1> to <8>, wherein the oxime compound comprises a compound represented by formula (OX-1); In formula (OX-1), X 1a R represents a divalent linking group containing at least one selected from the group consisting of aromatic rings and heterocycles. 1a R represents a hydrogen atom or an acyl group. 2a R represents an alkyl or aryl group. 3a and R 4a Each of these independently represents a hydrogen atom or an alkyl group, and Alk1 and Alk 2 each independently represents an alkyl group, and R 3a and R 4a may combine to form a ring, and Alk 1 and Alk 2 may combine to form a ring, and n represents 0 or 1. <10> The photocurable composition according to any one of <1> to <9>, comprising a resin having an alkyleneoxy group. <11> The photocurable composition according to any one of <1> to <10>, comprising a resin having a phosphate group and an alkyleneoxy group. <12> The photocurable composition according to any one of <1> to <11>, further comprising a coloring material. <13> A film obtained by using the photocurable composition according to any one of <1> to <12>. <14> An optical filter having the film according to <13>. <15> A solid-state imaging device having the film according to <13>. <16> An image display device having the film according to <13>.
[0010] According to the present invention, a photocurable composition excellent in sensitivity can be provided. Further, the present invention can provide a film, an optical filter, a solid-state imaging device, and an image display device using the photocurable composition.
[0011] The present invention will be described in detail below. In this specification, "~" is used to mean that the numerical values before and after it are included as the lower and upper limits. In the notation of groups (atomic groups) in this specification, notations that do not specify substituted or unsubstituted include both groups (atomic groups) with substituents and groups (atomic groups) without substituents. For example, "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include the emission line spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" refers to both acrylate and methacrylate, or either of them; "(meth)acrylic" refers to both acrylic and methacrylic, or either of them; and "(meth)acryloyl" refers to both acryloyl and methacryloyl, or either of them. In this specification, Me in structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, weight-average molecular weight and number-average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography). In this specification, total solids refer to the total mass of components of a composition excluding the solvent. In this specification, pigment refers to a colorant that is poorly soluble in solvents. In this specification, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as the intended function of that process is achieved.
[0012] <Photocurable Composition> The photocurable composition of the present invention is a photocurable composition comprising a polymerizable monomer and a photopolymerization initiator, wherein the polymerizable monomer comprises polymerizable monomer a having an amino group, an alkylene oxy group and an ethylenically unsaturated bond-containing group, and the photopolymerization initiator comprises an oxime compound.
[0013] The photocurable composition of the present invention exhibits excellent sensitivity. The reason for this effect is presumed to be as follows: In radical polymerization, polymerization is inhibited by oxygen (oxygen inhibition). Since oxygen is in a triplet state in its ground state, it is highly reactive with radicals and readily reacts with radical active species to form hydroxyperoxy radicals. These hydroxyperoxy radicals have poor reactivity with polymerizable groups such as (meth)acryloyl groups, thus inhibiting the progress of the polymerization reaction. The polymerizable monomer a used in the present invention has an amino group and an alkylene oxy group, so it is presumed that hydrogen is easily abstracted away to generate carbon radicals. Therefore, it is presumed that polymerization is initiated by the newly generated carbon radicals, which are created when the generated hydroxyperoxy radicals abstract hydrogen from the polymerizable monomer a. It is also presumed that the generated carbon radicals can capture oxygen and reduce the oxygen concentration. Furthermore, when oxime compounds decompose upon exposure, they generate both polymerization-active radicals and polymerization-inactive nitrogen radicals. It is presumed that the polymerization-inactive nitrogen radicals generated from the oxime compounds abstract hydrogen from the polymerizable monomer a, thereby generating polymerization-active carbon radicals. These mechanisms are presumed to explain the high sensitivity of the photocurable composition of the present invention.
[0014] Because the photocurable composition of the present invention has excellent sensitivity, exposure allows sufficient polymerization to proceed even at the bottom of the film (support side). Therefore, the photocurable composition of the present invention can form a film with excellent adhesion to the support.
[0015] Furthermore, by using the photocurable composition of the present invention, the occurrence of pixel defects during development can be more effectively suppressed. This is presumed to be because the polymerizable monomer a has an alkylene oxy group, which improves the flexibility of the resulting film.
[0016] The photocurable composition of the present invention preferably further contains a colorant. The photocurable composition containing a colorant is preferably used as a photocurable composition for optical filters. Examples of optical filters include color filters, infrared transmission filters, and infrared cut filters, and a color filter is preferred.
[0017] Examples of color filters include filters having colored pixels that transmit light of a specific wavelength. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. The colored pixels of a color filter can be formed using a photocurable composition containing a chromatic colorant.
[0018] The maximum absorption wavelength of the infrared cut filter is preferably in the range of 700 to 1800 nm, more preferably in the range of 700 to 1300 nm, and even more preferably in the range of 700 to 1000 nm. Furthermore, the transmittance of the infrared cut filter over the entire range of wavelengths from 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. Furthermore, the transmittance at at least one point in the range of wavelengths from 700 to 1800 nm is preferably 20% or less. In addition, the ratio of the absorbance Amax at the maximum absorption wavelength of the infrared cut filter to the absorbance A550 at a wavelength of 550 nm (absorbance Amax / absorbance A550) is preferably 20 to 500, more preferably 50 to 500, even more preferably 70 to 450, and particularly preferably 100 to 400. The infrared cut filter can be formed using a photocurable composition containing an infrared absorbing colorant.
[0019] An infrared transmission filter is a filter that transmits at least a portion of infrared light. Preferably, an infrared transmission filter is a filter that blocks at least a portion of visible light and transmits at least a portion of infrared light. Preferred infrared transmission filters include filters that satisfy spectral characteristics such as a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1300 nm. Preferably, an infrared transmission filter is a filter that satisfies any of the following spectral characteristics (1) to (5): (1): A filter in which the maximum transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the minimum transmittance in the wavelength range of 800 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more). (2) A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 750 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 900 to 1500 nm. (3) A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 830 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1000 to 1500 nm. (4) A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 950 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1500 nm. (5) A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 1050 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1200 to 1500 nm.
[0020] The photocurable composition of the present invention can also be used in light-shielding films and the like.
[0021] The solid content concentration of the photocurable composition of the present invention is preferably 5 to 30% by mass. The lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.
[0022] The following describes each component used in the photocurable composition of the present invention.
[0023] <<Polymerizable Monomers>> The photocurable composition of the present invention contains polymerizable monomers. Examples of polymerizable monomers include compounds having an ethylenically unsaturated bond-containing group. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, allyl groups, (meth)acryloyl groups, and styrene groups. The polymerizable monomer used in the present invention is preferably a radical polymerizable monomer.
[0024] (Polymerizable monomer a (specific amine monomer) having an amino group, an alkylene oxy group, and an ethylenically unsaturated bond-containing group) In the photocurable composition of the present invention, polymerizable monomers are used that include polymerizable monomer a (hereinafter also referred to as a specific amine monomer) having an amino group, an alkylene oxy group, and an ethylenically unsaturated bond-containing group.
[0025] Examples of ethylenically unsaturated bond-containing groups found in specific amine monomers include vinyl groups, allyl groups, (meth)acryloyl groups, and styrene groups, with (meth)acryloyl groups being preferred.
[0026] The alkylene oxy group of the specific amine monomer preferably has 2 or more carbon atoms, more preferably 2 to 10, even more preferably 2 to 5, and even more preferably 2 or 3. The alkylene oxy group is preferably linear or branched, and more preferably linear. The alkylene oxy group of the specific amine monomer is preferably an ethylene oxy group or a propylene oxy group, and more preferably an ethylene oxy group.
[0027] The number of alkylene oxy groups in the specific amine monomer is preferably 1 to 150. The lower limit is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. The upper limit is preferably 100 or less, more preferably 75 or less, even more preferably 40 or less, and particularly preferably 25 or less.
[0028] The alkylene oxy group of the specific amine monomer is preferably a polyalkylene oxy group. In this specification, a polyalkylene oxy group means a group in which two or more alkylene oxy groups are directly bonded. The alkylene groups in the multiple alkylene oxy groups contained in the polyalkylene oxy group may be the same or different. When the polyalkylene oxy group contains multiple types of alkylene oxy groups with different alkylene groups, the arrangement of the alkylene oxy groups in the polyalkylene oxy group may be a random arrangement, an arrangement with blocks, or an arrangement with a pattern such as alternating.
[0029] The specific amine monomer preferably contains a group represented by formula (L-101).
[0030] - (L 101 ) q -...(L-101)
[0031] In formula (L-101), L 101 represents an alkylene oxy group, q represents an integer greater than or equal to 1, and q L 101 They may be the same or they may be different.
[0032] L in equation (L-101) 101 The alkylene oxy group represented by is preferably 2 or more carbon atoms, more preferably 2 to 10, even more preferably 2 to 5, and even more preferably 2 or 3. The alkylene oxy group is preferably linear or branched, and more preferably linear. 101 The alkylene oxy group represented is preferably an ethylene oxy group.
[0033] In formula (L-101), q is preferably 1 to 75, more preferably 1 to 40, and even more preferably 1 to 25.
[0034] The specific amine monomer is preferably a compound represented by formula (1) or formula (2).
[0035] In equation (1), n1 represents an integer from 0 to 2, n2 represents an integer from 1 to 3, n1 + n2 is 3, m1 represents an integer from 1 to 5, L 1 This represents a linking group with m1+1 valency, and if n2 is 2 or more, there are multiple L 1 They may be the same or they may be different. 1 This represents the group represented by formula (A-1), and if m1 is 2 or more, there are multiple A 1 They may be the same or they may be different, R 1 R represents a substituent, and if n1 is 2, there are multiple R 1 They may be the same or they may be different, R 1 They may be bonded together to form a ring, R 2 R represents a hydrogen atom or substituent, and if n2 is 2 or more, there are multiple R atoms. 2 They may be the same or different; however, if n1 is 1 or 2, there are n1 R 1 At least one of them is a group having an alkylene oxy group, or n2 L 1 At least one of them is a linking group having an alkylene oxy group, and when n1 is 0, n2 L 1 At least one of them is a linking group having an alkylene oxy group; in formula (2), n11 represents 0 or 1, n12 represents 1 or 2, n11 + n12 is 2, m11 represents an integer from 1 to 5, s11 represents an integer from 2 to 100, L 11 This represents a linking group with m11+1 valency, and there are multiple L 11 They may be the same or they may be different. 11 This represents the base represented by formula (A-1), and there are multiple A 11 They may be the same or they may be different, R11 R represents a substituent, and there are multiple R's. 11 They may be the same or they may be different, R 12 R represents a hydrogen atom or substituent, and there are multiple R's. 12 They may be the same or they may be different, L 12 R represents a linking group with s11 valency; however, if n11 is 1, there are multiple R groups. 11 At least one of the groups has an alkylene oxy group, or there are multiple L groups. 11 At least one of them is a linking group having an alkylene oxy group, or L 12 The linking group has an alkylene oxy group, and if n11 is 0, there are multiple L 11 At least one of them is a linking group having an alkylene oxy group, or L 12 This is a linking group having an alkylene oxy group.
[0036] In formula (A-1), R a1 Y represents a hydrogen atom or substituent. a1 represents -O- or -NH-, and * represents a bonding hand.
[0037] -Regarding equation (1)- In equation (1), n1 represents an integer from 0 to 2, n2 represents an integer from 1 to 3, and n1 + n2 is 3. It is preferable that n1 is 1 or 2, and more preferably 1. It is preferable that n2 is 1 or 2, and more preferably 2.
[0038] In formula (1), m1 represents an integer from 1 to 5, preferably an integer from 2 to 5, more preferably an integer from 3 to 5, even more preferably 4 or 5, and particularly preferably 5.
[0039] L in equation (1) 1 The m1+1 valent linking groups represented by include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, heterocyclic groups, -O-, -S-, -CO-, -COO-, -OCO-, and -SO 2Examples include -, -NH-, -NHCO-, -CONH-, -NHCONH-, -NHCOO-, -OCONH-, and combinations of two or more of these groups.
[0040] The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group may also be linear, branched, or cyclic. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, even more preferably 1 to 10, and particularly preferably 1 to 5. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 12, and even more preferably 6. The heterocyclic group is preferably a monocyclic or a fused ring with 2 to 4 condensation units. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. The heteroatoms constituting the ring of the heterocyclic group are preferably nitrogen, oxygen, or sulfur atoms. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12. The aliphatic hydrocarbon group, aromatic hydrocarbon group, and heterocyclic group may have substituents. Examples of substituents include hydroxyl groups, alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, halogen atoms, cyano groups, and nitro groups.
[0041] L 1 It is preferable that the linking group contains an alkylene oxy group. The alkylene oxy group has two or more carbon atoms, more preferably two to ten, even more preferably two to five, and even more preferably two or three. The alkylene oxy group is preferably linear or branched, and more preferably linear.
[0042] L 1 Preferably, it contains a group represented by the above formula (L-101).
[0043] L 1 It is also preferable that the group includes a ring structure. Examples of ring structures include aliphatic rings and aromatic rings, with aromatic rings being preferred and aromatic hydrocarbon rings being more preferred.
[0044] L 1 It is also preferable that the linking group includes an alkylene oxy group and a ring structure.
[0045] If n² in equation (1) is 2 or greater, there are multiple L 1 They may be the same or they may be different.
[0046] This represents the group represented by formula (A-1) in formula (1). Details of the group represented by formula (A-1) will be described later. If m1 in formula (1) is 2 or more, there are multiple A 1 They may be the same or they may be different.
[0047] R in equation (1) 1 Examples of substituents represented by include hydrocarbon groups, heteroaryl groups, and groups having alkylene oxy groups.
[0048] Examples of the hydrocarbon groups mentioned above include alkyl groups, aryl groups, and groups combining these. The number of carbon atoms in an alkyl group is preferably 1 to 30. The upper limit is preferably 25 or less, and more preferably 20 or less. The lower limit is preferably 3 or more, more preferably 5 or more, and even more preferably 8 or more. The alkyl group may be linear, branched, or cyclic, but it is preferably linear or branched, and more preferably linear. The number of carbon atoms in an aryl group is preferably 6 to 30, more preferably 6 to 20, even more preferably 6 to 12, and particularly preferably 6.
[0049] The above hydrocarbon group may have substituents. Examples of substituents include the substituent T shown below. Substituents T include heteroaryl groups, halogen atoms, cyano groups, nitro groups, and -ORt 1 , -CORt 1 , -COORt 1 , -OCORt 1 , -NRt 1 Rt 2 ,-NHCORT 1 , -CONRt 1 Rt 2 ,-NHCONRt 1 Rt2 ,-NHCOORt 1 , -SRt 1 , -SO 2 Rt 1 , -SO 2 ORt 1 , - NHSO 2 Rt 1 and -SO 2 NRt 1 Rt 2 This is one example. Rt 1 and Rt 2 Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group. 1 and RT 2 They may combine to form a ring.
[0050] Examples of groups having the alkylene oxy group mentioned above include the group represented by formula (R-101).
[0051] -L r101 - (L r102 ) r -R r101 ...(R-101)
[0052] In formula (R-101), L r101 L represents a single bond or an alkylene group. r102 represents an alkylene oxy group, R r101 represents a hydrogen atom or substituent, and r represents an integer of 1 or more.
[0053] L in formula (R-101) r101 The number of carbon atoms in the alkylene group represented by is preferably 1 to 20. The upper limit is preferably 15 or less, and more preferably 10 or less. The alkylene group may be linear, branched, or cyclic, but it is preferably linear or branched, and more preferably linear.
[0054] L in formula (R-101) r102 The alkylene oxy group represented by is preferably 2 or more carbon atoms, more preferably 2 to 10, even more preferably 2 to 5, and even more preferably 2 or 3. The alkylene oxy group is preferably linear or branched, and more preferably linear.r102 The alkyleneoxy group represented by is preferably an ethyleneoxy group.
[0055] In formula (R-101), r represents an integer of 1 or more, preferably 1 to 75, more preferably 1 to 40, and even more preferably 1 to 25.
[0056] For R in formula (R-101) r101 Examples of the substituent represented by include an alkyl group, an aryl group, and the above-described substituent T. The preferred ranges of the alkyl group and the aryl group are the same as those described above. The alkyl group and the aryl group may further have a substituent. Examples of the further substituent include the above-described substituent T.
[0057] For R in formula (1) 1 The ClogP value of is preferably 3 to 12. For R 1 If the ClogP value of is 3 or more, the resistance of the film obtained using the photocurable composition to the developer is good, and a film having excellent adhesion can be formed. For R 1 If the ClogP value of is 12 or less, the dissolved oxygen amount of the specific amine monomer is high, and the sensitivity of the photocurable composition can be further increased. For R 1 The upper limit of the ClogP value of is preferably 11.5 or less, more preferably 11 or less. For R 1 The lower limit of the ClogP value of is preferably 3.5 or more, more preferably 4 or more. In this specification, the ClogP value of R 1 is a value calculated by replacing the bond with a hydrogen atom. Examples of the group having a ClogP value of 3 to 12 include the groups shown below.
[0058] For R 1 is preferably an unsubstituted alkyl group having 8 or more carbon atoms, more preferably an unsubstituted alkyl group having 8 to 30 carbon atoms, even more preferably an unsubstituted alkyl group having 8 to 25 carbon atoms, and still more preferably an unsubstituted alkyl group having 8 to 20 carbon atoms, because it can improve the resistance of the film to the developer and form a film having more excellent adhesion.
[0059] If n1 in equation (1) is 2, then there are multiple R 1 They may be the same or they may be different, R 1 The elements may be joined together to form a ring. The formed ring is preferably a five-membered or six-membered ring.
[0060] R in equation (1) 2 R represents a hydrogen atom or substituent. 2 Examples of substituents represented by include alkyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 3, and even more preferably 1. 2 It is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
[0061] If n² in equation (1) is 2 or greater, there are multiple R 2 They may be the same or they may be different.
[0062] In equation (1), if n1 is 1 or 2, there are n1 R 1 At least one of them is a group having an alkylene oxy group, or n2 L 1 At least one of them is a linking group having an alkylene oxy group. That is, when n1 is 1 or 2, R 1 and L 1 At least one of them contains an alkylene oxy group. 1 and L 1 Only one of them may contain an alkylene oxy group, R 1 and L 1 It may contain an alkylene oxy group.
[0063] In equation (1), when n1 is 0, n2 L 1 At least one of these is a linking group having an alkylene oxy group.
[0064] -Regarding equation (2)- L in equation (2) 11 , R 11 , R 12 and A 11 L is in equation (1) 1 , R 1 , R2 and A 1 This is synonymous with the same thing, and the preferred range is also similar.
[0065] In equation (2), n11 represents 0 or 1, n12 represents 1 or 2, and n11 + n12 is 2. It is preferable that n11 and n12 are 1.
[0066] In formula (2), m11 represents an integer from 1 to 5, preferably an integer from 2 to 5, more preferably an integer from 3 to 5, even more preferably 4 or 5, and particularly preferably 5.
[0067] In formula (2), s11 represents an integer between 2 and 100, preferably between 2 and 10, more preferably between 2 and 6, even more preferably between 2 and 4, and particularly preferably 2.
[0068] L in equation (2) 12 The s11 valent linking groups represented by are, in table form, aliphatic hydrocarbon groups, aromatic hydrocarbon groups, heterocyclic groups, -O-, -S-, -CO-, -COO-, -OCO-, -SO 2 Examples include -, -NH-, -NHCO-, -CONH-, -NHCONH-, -NHCOO-, -OCONH-, and combinations of two or more of these groups.
[0069] The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group may also be linear, branched, or cyclic. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, even more preferably 1 to 10, and particularly preferably 1 to 5. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 12, and even more preferably 6. The heterocyclic group is preferably a monocyclic or a fused ring with 2 to 4 condensation units. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. The heteroatoms constituting the ring of the heterocyclic group are preferably nitrogen, oxygen, or sulfur atoms. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12. The aliphatic hydrocarbon group, aromatic hydrocarbon group, and heterocyclic group may have substituents. Examples of substituents include hydroxyl groups, alkyl groups, alkoxy groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, halogen atoms, cyano groups, and nitro groups.
[0070] L 12 It is preferable that it contains an alkylene oxy group. The alkylene oxy group preferably has 2 or more carbon atoms, more preferably 2 to 10, even more preferably 2 to 5, and even more preferably 2 or 3 carbon atoms. The alkylene oxy group is preferably linear or branched, and more preferably linear.
[0071] L 12 Preferably, it contains a group represented by the above formula (L-101).
[0072] L 12 It is also preferable that the group includes a ring structure. Examples of ring structures include aliphatic rings and aromatic rings, with aromatic rings being preferred and aromatic hydrocarbon rings being more preferred.
[0073] L 12 It is also preferable that the group includes an alkylene oxy group and a ring structure.
[0074] In equation (2), if n11 is 1, there are multiple R 11At least one of the groups has an alkylene oxy group, or there are multiple L groups. 11 At least one of them is a linking group having an alkylene oxy group, or L 12 This is a linking group having an alkylene oxy group. That is, when n11 is 1, R 11 , L 11 and L 12 At least one of them contains an alkylene oxy group. 11 , L 11 and L 12 Only one of them may contain an alkylene oxy group, R 11 and L 11 It may contain an alkylene oxy group, R 11 and L 12 L may contain an alkylene oxy group. 11 and L 12 It may contain an alkylene oxy group, R 11 , L 11 and L 12 Each of these may contain an alkylene oxy group.
[0075] In equation (2), if n11 is 0, there are multiple L 11 At least one of them is a linking group having an alkylene oxy group, or L 12 This is a linking group having an alkylene oxy group. That is, when n11 is 0, L 11 and L 12 At least one of them contains an alkylene oxy group. 11 and L 12 Only one of them may contain an alkylene oxy group, L 11 and L 12 It may contain an alkylene oxy group.
[0076] -Regarding the base represented by equation (A-1)- R of equation (A-1) a1 R represents a hydrogen atom or substituent. a1 Examples of substituents represented by include alkyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 3, and even more preferably 1. a1Y in formula (A-1) is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom. a1 represents -O- or -NH-, and -O- is preferred.
[0077] The specific amine monomer is preferably a compound containing two or more ethylenically unsaturated bond-containing groups, more preferably a compound containing three or more, and even more preferably a compound containing six or more, for the reason that the sensitivity of the photocurable composition can be further enhanced. The upper limit of the number of ethylenically unsaturated bond-containing groups contained in the specific amine monomer is preferably 100 or less, more preferably 50 or less, and even more preferably 20 or less.
[0078] The specific amine monomer is preferably a compound containing an aromatic ring. According to this embodiment, the sensitivity of the photocurable composition can be further increased. When the specific amine monomer is a compound containing an aromatic ring, the number of aromatic rings contained in the specific amine monomer is preferably 1 to 30. The lower limit is preferably 2 or more, and more preferably 4 or more. The upper limit is preferably 20 or less, and more preferably 15 or less, from the viewpoint of adhesion.
[0079] The pKaH of the specific amine monomer is preferably 5.5 or higher, more preferably 6.5 or higher, and even more preferably 7.5 or higher, because this enhances the effect of suppressing oxygen inhibition by the amine and further increases the sensitivity of the photocurable composition. Note that pKaH is a value representing the pKa of the conjugate acid of the base. In this specification, the pKaH value of the specific amine monomer is the value calculated according to the method described in A Web Server for Small Molecular pKa Prediction Using a Graph-Convolutional Neural Network J. Chem. Inf. Model. 2021, 61, 7, 3159-3165.
[0080] The ethylenically unsaturated bond content value (C=C value) of a specific amine monomer is preferably 0.5 mmol / g or more, more preferably 1 mmol / g or more, and even more preferably 1.5 mmol / g or more, for the reason that it allows for the formation of a film with superior adhesion. The upper limit is preferably 11 mmol / g or less, more preferably 10 mmol / g or less, and even more preferably 9 mmol / g or less, for the reason that it allows for the formation of a film with superior adhesion. The ethylenically unsaturated bond content value of a specific amine monomer is a numerical value representing the molar amount of ethylenically unsaturated bond-containing groups per gram of solid content of the specific compound.
[0081] The amine value of the specific amine monomer is preferably 200 mg KOH / g or less, more preferably 130 mg KOH / g or less, and even more preferably 80 mg KOH / g or less, as this allows for the formation of a film with superior adhesion. The lower limit of the amine value is preferably 1 mg KOH / g or more, more preferably 2.5 mg KOH / g or more, and even more preferably 5 mg KOH / g or more, from the viewpoint of sensitivity.
[0082] The ratio of the C=C value to the amine value of a specific amine monomer (amine value / C=C value) is preferably 0.5 to 250. If the above ratio is 0.5 or higher, the sensitivity of the photocurable composition can be further increased. If the above ratio is 250 or lower, a film with better adhesion can be formed. The lower limit of the above ratio is preferably 1 or higher, and more preferably 3 or higher. The upper limit of the above ratio is preferably 100 or lower, and more preferably 50 or lower.
[0083] The hydroxyl value of the specific amine monomer is preferably 150 mg KOH / g or less, more preferably 100 mg KOH / g or less, and even more preferably 50 mg KOH / g or less, because it allows for the formation of a film with superior adhesion.
[0084] The molecular weight of the specific amine monomer is preferably 100 to 5000, and more preferably 200 to 3000.
[0085] It is also preferable to use specific amine monomers in combination with compounds having different numbers of ethylenically unsaturated bond-containing groups. One preferred embodiment is the combination of a specific amine monomer having six or more ethylenically unsaturated bond-containing groups (hereinafter also referred to as specific amine monomer a1) and a specific amine monomer having one to five ethylenically unsaturated bond-containing groups (hereinafter also referred to as specific amine monomer a2). According to this embodiment, by using multiple polymerizable monomers in combination, the fluidity of the film can be improved and the polymerization rate can be further increased. When specific amine monomer a1 and specific amine monomer a2 are used in combination, the ratio is preferably 1 to 2000 parts by mass of specific amine monomer a2 per 100 parts by mass of specific amine monomer a1, more preferably 2.5 to 1500 parts by mass, and even more preferably 5 to 1000 parts by mass.
[0086] Specific amine monomers can be synthesized by Michael addition reaction between the following starting amines and starting polyfunctional monomers. The starting amines are primary amino groups (-NH 2 The compound has at least one selected from a amine and a secondary amino group (-NH-), and the starting polyfunctional monomer is a compound having two or more ethylenically unsaturated bond-containing groups in one molecule. However, at least one of the starting amine and the starting polyfunctional monomer is a compound having an alkylene oxy group.
[0087] Specific amine monomers can also be synthesized by reacting compound A1 and compound A2 as shown below. Compound A1 is an amino group-containing polyfunctional alcohol, and compound A2 is a (meth)acrylate chloride compound or a (meth)acrylate isocyanate compound. However, at least one of compound A1 and compound A2 is a compound having an alkylene oxy group.
[0088] Specific amine monomers can also be synthesized by dehydration condensation of an amino group-containing polyfunctional carboxylic acid and an alcohol compound having an ethylenically unsaturated bond-containing group. However, at least one of the amino group-containing polyfunctional carboxylic acid and the alcohol compound having an ethylenically unsaturated bond-containing group must be a compound having an alkylene oxy group.
[0089] Specific amine monomers can also be synthesized by dehydration condensation of an amino group-containing polyfunctional alcohol and a carboxylic acid compound having an ethylenically unsaturated bond-containing group. However, at least one of the amino group-containing polyfunctional alcohol and the carboxylic acid compound having an ethylenically unsaturated bond-containing group must be a compound having an alkylene oxy group.
[0090] Specific examples of specific amine monomers include M1 to M52 described in the examples below, and compounds with structures obtained by reacting a polyfunctional starting material monomer with multiple starting material amines.
[0091] The specific amine monomer may include by-products generated during the synthesis of the specific amine monomer described above. That is, the photocurable composition of the present invention may include by-products generated during the synthesis of the specific amine monomer described above. Examples of by-products include compounds with structures obtained by the reaction of one starting polyfunctional monomer with multiple starting amines.
[0092] (Other polymerizable monomers) The photocurable composition of the present invention may contain polymerizable monomers other than the specified amine monomers described above (hereinafter also referred to as other polymerizable monomers).
[0093] The molecular weight of the other polymerizable monomer is preferably between 100 and 3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, and even more preferably 250 or more.
[0094] Other polymerizable monomers are preferably compounds containing two or more ethylenically unsaturated bond-containing groups, more preferably compounds containing two to fifteen ethylenically unsaturated bond-containing groups, and even more preferably compounds containing two to six ethylenically unsaturated bond-containing groups. Furthermore, other polymerizable monomers are preferably 2 to 15-functional (meth)acrylate compounds, and more preferably 2 to 6-functional (meth)acrylate compounds. Specific examples of other polymerizable monomers include the compounds described in paragraphs 0075 to 0083 of International Publication No. 2022 / 065215 and the compounds described in Taiwan Patent Application Publication No. 201832008.
[0095] Other polymerizable monomers that are preferred include dipentaerythritol tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and compounds in which the (meth)acryloyl groups of these are linked via ethylene glycol and / or propylene glycol residues (for example, SR454 and SR499, commercially available from Sartomer).Other polymerizable monomers include diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available as M-460; manufactured by Toagosei), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., NK Ester A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronics TO-2349 (manufactured by Toagosei Co., Ltd.), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, and LINC-20. 2UA (manufactured by Kyoeisha Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (both manufactured by Taisei Fine Chemical Co., Ltd.), Light Acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), Aronics M-510, 520 (manufactured by Toagosei Co., Ltd., polymerizable monomer with acidic group), Etercure 6361-100 (Eternal Materials Inc. (polymerizable monomer having a hyperbranched structure), EBECRYL80 (amine-containing tetrafunctional monomer, manufactured by Daicel-Orkenes Inc.), EBECRYL7100 (amine-containing difunctional monomer, manufactured by Daicel-Orkenes Inc.), CN371NS (amine-containing difunctional monomer, manufactured by Arkema Inc.), HOA-MPL (2-acryloyloxyethyl phthalic acid, manufactured by Kyoeisha Chemical Co., Ltd.), HOA-MPE (2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, manufactured by Kyoeisha Chemical Co., Ltd.), dendrimer structure described in Japanese Patent Publication No. 2023-043479 Alternatively, polymerizable monomers having a hyperbranch structure, polymerizable monomers described in Japanese Patent Publication No. 2023-529984, polymerizable monomers described in International Publication No. 2023 / 190562, (meth)acrylate compounds described in Japanese Patent Application Publication No. 2023-173204, polymerizable compounds containing urethane bonds described in Japanese Patent Application Publication No. 2024-070237, EBECRYL 5129 (manufactured by Daicel Ornex Co., Ltd.), EBECRYL 220 (manufactured by Daicel Ornex Co., Ltd.), KUA-9N (manufactured by KSM Co., Ltd.), polymerizable compounds described in Japanese Patent Application Publication No. 2024-085753, etc. may also be used.
[0096] Other polymerizable monomers can also be used, specifically those having a fluorene skeleton. The polymerizable monomer having a fluorene skeleton is preferably a bifunctional polymerizable monomer. Examples of commercially available polymerizable monomers having a fluorene skeleton include Ogusol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).
[0097] When the photocurable composition of the present invention contains the other polymerizable monomers described above, it is preferable that either the specified amine monomer or the other polymerizable monomer described above contains a compound having six or more ethylenically unsaturated bond-containing groups, and the other contains a compound having one to five ethylenically unsaturated bond-containing groups. In this embodiment, it is preferable that the specified amine monomer described above contains a compound having six or more ethylenically unsaturated bond-containing groups, for the reason that the effects of the present invention are more pronounced.
[0098] The content of polymerizable monomers in the total solids of the photocurable composition is preferably 1 to 20% by mass. The upper limit is preferably 15% by mass or less, and more preferably 12% by mass or less. The lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more.
[0099] The content of the above-mentioned specific amine monomer in the polymerizable monomer is preferably 50% by mass or more, more preferably 75% by mass or more, and even more preferably 90% by mass or more.
[0100] The photocurable composition of the present invention preferably contains substantially no other polymerizable monomers. In this embodiment, the effects of the present invention are more pronounced. In this specification, "substantially containing no other polymerizable monomers" means that the content of other polymerizable monomers in the total solid content of the photocurable composition is 0.1% by mass or less, preferably 0.01% by mass or less, and even more preferably no other polymerizable monomers.
[0101] The photocurable composition of the present invention may contain only one polymerizable monomer or two or more polymerizable monomers. When two or more polymerizable monomers are included, it is preferable that their total amount falls within the above range.
[0102] <<Photopolymerization Initiator>> The photocurable composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator.
[0103] The photopolymerization initiator used in the photocurable composition of the present invention contains an oxime compound.
[0104] Examples of oxime compounds include the compounds described in paragraph 0142 of International Publication No. 2022 / 085485, the compounds described in Japanese Patent No. 5430746, the compounds described in Japanese Patent No. 5647738, the compounds represented by general formula (1) and the compounds described in paragraphs 0022 to 0024 of Japanese Patent Publication No. 2021-173858, the compounds represented by general formula (1) and the compounds described in paragraphs 0117 to 0120 of Japanese Patent Publication No. 2021-170089, the oxime-based photopolymerization initiators described in Japanese Patent Publication No. 2013-190459, and Polymers described in Japanese Patent Publication No. 2020-172619, compounds represented by formula 1 described in International Publication No. 2020 / 152120, compounds described in Japanese Patent Publication No. 2021-181406, photopolymerization initiators described in Japanese Patent Publication No. 2022-013379, compounds represented by formula (1) described in Japanese Patent Publication No. 2022-015747, fluorine-containing fluorene oxime ester photoinitiators described in Japanese Patent Publication No. 2021-507058, initiators described in Chinese Patent Application Publication No. 110764367, Japanese Patent Publication No. 2022- The initiator described in Patent Publication No. 518535, the initiator described in International Publication No. 2021 / 175855, the compound described in Taiwan Patent Application Publication No. 202200534, the compound described in Japanese Patent Application Publication No. 2022-078550, the compound described in Korean Published Patent No. 10-2017-0087330, the compound described in International Publication No. 2022 / 075452, the oxime ester compound described in Chinese Patent Application Publication No. 110066225, the compound described in Korean Published Patent No. 10-2022-0076157 Compounds having a triarylamine or N-arylcarbazole skeleton, as described in paragraphs 0042 to 0062 of International Publication No. 2019 / 013112, oxime ester-based photopolymerization initiators described in Japanese Patent No. 7219378, photopolymerization initiators described in Korean Published Patent No. 10-2021-0146174, photopolymerization initiators described in International Publication No. 2019 / 013112, photopolymerization initiators described in Japanese Patent Publication No. 2023-033731, initiators described in Japanese Patent Publication No. 2022-515524, initiators described in Japanese Patent Publication No. 2023-517304.Examples include the initiator described in Chinese Patent Application Publication No. 114149517, the compound described in Japanese Patent Publication No. 2023-159489, the compound described in Japanese Patent Publication No. 2023-159487, the compound described in Taiwan Patent Application Publication No. 202336003, the compound described in Chinese Patent Application Publication No. 113527138, the oxime compound described in Chinese Patent Application Publication No. 111752099, the photopolymerization initiator described in Japanese Patent Publication No. 2024-124479, the photopolymerization initiator described in Japanese Patent Publication No. 2024-535245, and the oxime ester compound described in Japanese Patent Publication No. 2024-149305.
[0105] Specific examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one, and 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime). Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04, Irgacure OXE05 (all manufactured by BASF), TR-PBG-301, TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-3054, TR-PBG-3057, TR-PBG-314, TR-PBG-327, TR-PBG-345, TR-PBG-346, TR- Examples include PBG-358, TR-PBG-365, TR-PBG-380, TR-PBG-610, TR-PBG-A, TR-PBG-B (all manufactured by TRONLY), and ADEKA Optomer N-1919 (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in Japanese Patent Publication No. 2012-014052). Furthermore, it is also preferable to use compounds that do not produce color or compounds that are highly transparent and resistant to discoloration as oxime compounds. Examples of commercially available products include ADEKA Arclus NCI-730, NCI-831, NCI-831E, and NCI-930 (all manufactured by ADEKA Corporation).
[0106] As oxime compounds, you may also use oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring, oxime compounds having a fluorine atom, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, oxime compounds in which a substituent having a hydroxyl group is attached to the carbazole skeleton, and compounds described in paragraphs 0143 to 0149 of International Publication No. 2022 / 085485.
[0107] The oxime compound is preferably a compound represented by formula (OX-1). By using such an oxime compound as a photopolymerization initiator, a photocurable composition with higher sensitivity can be obtained.
[0108] In formula (OX-1), X 1a R represents a divalent linking group containing at least one selected from the group consisting of aromatic rings and heterocycles. 1a R represents a hydrogen atom or an acyl group. 2a R represents an alkyl or aryl group. 3a and R 4a Each of these independently represents a hydrogen atom or an alkyl group, and Alk 1 and Alk 2 Each of these independently represents an alkyl group, and R 3a and R 4a They may be bonded together to form a ring, Alk 1 and Alk 2 The elements may be joined together to form a ring, and n represents either 0 or 1.
[0109] X in equation (OX-1) 1a Examples of divalent linking groups represented by include divalent aromatic ring groups, divalent heterocyclic groups, divalent groups formed by linking two or more aromatic ring groups via single bonds or linking groups, divalent groups formed by linking two or more heterocyclic groups via single bonds or linking groups, and divalent groups formed by linking an aromatic ring group and a heterocyclic group via single bonds or linking groups. Examples of linking groups that link aromatic ring groups to each other, heterocyclic groups to each other, or an aromatic ring group and a heterocyclic group include -CH 2 -, -O-, -CO-, -S-, -NR x - And combinations thereof, etc. are examples. x This represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.
[0110] X in equation (OX-1) 1aIt is preferably a group represented by any of formulas (X-1) to (X-13), more preferably a group represented by formula (X-1), formula (X-2), formula (X-4), formula (X-6), or formula (X-8), and even more preferably a group represented by formula (X-2) or formula (X-6).
[0111] In the formula R X1 ~R X9 Each of these independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and * represents a bond.
[0112] R X1 ~R X9 The alkyl group represented by is preferably 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, and heteroaryl groups.
[0113] R X1 ~R X9 The number of carbon atoms in the alkenyl group represented by is preferably 2 to 15, and more preferably 2 to 10. The alkenyl group may be linear, branched, or cyclic. The alkenyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, and heteroaryl groups.
[0114] R X1 ~R X9 The alkynyl group represented by is preferably 2 to 15 carbon atoms, and more preferably 2 to 10 carbon atoms. The alkynyl group may be linear, branched, or cyclic. The alkynyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, and heteroaryl groups.
[0115] R X1 ~R X9The number of carbon atoms in the aryl group represented by is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and heteroaryl groups.
[0116] R X1 ~R X9 The heteroaryl group represented by is preferably a five-membered or six-membered ring. The heteroatoms of the heteroaryl group are preferably oxygen, nitrogen, and sulfur atoms. The number of heteroatoms of the heteroaryl group is preferably 1 to 3. The heteroaryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.
[0117] R in equation (OX-1) 1a represents a hydrogen atom or an acyl group, and an acyl group is preferred.
[0118] R in equation (OX-1) 2a R represents an alkyl group or an aryl group, and is preferably an alkyl group because the generated radical is highly reactive. 2a The number of carbon atoms in the alkyl group represented by is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have substituents, but is preferably an unsubstituted alkyl group. 2a The alkyl group represented by is preferably an unsubstituted linear or branched alkyl group, and more preferably an unsubstituted linear alkyl group. 2a The number of carbon atoms in the aryl group represented by is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents, but it is preferably an unsubstituted aryl group.
[0119] R in equation (OX-1) 3a and R 4aEach of these independently represents a hydrogen atom or an alkyl group, and a hydrogen atom is preferred. 3a and R 4a The number of carbon atoms in the alkyl group represented by is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have substituents, but is preferably an unsubstituted alkyl group. 3a and R 4a These may be bonded together to form a ring. The formed ring is preferably a five-membered or six-membered ring, and more preferably a five-membered or six-membered aliphatic hydrocarbon ring.
[0120] Alk in equation (OX-1) 1 and Alk 2 Each of these independently represents an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have substituents, but is preferably an unsubstituted alkyl group. Alk 1 and Alk 2 The elements may be bonded together to form a ring, and it is preferable that a ring is formed. The formed ring is preferably a five-membered or six-membered ring, more preferably a five-membered or six-membered aliphatic hydrocarbon ring, and even more preferably a cyclopentane ring or a cyclohexane ring.
[0121] In formula (OX-1), n represents either 0 or 1, and is preferably 0.
[0122] Specific examples of compounds represented by formula (OX-1) include the compounds described in paragraphs 0092 to 0096 of Japanese Patent Publication No. 2012-113104 and the compounds described in paragraph 0041 of Japanese Patent Publication No. 2012-189997.
[0123] The oxime compound can also be a compound represented by formula (OX-2).
[0124]
[0125] In formula (OX-2), R 1b and R 2b Each of these independently represents a substituent, R 3b ~R 7b Each of these independently represents a hydrogen atom or a substituent, and Ar 1b represents an optionally substituted aryl group or an optionally substituted heteroaryl group, and n represents 0 or 1.
[0126] R 1b and R 2b The substituents represented by include alkyl groups and aryl groups, with alkyl groups being preferred. The number of carbon atoms in the alkyl group is preferably 1 to 15, and more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, alkenyl groups, alkynyl groups, and heteroaryl groups. The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and heteroaryl groups.
[0127] R 3b ~R 7b The substituents represented by include halogen atoms, alkyl groups, and aryl groups. Examples of alkyl groups and aryl groups are those mentioned above. 3b ~R 7b It is preferable that it is a hydrogen atom.
[0128] Ar 1b Ar represents an optionally substituted aryl group or an optionally substituted heteroaryl group. 1bIt is preferable that the group is an aryl group which may have substituents. The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylthio groups, arylthio groups, nitro groups, and acyl groups, with acyl groups being preferred.
[0129] The oxime compound can also be a compound represented by formula (OX-3).
[0130]
[0131] In formula (OX-3), Ar 1c Ar represents an aromatic ring group with (k+m+1) valency or a heterocyclic ring group with (k+m+1) valency. 2c R represents a (k+2) valent aromatic ring group or a (k+2) valent heterocyclic group, 1c ~R 3c Each of these independently represents a substituent, L 1c is a single bond or CR 11c R 12c Represents R 11c and R 12c Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, X 1c ha-CH 2 It represents -, -N-, -O-, or -S-, where k represents 0 or 1, m represents an integer from 0 to 4, and n represents 0 or 1.
[0132] R 1c and R 2cThe substituents represented by include alkyl groups and aryl groups, with alkyl groups being preferred. The number of carbon atoms in the alkyl group is preferably 1 to 15, and more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, alkenyl groups, alkynyl groups, and heteroaryl groups. The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and heteroaryl groups. 2c It is preferable that the alkyl group has a branched or cyclic structure.
[0133] R 3c Examples of substituents represented by include halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, and acyl groups, with acyl groups being preferred.
[0134] L 1c is a single bond or CR 11c R 12c Represents R 11c and R 12c Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group. 11c and R 12c The alkyl and aryl groups in R 1c and R 2c This is synonymous with alkyl and aryl groups in [the given context]. When k is 1, L 1c It is preferable that the bond is a single bond.
[0135] X 1c is, -CH 2 It represents -, -N-, -O-, or -S-, with -O- or -S- being preferred.
[0136] Ar 1crepresents a (k+m+1) valent aromatic ring group or a (k+m+1) valent heterocyclic group, and is preferably a (k+m+1) valent aromatic ring group. The aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.
[0137] Ar 2c represents a (k+2) valent aromatic ring group or a (k+2) valent heterocyclic group, and is preferably a (k+2) valent aromatic ring group. The aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.
[0138] k represents 0 or 1, preferably 0. m represents an integer from 0 to 4, preferably 0 or 1, more preferably 1. n represents 0 or 1, preferably 0.
[0139] As the oxime compound, a ketoxime ester compound having an allyl oil oxy group at the ortho position, represented by formula (OX-4), can be used. Examples of such compounds include those described in Chinese Patent Application Publication No. 117342977.
[0140] In formula (OX-4), R 1d and R 2d Each of these independently represents an alkyl group, an aryl group, or a heterocyclic group; R 3d , R 4d , R 5d , R 6d These are, independently, hydrogen atoms, halogen atoms, CN, and NO. 2 CF 3 ,R,OR,SR,SOR,SO 2 R represents R or NRR', where R and R' each independently represent an alkyl group or an aryl group, and when R and R' are present together, R and R' may be bonded to form a ring, and one or more -CH groups in the alkyl group or aryl group represented by R and R' 2 Each of the hyphens may be independently substituted with -O-, -N-, -S-, -CO-, -COO-, -OCO-, or a benzene ring; R 7d , R8d and R 9d Each of these independently represents either a hydrogen atom or a methyl group.
[0141] The oxime compound can be a compound represented by formula (OX-5). Examples of such compounds are those described in International Publication No. 2024 / 101219.
[0142] In formula (OX-5), R 1e ~R 5e Each of these independently represents a hydrocarbon group which may have substituents, and n represents an integer from 0 to 4.
[0143] Specific examples of oxime compounds include the following compounds.
[0144]
[0145]
[0146]
[0147]
[0148]
[0149] The photocurable composition of the present invention may further contain compounds other than oxime compounds (hereinafter also referred to as other photopolymerization initiators).
[0150] Other photopolymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, hexaarylbiimidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds, glyoxylate compounds, and 3-aryl-substituted coumarin compounds. Glyoxylate compounds, α-hydroxyketone compounds, α-aminoketone compounds, or acylphosphine compounds are preferred, and glyoxylate compounds, α-hydroxyketone compounds, or α-aminoketone compounds are more preferred.
[0151] Specific examples of hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole.
[0152] Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins B.V.), and Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all manufactured by BASF). Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins B.V.), and Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (all manufactured by BASF). Commercially available acylphosphine compounds include Omnirad 819 and Omnirad TPO (both manufactured by IGM Resins B.V.), and Irgacure 819 and Irgacure TPO (both manufactured by BASF). Examples of commercially available glyoxylate compounds include Esacure 563 (manufactured by IGM Resins B.V.).
[0153] Other photopolymerization initiators that can be used include the photopolymerization initiator described in Japanese Patent Publication No. 2024-537185 and the aminoketone compound described in Japanese Patent Publication No. 2024-534719.
[0154] The content of the photopolymerization initiator in the total solids of the photocurable composition is preferably 0.1 to 10% by mass. The upper limit is preferably 8% by mass or less, and more preferably 6% by mass or less, for the reason that a film with better adhesion can be formed. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more, from the viewpoint of sensitivity. The total content of polymerizable monomer and photopolymerization initiator in the total solids of the photocurable composition is preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 17.5% by mass or less, and particularly preferably 15% by mass or less. The photocurable composition of the present invention may contain only one type of photopolymerization initiator, or it may contain two or more types. If two or more types are included, it is preferable that their total amount be within the above range.
[0155] The content of the oxime compound in the total solid content of the photocurable composition is preferably 0.1 to 10% by mass. The upper limit is preferably 8% by mass or less, and more preferably 6% by mass or less, for the reason that a film with better adhesion can be formed. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more, from the viewpoint of sensitivity. The photocurable composition of the present invention may contain only one oxime compound or may contain two or more. If it contains two or more, it is preferable that their total amount is within the above range.
[0156] The content of the oxime compound in the photopolymerization initiator contained in the photocurable composition is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 99% by mass or more, for the reason that the effects of the present invention are more pronounced.
[0157] If the photocurable composition of the present invention contains other photopolymerization initiators, the content of the other photopolymerization initiators is preferably 10 parts by mass or less per 100 parts by mass of the oxime compound. The upper limit is preferably 5 parts by mass or less, and more preferably 1 part by mass or less. The lower limit is preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more.
[0158] The photocurable composition of the present invention preferably contains substantially no other photopolymerization initiators. In this embodiment, the effects of the present invention are more pronounced. In this specification, "substantially containing no other photopolymerization initiators" means that the content of other photopolymerization initiators in the total solid content of the photocurable composition is 0.1% by mass or less, preferably 0.01% by mass or less, and even more preferably no other photopolymerization initiators.
[0159] <<Solvent>> The photocurable composition of the present invention preferably contains a solvent. Examples of solvents include organic solvents. The type of solvent is not particularly limited as long as it satisfies the solubility of each component and the applicability of the composition. Examples of organic solvents include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For further details, refer to paragraph 0223 of International Publication No. 2015 / 166779, which is incorporated herein by reference. In addition, ester solvents and ketone solvents substituted with cyclic alkyl groups can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene Examples include propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol.However, the amount of aromatic hydrocarbons used as organic solvents (benzene, toluene, xylene, ethylbenzene, etc.) may be reduced for environmental reasons (for example, it may be reduced to 50 ppm by mass (parts per million) or less, 10 ppm by mass or less, or 1 ppm by mass or less relative to the total amount of organic solvent).
[0160] It is preferable that the metal content of the organic solvent be low. The metal content of the organic solvent is preferably, for example, 10 ppb (parts per billion) or less by mass. If necessary, an organic solvent with a metal content at the ppt (parts per trillion) level by mass may be used; such organic solvents are provided, for example, by Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015).
[0161] Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin-film distillation, etc.) and filtration using a filter. The pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.
[0162] Organic solvents may contain isomers (compounds with the same number of atoms but different structures). Furthermore, they may contain only one type of isomer or multiple types.
[0163] It is preferable that the peroxide content in the organic solvent is 0.8 mmol / L or less, and more preferably that it is substantially peroxide-free.
[0164] The solvent content in the photocurable composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 90% by mass.
[0165] The photocurable composition of the present invention preferably contains substantially no environmentally regulated substances from the viewpoint of environmental regulations. In this invention, "substantially free of environmentally regulated substances" means that the content of environmentally regulated substances in the photocurable composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, more preferably 10 ppm by mass or less, and particularly preferably 1 ppm by mass or less. Examples of environmentally regulated substances include benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene, etc. These substances are registered as environmentally regulated substances under the REACH (Registration Evaluation Authorization and Restriction of Chemicals) regulations, the PRTR (Pollutant Release and Transfer Register) law, and the VOC (Volatile Organic Compounds) regulations, and their usage and handling methods are strictly regulated. These compounds are sometimes used as solvents when manufacturing components used in photocurable compositions, and may be mixed into the photocurable composition as residual solvents. From the standpoint of human safety and environmental considerations, it is preferable to reduce these substances as much as possible. One method for reducing environmentally regulated substances is to heat or reduce the pressure in the system to above the boiling point of the environmentally regulated substance and then distill off the environmentally regulated substance from the system. Furthermore, when removing small amounts of environmentally regulated substances by distillation, it is useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in question in order to increase efficiency. In addition, if the mixture contains compounds that exhibit radical polymerization, polymerization inhibitors may be added during reduced-pressure distillation to suppress the progression of radical polymerization reactions and the resulting crosslinking between molecules. These distillation methods can be implemented at any stage, including the raw material stage, the product stage (e.g., the polymerized resin solution or polyfunctional monomer solution), or the stage of the photocurable composition prepared by mixing these compounds.
[0166] <<Colorants>> The photocurable composition of the present invention preferably contains a colorant. Examples of colorants include white colorants, black colorants, chromatic colorants, and infrared absorbing colorants. Pigment derivatives can also be used as colorants. Examples of pigment derivatives include compounds having a structure in which an acidic group or a basic group is bonded to a pigment skeleton. Details of pigment derivatives will be described later. In this invention, the white colorant includes not only pure white but also light gray colorants that are close to white (e.g., off-white, light gray, etc.).
[0167] The colorant may be a pigment or a dye. Pigments and dyes may be used in combination. The pigment may be either an inorganic pigment or an organic pigment, but organic pigments are preferred from the viewpoint of a wide range of color variations, ease of dispersion, and safety. When pigments and dyes are used in combination, the dye content is preferably 5 to 100 parts by mass per 100 parts by mass of pigment. The upper limit is preferably 80 parts by mass or less, and more preferably 60 parts by mass or less. The lower limit is preferably 10 parts by mass or more, and more preferably 15 parts by mass or more.
[0168] The colorant preferably contains a pigment, and more preferably contains both a pigment and a pigment derivative. In particular, when a chromatic pigment or an infrared-absorbing pigment is used as the pigment, the colorant included in the photocurable composition preferably contains both a pigment and a pigment derivative. Furthermore, when a chromatic colorant is used as the colorant, the colorant included in the photocurable composition preferably contains a pigment, a dye, and a pigment derivative. The content of the pigment derivative is preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass, per 100 parts by mass of pigment. Only one type of pigment derivative may be used, or two or more types may be used in combination.
[0169] The average primary particle diameter of pigments and pigment derivatives is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, and more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. In this specification, the primary particle diameter of pigments and pigment derivatives can be determined by observing the primary particles of pigments and pigment derivatives with a transmission electron microscope and obtaining the resulting photographs. Specifically, the projected area of the primary particles of the pigment is determined, and the corresponding equivalent circle diameter is calculated as the primary particle diameter of the pigment. In addition, the average primary particle diameter in this invention is the arithmetic mean of the primary particle diameters of 400 primary particles of pigment. Furthermore, primary particles of pigment refer to independent particles that are not aggregated. The same applies to the average primary particle diameter of pigment derivatives.
[0170] The crystallite size of pigments and pigment derivatives is preferably 0.1 to 50 nm, more preferably 0.5 to 30 nm, and even more preferably 1 to 15 nm. The crystallite size can be determined from the full width at half maximum of the diffraction angle peak using an X-ray diffractometer, and is calculated using Scherrer's formula. The crystallite size of pigments and pigment derivatives can be adjusted by known methods such as adjusting the manufacturing conditions or grinding after manufacturing.
[0171] The specific surface area of pigments and pigment derivatives is 1 to 300 m². 2 It is preferable that it be / g. The lower limit is 10m 2 It is preferable that it be 30m or more per gram. 2 It is more preferable that the amount is 1 / g or more. The upper limit is 250m 2 It is preferable that the amount is less than or equal to 200m 2 It is more preferable that the value be less than or equal to / g. The specific surface area can be measured according to the BET (Brunauer, Emmett, and Teller) method and DIN 66131: determination of the specific surface area of solids by gas adsorption.
[0172] (Chromatic pigments) Examples of chromatic pigments include pigments that have a maximum absorption wavelength in the range of 400 to 700 nm. Examples include green pigments, red pigments, yellow pigments, purple pigments, blue pigments, and orange pigments.
[0173] Examples of red colorants include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, and thioindigo compounds. Diketopyrrolopyrrole compounds, anthraquinone compounds, and azo compounds are preferred, and diketopyrrolopyrrole compounds are more preferred. Furthermore, the red colorant is preferably a pigment (red pigment), and more preferably a diketopyrrolopyrrole pigment.
[0174] Specific examples of red pigments include C.I. (Color Index) Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, Examples of red pigments include 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, 279, 291, 294, 295, 296, and 297. In addition, as red colorants, compounds described in paragraph 0034 of International Publication No. 2022 / 085485 and brominated diketopyrrolopyrrole compounds described in Japanese Patent Application Publication No. 2020-085947 can also be used.
[0175] As the red colorant, C.I. Pigment Red 122, 177, 224, 254, 255, 264, 269, 272, and 291 are preferred, C.I. Pigment Red 254, 264, and 272 are more preferred, and C.I. Pigment Red 254 and 264 are even more preferred.
[0176] Examples of green colorants include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred. Furthermore, the green colorant is preferably a pigment (green pigment), and more preferably a phthalocyanine pigment.
[0177] Specific examples of green colorants include green pigments such as C.I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66. Alternatively, zinc phthalocyanine halides, which have an average of 10 to 14 halogen atoms, 8 to 12 bromine atoms, and 2 to 5 chlorine atoms per molecule, can be used as green colorants. Specific examples include the compounds described in International Publication No. 2015 / 118720. Furthermore, compounds described in paragraph 0029 of International Publication No. 2022 / 085485, aluminum phthalocyanine compounds described in Japanese Patent Publication No. 2020-070426, and diarylmethane compounds described in Japanese Patent Publication No. 2020-504758 can also be used as green colorants.
[0178] As for the green coloring agent, C.I. Pigment Green 7, 36, 58, 62, and 63 are preferred.
[0179] Examples of orange colorants include diketopyrrolopyrrole compounds and azo compounds. Preferably, the orange colorant is a pigment (orange pigment). Specific examples of orange colorants include C.I. Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, and 73 orange pigments.
[0180] Examples of yellow colorants include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds. The yellow colorant is preferably a pigment (yellow pigment). Specific examples of yellow colorants include C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125 Examples of yellow pigments include 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232, 233, 234, 235, and 236.
[0181] As a yellow coloring agent, a nickel azobarbiturate complex with the following structure can also be used.
[0182] As a yellow coloring agent, the compounds described in paragraphs 0031 to 0033 of International Publication No. 2022 / 085485, the methine dye described in Japanese Patent Publication No. 2019-073695, and the methine dye described in Japanese Patent Publication No. 2019-073696 can be used.
[0183] Examples of purple colorants include oxazine compounds, quinacridone compounds, perylene compounds, and indigo compounds, with oxazine compounds being preferred. The purple colorant is preferably a pigment (purple pigment). Specific examples of purple colorants include C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.
[0184] Examples of blue colorants include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred. The blue colorant is preferably a pigment (blue pigment). Specific examples of blue colorants include blue pigments such as C.I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, and 88. Furthermore, aluminum phthalocyanine compounds containing phosphorus atoms can also be used as blue colorants. Specific examples include the compounds described in paragraphs 0022-0030 of Japanese Patent Publication No. 2012-247591 and paragraph 0047 of Japanese Patent Publication No. 2011-157478.
[0185] Dyes can also be used as chromatic colorants. There are no particular restrictions on the dyes used, and known dyes can be used. Examples include pyrazole azo dyes, anilino azo dyes, triarylmethane dyes, anthraquinone dyes, anthrapyridone dyes, benzylidene dyes, oxonol dyes, pyrazolotriazole azo dyes, pyridone azo dyes, cyanine dyes, phenothiazine dyes, pyrrolopyrazole azomethine dyes, xanthene dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, and pyromethene dyes. Xanthene dyes are preferred.
[0186] A pigment polymer can also be used as a chromatic colorant. The pigment polymer is preferably a dye that is dissolved in a solvent before use. The pigment polymer may also form particles. When the pigment polymer is in particle form, it is usually used in a dispersed state in a solvent. Particle-form pigment polymers can be obtained, for example, by emulsion polymerization, and the compound and production method described in Japanese Patent Application Publication No. 2015-214682 are specific examples. The pigment polymer has two or more pigment structures in one molecule, and preferably three or more pigment structures. There is no particular upper limit, but it can be 100 or less. The multiple pigment structures in one molecule may be the same pigment structure or different pigment structures. The weight-average molecular weight (Mw) of the pigment polymer is preferably 2000 to 50000. The lower limit is more preferably 3000 or more, and even more preferably 6000 or more. The upper limit is more preferably 30000 or less, and even more preferably 20000 or less. The pigment polymer can also be a compound described in Japanese Patent Publication No. 2011-213925, Japanese Patent Publication No. 2013-041097, Japanese Patent Publication No. 2015-028144, Japanese Patent Publication No. 2015-030742, International Publication No. 2016 / 031442, etc.
[0187] As chromatic colorants, the following are used: the triarylmethane dye polymer described in Korean Published Patent No. 10-2020-0028160, the xanthene compound described in Japanese Patent Publication No. 2020-117638, the phthalocyanine compound described in International Publication No. 2020 / 174991, the isoindoline compound described in Japanese Patent Publication No. 2020-160279 or salts thereof, the compound represented by Formula 1 described in Korean Published Patent No. 10-2020-0069442, the compound represented by Formula 1 described in Korean Published Patent No. 10-2020-0069730, and the compound described in Korean Published Patent No. 10- Compound represented by formula 1 described in Japanese Patent Publication No. 2020-0069070, compound represented by formula 1 described in Korean Published Patent No. 10-2020-0069067, compound represented by formula 1 described in Korean Published Patent No. 10-2020-0069062, zinc halide phthalocyanine pigment described in Japanese Patent No. 6809649, isoindoline compound described in Japanese Patent Publication No. 2020-180176, phenothiazine compound described in Japanese Patent Publication No. 2021-187913, zinc halide phthalocyanine described in International Publication No. 2022 / 004261, International Publication Zinc halide phthalocyanine described in Japanese Patent Publication No. 2021 / 250883, quinophthalone compound represented by formula 1 in Korean Published Patent No. 10-2020-0030759, polymer dye described in Korean Published Patent No. 10-2020-0061793, chromatic colorant described in Japanese Patent Publication No. 2022-029701, isoindoline compound described in International Publication No. 2022 / 014635, aluminum phthalocyanine compound described in International Publication No. 2022 / 024926, compound described in Japanese Patent Publication No. 2022-045895, International Publication No. 2022 / 05005 The compound described in No. 1, the compound described in JP 2020-090676, the compound described in JP 2020-055956, the compound described in JP 2021-031681, the compound described in JP 2022-056354, the compound described in U.S. Patent Application Publication No. 2021 / 0355327, the compound described in International Publication No. 2022 / 065357, the compound described in JP 2020-045436, the compound described in Korean Published Patent No. 10-2021-0146726, the compound described in JP 2018-178039,Compounds described in Chinese Patent Application Publication No. 113881244, compounds described in Chinese Patent Application Publication No. 113881245, compounds described in Chinese Patent Application Publication No. 113881246, compounds described in Japanese Patent Publication No. 2022-104822, compounds described in Japanese Patent Publication No. 2022-096701, compounds described in Japanese Patent Publication No. 2020-023652, green pigments described on pages 80-84 of the Journal of the Color Materials Association (published in 2022), compounds described in Japanese Patent Publication No. 2022-143135, compounds described in Japanese Patent Publication No. 2022-140287, International Publication No. The compound described in JP 2022 / 136308, the perylene compound described in Chinese Patent Application Publication No. 113061349, the cyanide pigment described in Korean Published Patent No. 10-2017-0018993, the isoindoline compound described in JP 2020-180176, the compound described in JP 2023-013209, the compound described in JP 2023-013166, the xanthene compound described in International Publication No. 2023 / 286526, the compound described in JP 2021-155746, the compound described in JP 2021-155747, JP The compounds described in Japanese Patent Publication No. 2021-155748, the compounds described in Japanese Patent Application Publication No. 2021-155749, the compounds described in International Publication No. 2018 / 051876, the compounds described in Japanese Patent Application Publication No. 2020-083981, the compounds described in Japanese Patent Application Publication No. 2023-056463, the compounds described in Japanese Patent Publication No. 2023-515473, the dioxane compounds described in Japanese Patent Publication No. 2022-549530, the pigment preparations described in Japanese Patent Application Publication No. 2022-061494, the diketopyrrolopyrrole pigments described in Japanese Patent Application Publication No. 2023-057917, and the compounds described in Japanese Patent Application Publication No. 2023-061273 The diketopyrrolopyrrole compounds described, the phthalocyanine described in Japanese Patent Publication No. 2023-519314, the quinophthalone described in Japanese Patent Application Publication No. 2023-080419, the phthalocyanine compounds described in Japanese Patent Application Publication No. 2023-103177, the isoindoline compounds described in Japanese Patent Application Publication No. 2020-026521, the squarylium compounds described in Korean Published Patent No. 10-2023-0043000, the squarylium compounds described in Korean Published Patent No. 10-2023-0050069, the diketopyrrolopyrrole compounds described in Japanese Patent Application Publication No. 2023-127878,Triarylmethane compounds described in Japanese Patent Publication No. 2023-150459, Triarylmethane compounds described in Japanese Patent Publication No. 2023-149735, Core-shell dyes described in Japanese Patent Publication No. 2023-123349, Xanthene compounds described in Japanese Patent Publication No. 2023-543717, Compounds described in Chinese Patent Application Publication No. 116102441, Compounds described in Japanese Patent Publication No. 2023-150459, Compounds described in Japanese Patent Publication No. 2023-167345, Compounds described in Korean Published Patent No. 10-2023-0061078, Compounds described in Japanese Patent Publication No. 2020-183509, colorants described in Japanese Patent Publication No. 2020-079395, compounds represented by formula (1) described in U.S. Patent Application Publication No. 2022 / 0119643, dyes described in Japanese Patent Publication No. 2023-048989, compounds described in Japanese Patent Publication No. 2024-014738, pigments described in Chinese Patent Application Publication No. 115873417, compounds described in Japanese Patent Publication No. 2024-043497, compounds described in Japanese Patent Publication No. 2021-157040, azo compounds described in Japanese Patent Publication No. 2024-063075 Pigments, compounds described in Japanese Patent Publication No. 2022-018967, quinophthalone pigments described in Japanese Patent Publication No. 2024-057558, compounds described in International Publication No. 2020 / 170957, compounds described in Chinese Patent Application Publication No. 117209388, isoindoline compounds described in Japanese Patent Publication No. 2024-079043, phthalocyanine dyes described in Korean Patent Publication No. 10-2022-0026920, compounds described in International Publication No. 2020 / 203514, squarylium compounds described in Japanese Patent Publication No. 2020-183510 The following can also be used: a squarylium compound described in Korean Published Patent No. 10-2024-0030438, a dye described in Chinese Patent Application Publication No. 115947727, a phthalocyanine compound described in Chinese Patent Application Publication No. 117700418, a xanthene compound described in Japanese Patent Application Publication No. 2024-144198, a xanthene compound described in Japanese Patent Application Publication No. 2020-125455, an acidic dye described in Japanese Patent Application Publication No. 2024-132917, a triarylmethane compound described in Japanese Patent Application Publication No. 2024-132927, etc. Furthermore, the chromatic colorant may be a rotaxane. The pigment skeleton may be used in the cyclic structure of the rotaxane.It may be used in a rod-shaped structure, or in both structures.
[0188] Two or more chromatic pigments may be used in combination. Furthermore, when two or more chromatic pigments are used in combination, the combination of two or more chromatic pigments may form black. Examples of such combinations include the following embodiments (1) to (7). When a photocurable composition contains two or more chromatic pigments and exhibits black in combination with two or more chromatic pigments, the photocurable composition can be preferably used as a photocurable composition for forming an infrared transmission filter. (1) Embodiment containing a red pigment and a blue pigment. (2) Embodiment containing a red pigment, a blue pigment, and a yellow pigment. (3) Embodiment containing a red pigment, a blue pigment, a yellow pigment, and a purple pigment. (4) Embodiment containing a red pigment, a blue pigment, a yellow pigment, a purple pigment, and a green pigment. (5) Embodiment containing a red pigment, a blue pigment, a yellow pigment, and a green pigment. (6) An embodiment containing a red colorant, a blue colorant, and a green colorant. (7) An embodiment containing a yellow colorant and a purple colorant.
[0189] (White pigments) Examples of white pigments include inorganic pigments such as titanium dioxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, and zinc sulfide. White pigments can be those described in paragraphs 0040-0043 of International Publication No. 2022 / 085485.
[0190] (Black Colorant) The black colorant is not particularly limited and any known colorant may be used. The black colorant may be an inorganic black colorant or an organic black colorant. The black colorant is preferably a pigment. In this specification, the term "black colorant" refers to a colorant that exhibits absorption over the entire wavelength range of 400 to 700 nm.
[0191] Examples of inorganic black colorants include carbon black, titanium black, and graphite, with carbon black and titanium black being preferred, and titanium black being more preferred. Titanium black refers to black particles containing titanium atoms, with lower-order titanium oxide and titanium oxynitride being preferred. The titanium black used can be the titanium black described in paragraph 0044 of International Publication No. 2022 / 085485. Zirconium nitride powder described in Japanese Patent Application Publication No. 2023-048173 can also be used as the inorganic black colorant.
[0192] Examples of organic black colorants include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred. The organic black colorant can be a compound described in paragraph 0166 of International Publication No. 2022 / 065215. Alternatively, perylene black (Lumogen Black FK4280, etc.) described in paragraphs 0016-0020 of Japanese Patent Publication No. 2017-226821, black azo pigment described in Japanese Patent Publication No. 2022-121935, diketopyrrolopyrrole compounds described in Japanese Patent Publication No. 2021-172735, and bipyrrolinone compounds described in Japanese Patent Publication No. 2024-530550 may also be used as organic black colorants.
[0193] For the black pigment, you can also use the black pigments listed in sections 294-307 of the Journal of the Japan Society of Colorants, Vol. 96, No. 9, 2023.
[0194] (Infrared Absorbing Colorants) The infrared absorbing colorant is preferably a compound having a maximum absorption wavelength longer than 700 nm. The infrared absorbing colorant is preferably a compound having a maximum absorption wavelength in the range of 700 nm to 1800 nm, more preferably a compound having a maximum absorption wavelength in the range of 700 nm to 1400 nm, even more preferably a compound having a maximum absorption wavelength in the range of 700 nm to 1200 nm, and particularly preferably a compound having a maximum absorption wavelength in the range of 700 nm to 1000 nm. Furthermore, the absorbance A of the infrared absorbing colorant at a wavelength of 500 nm is also specified. 1 and absorbance A at the maximum absorption wavelength 2 Ratio A1 / A 2 It is preferable that the ratio is 0.08 or less, and more preferably 0.04 or less. Furthermore, the infrared absorbing colorant is preferably a pigment, and more preferably an organic pigment.
[0195] Examples of infrared absorbing colorants include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, crokonium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, and metal borides. Specific examples of these include the compounds described in paragraph 0114 of International Publication No. 2022 / 065215. Furthermore, examples of infrared absorbing colorants include the compounds described in paragraph 0121 of International Publication No. 2022 / 065215, and the squarylium compounds described in Japanese Patent Publication No. 2020-075959. Copper complex described in Korean Published Patent No. 10-2019-0135217, croconic acid compound described in Japanese Patent Application Publication No. 2021-195515, infrared absorbing dye described in Japanese Patent Application Publication No. 2022-022070, croconium compound described in International Publication No. 2019 / 021767, compound described in Japanese Patent Application Publication No. 2019-127549, International Publication No. 2022 / 059619 The compounds described in JP 2022-151682, the compounds described in JP 2022-188858, the compounds described in JP 2022-184710, the compounds described in JP 2022-189736, the compounds described in JP 2023-004570, the compounds described in International Publication No. 2019 / 230660 Qualyllium compounds, compounds described in International Publication No. 2020 / 218615, diiminium compounds described in Japanese Patent Publication No. 2023-068643, squarylium compounds described in Japanese Patent Publication No. 2023-052770, phthalocyanine compounds described in Korean Patent Publication No. 10-2022-0163680, indigo monoboron complexes described in Japanese Patent Publication No. 2023-073064, phthalocyanine compounds described in Japanese Patent Publication No. 2023-066025, phthalocyanine compounds described in Japanese Patent Publication No. 2020-041127, indigo compounds described in Japanese Patent Publication No. 2023-073064, indigo compounds described in Korean Patent Publication No. 10-2023-0016355, squarylium compounds described in International Publication No. 2019 / 230570,Diiminium compounds described in Japanese Patent Publication No. 2023-095824, compounds described in Japanese Patent Publication No. 2023-159964, compounds described in Japanese Patent Publication No. 2023-176615, compounds described in Japanese Patent Publication No. 2024-500537, phthalocyanine compounds described in Japanese Patent Publication No. 2024-019936, compounds described in Korean Registered Patent No. 10-2575190, and compounds described in Japanese Patent Publication No. 2024-017061 Rimethin compounds, boron derivatives described in Chinese Patent Application Publication No. 116715690, phthalocyanine compounds described in Japanese Patent Publication No. 2024-020454, compounds described in Chinese Patent Application Publication No. 116891482, compounds described in Japanese Patent Publication No. 2024-511242, compounds described in Japanese Patent Publication No. 2024-047265, compounds described in Japanese Patent Publication No. 2024-043503, Japanese Patent Publication No. 2021-0 The extended phthalocyanine described in Publication No. 47255, the compound described in International Publication No. 2024 / 058103, the compound described in Japanese Patent Application Publication No. 2024-071077, the compound described in U.S. Patent Application Publication No. 2021 / 0036251, the compound described in Japanese Patent Application Publication No. 2024-079641, the cyanine compound described in International Publication No. 2024 / 106293, and the compound described in Korean Registered Patent No. 10-2622663 Squallium compounds, the squarylium compounds described in Japanese Patent Publication No. 2024-071077, the cyanine compounds described in International Publication No. 2024 / 128016, the anthraquinone dyes described in International Publication No. 2024 / 041944, the xanthene compounds described in U.S. Patent Application Publication No. 2024 / 0124714, and the tropylium compounds described in Japanese Patent Publication No. 2024-126341 can also be used.
[0196] (Pigment Derivatives) In the present invention, pigment derivatives can also be used as colorants. In the present invention, it is preferable to use pigments and pigment derivatives in combination. Examples of pigment derivatives include compounds having a structure in which an acidic group or a basic group is bonded to the pigment skeleton.
[0197] Examples of the above-mentioned pigment structures include quinoline pigment structure, benzimidazolone pigment structure, benzoisoindole pigment structure, benzothiazole pigment structure, iminium pigment structure, squarylium pigment structure, crokonium pigment structure, oxonol pigment structure, pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, azo pigment structure, azomethine pigment structure, phthalocyanine pigment structure, naphthalocyanine pigment structure, anthraquinone pigment structure, quinacridone pigment structure, dioxazine pigment structure, perinone pigment structure, perylene pigment structure, thiaidine indigo pigment structure, thioindigo pigment structure, isoindoline pigment structure, isoindolinone pigment structure, quinophthalone pigment structure, dithiol pigment structure, triarylmethane pigment structure, pyromethene pigment structure, and the like.
[0198] Examples of acidic groups found in pigment derivatives include carboxyl groups, sulfo groups, phosphate groups, boronic acid groups, imido acid groups, and salts thereof. Examples of atoms or groups of atoms constituting the salt include alkali metal ions (Li + Na + _K + (Ca) 2+ Mg 2+ Examples include ammonium ions, imidazolium ions, pyridinium ions, and phosphonium ions. Examples of imido acid groups include -SO 2 NHSO 2 R X1 , -CONHSO 2 R X2 , -CONHCOR X3 or -SO 2 NHCOR X4 A group represented by -SO is preferred, 2 NHSO 2 R X1 , -CONHSO 2 R X2 , or -SO 2 NHCOR X4 A group represented by -SO is more preferred. 2 NHSO 2 R X1 or -CONHSO 2 R X2 This is even more preferable. X1 ~RX4 Each of these independently represents an alkyl group or an aryl group. X1 ~R X4 The alkyl and aryl groups represented by may have substituents. The substituents are preferably halogen atoms, and more preferably fluorine atoms. X1 ~R X4 Each of these is preferably an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom, and more preferably an alkyl group containing a fluorine atom. The alkyl group containing a fluorine atom has 1 to 10 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. The aryl group containing a fluorine atom has 6 to 20 carbon atoms, more preferably 6 to 12, and even more preferably 6.
[0199] Basic groups found in pigment derivatives include amino groups, pyridinyl groups and their salts, ammonium groups, and phthalimidomethyl groups. Atoms or groups of atoms that make up the salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
[0200] As for the amino group, -NR x11 R x12 Examples include the group represented by and the cyclic amino group.
[0201] -NR x11 R x12 In the group represented by R x11 and R x12 Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and is preferably an alkyl group. That is, the amino group is preferably a dialkylamino group. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but linear or branched is preferred, and linear is more preferred. The alkyl group may have substituents. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The aryl group may have substituents.
[0202] Examples of cyclic amino groups include pyrrolidine, piperidine, piperazine, and morpholine groups. These groups may also have substituents.
[0203] Specific examples of pigment derivatives include the compound described in paragraph 0124 of International Publication No. 2022 / 085485, the benzimidazolone compound or salt thereof described in Japanese Patent Publication No. 2018-168244, the compound having an isoindoline skeleton as described in general formula (1) of Japanese Patent Publication No. 6996282, the compound described in Japanese Patent Publication No. 2019-172968, the compound described in Chinese Patent Application Publication No. 115124889, the quinophthalone-based dye derivative described in Japanese Patent Publication No. 2024-046989, and Japanese Patent Publication No. 2024-066 Examples include the compound described in Japanese Patent Publication No. 986, the compound described in Japanese Patent Application Publication No. 2024-066995, the compound described in Japanese Patent Application Publication No. 2022-018967, the compound described in Japanese Patent Application Publication No. 2024-066992, the pigment derivative described in Japanese Patent Application Publication No. 2024-115174, the pigment derivative described in Japanese Patent Application Publication No. 2024-149352, the pigment derivative described in Japanese Patent Application Publication No. 2024-149349, the naphthalocyanine derivative described in Japanese Patent Application Publication No. 7565524, and the pigment derivative described in Japanese Patent Application Publication No. 2024-149348.
[0204] The colorant content in the total solids of the photocurable composition is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 77.5% by mass or less, and even more preferably 75% by mass or less.
[0205] The pigment content in the total solids of the photocurable composition is preferably 30% by mass or more, more preferably 45% by mass or more, and even more preferably 55% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 77.5% by mass or less, and even more preferably 75% by mass or less.
[0206] The pigment content in the colorant is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 70 to 100% by mass. Furthermore, the total content of pigment and pigment derivative in the colorant is preferably 25 to 100% by mass, more preferably 55 to 100% by mass, and even more preferably 75 to 100% by mass.
[0207] <<Resin>> The photocurable composition of the present invention preferably contains a resin. The resin is used, for example, to disperse pigments and the like in the photocurable composition, or as a binder. A resin used mainly to disperse pigments and the like in a photocurable composition is also called a dispersant. However, such uses of the resin are just examples, and the resin can also be used for purposes other than those mentioned above. The photocurable composition of the present invention preferably contains a resin as a binder.
[0208] The weight-average molecular weight (Mw) of the resin is preferably between 3,000 and 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 4,000 or more, and more preferably 5,000 or more.
[0209] Examples of resins include (meth)acrylic resins, epoxy resins, (meth)acrylamide resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene etherphosphine oxide resins, polyimide resins, polyamide-imide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, siloxane resins, and urethane resins. Urethane resin is a polymer compound formed by the reaction of an isocyanate group and an alcohol group. Specifically, it is a polymer compound having a urethane bond (or carbamate bond) formed by reacting a compound having an isocyanate group (polyisocyanate) with a compound having an alcohol group (polyol). The urethane value of the urethane resin is preferably 0.5 to 6.0 mmol / g. The lower limit is preferably 1.0 mmol / g or more, more preferably 1.5 mmol / g or more, and even more preferably 2.0 mmol / g or more. The upper limit is preferably 5.0 mmol / g or less, more preferably 4.5 mmol / g or less, and even more preferably 4.0 mmol / g or less. The urethane value of the urethane resin is particularly preferably 2.0 to 4.0 mmol / g. The urethane value of the urethane resin is a numerical value that represents the molar amount of urethane bonds per gram of solid content of the urethane resin.
[0210] Furthermore, the resins include the resins described in paragraphs 0091 to 0099 of International Publication No. 2022 / 065215, the blocked polyisocyanate resin described in Japanese Patent Publication No. 2016-222891, the resin described in Japanese Patent Publication No. 2020-122052, the resin described in Japanese Patent Publication No. 2020-111656, the resin described in Japanese Patent Publication No. 2020-139021, and the resin described in Japanese Patent Publication No. 2017-138503. A resin comprising a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain; the resin described in paragraphs 0199 to 0233 of Japanese Patent Publication No. 2020-186373; the alkali-soluble resin described in Japanese Patent Publication No. 2020-186325; the resin represented by formula 1 described in Korean Published Patent No. 10-2020-0078339; and a copolymer containing epoxy groups and acid groups described in International Publication No. 2022 / 030445. , the resin described in Japanese Patent Publication No. 2018-135514, the copolymer described in Japanese Patent Publication No. 2020-041046, the resin described in Japanese Patent Publication No. 2023-033156, the resin described in Japanese Patent Publication No. 2023-030386, the resin described in Japanese Patent Publication No. 2023-027753, the resin described in Japanese Patent Publication No. 2020-139021, the resin described in Japanese Patent Publication No. 2023-074038, Japanese Patent Publication No. 2023-079666 The resins described in the publication, the cardo resin described in Chinese Patent Application Publication No. 115947929, the copolymer described in Japanese Patent Application Publication No. 2024-014141, the resin described in Japanese Patent Application Publication No. 2024-050148, the copolymer described in International Publication No. 2024 / 134926, the resin described in Japanese Patent Application Publication No. 2024-088596, and the compound represented by formula (1) described in Japanese Patent Application Publication No. 2024-128953 can also be used.
[0211] It is preferable to use a resin having acidic groups. Examples of acidic groups include carboxyl groups, phosphate groups, sulfo groups, and phenolic hydroxyl groups.
[0212] The acid value of the resin having acid groups is preferably 30 to 500 mg KOH / g. The lower limit is preferably 40 mg KOH / g or more, and more preferably 50 mg KOH / g or more. The upper limit is preferably 400 mg KOH / g or less, more preferably 300 mg KOH / g or less, and even more preferably 200 mg KOH / g or less. The weight-average molecular weight (Mw) of the resin having acid groups is preferably 5,000 to 100,000, and more preferably 5,000 to 50,000. The number-average molecular weight (Mn) of the resin having acid groups is preferably 1,000 to 20,000.
[0213] Resins having acidic groups preferably contain repeating units having acidic groups in their side chains, and more preferably contain repeating units having acidic groups in their side chains in an amount of 5 to 70 mol% of the total repeating units of the resin. The upper limit of the content of repeating units having acidic groups in their side chains is preferably 50 mol% or less, and more preferably 30 mol% or less. The lower limit of the content of repeating units having acidic groups in their side chains is preferably 10 mol% or more, and more preferably 20 mol% or more.
[0214] Regarding resins having acid groups, reference can be made to paragraphs 0558-0571 of Japanese Patent Application Publication No. 2012-208494 (paragraphs 0685-0700 of the corresponding US Patent Application Publication No. 2012 / 0235099) and paragraphs 0076-0099 of Japanese Patent Application Publication No. 2012-198408, the contents of which are incorporated herein by reference. Furthermore, commercially available resins having acid groups can also be used. There are no particular restrictions on the method of introducing acid groups into the resin, but for example, the method described in Japanese Patent No. 6349629 can be cited. In addition, as a method of introducing acid groups into the resin, a method can be cited in which an acid anhydride is reacted with a hydroxyl group produced by a ring-opening reaction of an epoxy group to introduce an acid group.
[0215] The photocurable composition of the present invention may also preferably contain a resin having a basic group. The resin having a basic group is preferably a resin containing repeating units having a basic group in its side chain, more preferably a copolymer having repeating units having a basic group in its side chain and repeating units not having a basic group, and even more preferably a block copolymer having repeating units having a basic group in its side chain and repeating units not having a basic group. The resin having a basic group can also be used as a dispersant. The amine value of the resin having a basic group is preferably 5 to 300 mg KOH / g. The lower limit is preferably 10 mg KOH / g or more, and more preferably 20 mg KOH / g or more. The upper limit is preferably 200 mg KOH / g or less, and more preferably 100 mg KOH / g or less.
[0216] Commercially available resins containing basic groups include DISPERBY K-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (all manufactured by Bic Chemie), and Solspers 112. Examples include 00, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100 (all manufactured by Lubrizol Japan), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), etc. Furthermore, the resin having basic groups may also be the block copolymer (B) described in paragraphs 0063 to 0112 of Japanese Patent Application Publication No. 2014-219665, the block copolymer A1 described in paragraphs 0046 to 0076 of Japanese Patent Application Publication No. 2018-156021, or the vinyl resin having basic groups described in paragraphs 0150 to 0153 of Japanese Patent Application Publication No. 2019-184763, the details of which are incorporated herein by reference.
[0217] The photocurable composition of the present invention may also preferably contain a resin having an acidic group and a resin having a basic group. According to this embodiment, the storage stability of the photocurable composition can be further improved. When a resin having an acidic group and a resin having a basic group are used in combination, the content of the resin having a basic group is preferably 20 to 500 parts by mass, more preferably 30 to 300 parts by mass, and even more preferably 50 to 200 parts by mass, per 100 parts by mass of the resin having an acidic group.
[0218] It is preferable to use a resin having alkylene oxy groups. The alkylene oxy groups can suppress oxygen inhibition, thereby achieving even higher sensitivity.
[0219] The alkylene oxy group preferably has 2 or more carbon atoms, more preferably 2 to 10, even more preferably 2 to 5, and even more preferably 2 or 3. The alkylene oxy group is preferably linear or branched, and more preferably linear.
[0220] Resins having alkylene oxy groups preferably also have acidic or basic groups, and more preferably acidic groups. Examples of acidic groups include carboxyl groups, phosphate groups, sulfo groups, and phenolic hydroxyl groups, with phosphate groups being preferred. In other words, resins having alkylene oxy groups are preferably resins having both phosphate groups and alkylene oxy groups. Resins having alkylene oxy groups and acidic or basic groups can be used as binders, but are preferably used as dispersants.
[0221] It is also preferable to use a resin having aromatic carboxyl groups as the resin. In a resin having aromatic carboxyl groups, the aromatic carboxyl groups may be included in the main chain of the repeating unit or in the side chain of the repeating unit. It is preferable that the aromatic carboxyl groups are included in the main chain of the repeating unit. In this specification, an aromatic carboxyl group is a group having a structure in which one or more carboxyl groups are bonded to an aromatic ring. In an aromatic carboxyl group, the number of carboxyl groups bonded to the aromatic ring is preferably 1 to 4, and more preferably 1 to 2. Examples of resins having aromatic carboxyl groups include the resins described in paragraphs 0082 to 0107 of International Publication No. 2021 / 166858.
[0222] It is also preferable to use a resin having crosslinkable groups. Examples of crosslinkable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, allyl groups, (meth)acryloyl groups, and styrene groups. Examples of cyclic ether groups include epoxy groups and oxetanyl groups. When using a resin having crosslinkable groups, the content of the resin having crosslinkable groups in the resin contained in the photocurable composition is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more.
[0223] The resin preferably includes a graft resin. Examples of graft resins include resins having repeating units with graft chains. In this specification, a graft chain refers to a polymer chain that branches off and extends from the main chain of the repeating unit. The graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and even more preferably 60 to 500 atoms excluding hydrogen atoms.
[0224] The graft chain preferably contains repeating units of at least one structure selected from the group consisting of polyester structures, polyether structures, poly(meth)acrylic structures, polystyrene structures, polyurethane structures, polyurea structures, and polyamide structures; more preferably contains repeating units of at least one structure selected from the group consisting of polyester structures, polyether structures, poly(meth)acrylic structures, and polystyrene structures; even more preferably contains repeating units of polyester structures or polyether structures; and particularly preferably contains repeating units of polyester structures.
[0225] When a colorant containing a pigment is used, the photocurable composition of the present invention may also preferably contain a resin as a dispersant. The dispersant content is preferably 1 to 45 parts by mass per 100 parts by mass of pigment. The upper limit is preferably 40 parts by mass or less, and more preferably 35 parts by mass or less. The lower limit is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more.
[0226] Examples of dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, an acidic dispersant (acidic resin) refers to a resin in which the amount of acidic groups is greater than the amount of basic groups. As an acidic dispersant (acidic resin), it is preferable that the amount of acidic groups is 70 mol% or more when the total amount of acidic groups and basic groups is set to 100 mol%. The acidic group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mg KOH / g. Furthermore, a basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater than the amount of acidic groups. As a basic dispersant (basic resin), it is preferable that the amount of basic groups exceeds 50 mol% when the total amount of acidic groups and basic groups is set to 100 mol%. The basic group of the basic dispersant is preferably an amino group.
[0227] The resin used as a dispersant is preferably a resin having an alkylene oxy group and an acidic or basic group.
[0228] The resin used as a dispersant is preferably a graft resin. The resin used as a dispersant is also preferably a resin having aromatic carboxyl groups.
[0229] The resin used as a dispersant is preferably a polyimine-based dispersant containing a nitrogen atom in at least one of its main chain and side chains. Preferably, the polyimine-based dispersant has a main chain having a substructure with functional groups having a pKa of 14 or less, and side chains with 40 to 10,000 atoms, and contains a basic nitrogen atom in at least one of its main chain and side chains. The basic nitrogen atom is not particularly limited as long as it exhibits basic properties. For polyimine-based dispersants, refer to paragraphs 0102 to 0166 of Japanese Patent Application Publication No. 2012-255128, the contents of which are incorporated herein by reference.
[0230] The resin used as a dispersant is preferably a resin with a structure in which multiple polymer chains are bonded to the core. Examples of such resins include dendrimers (including star-shaped polymers). Specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of Japanese Patent Application Publication No. 2013-043962.
[0231] The resin used as a dispersant is preferably a resin containing repeating units having ethylenically unsaturated bond-containing groups in their side chains. The content of repeating units having ethylenically unsaturated bond-containing groups in their side chains is preferably 10 mol% or more, more preferably 10 to 80 mol%, and even more preferably 20 to 70 mol% of the total repeating units of the resin.
[0232] As a dispersant, the resin described in Japanese Patent Publication No. 2018-087939, the block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077, polyethyleneimine having polyester side chains as described in International Publication No. 2016 / 104803, the block copolymer described in International Publication No. 2019 / 125940, the block polymer having acrylamide structural units as described in Japanese Patent Publication No. 2020-066687, and the acrylic polymer described in Japanese Patent Publication No. 2020-066688. Block polymers having lylamide structural units, dispersants described in International Publication No. 2016 / 104803, triazine compounds described in Korean Patent Publication No. 10-2017-0129400, dispersants described in Japanese Patent Application Publication No. 2024-050950, triazine compounds described in Korean Patent Publication No. 10-2017-0129416, aryl-modified branched reaction products described in Japanese Patent Application Publication No. 2024-510115, pigment dispersants described in Chinese Patent Application Publication No. 109554004, and the like can also be used.
[0233] Dispersants are also available commercially, and specific examples include the DISPERBYK series from BYK Chemie, the SOLSPERSE series from Lubrizol Nippon, the Efka series from BASF, and the Azisper series from Ajinomoto Fine Techno Co., Ltd. In addition, the products described in paragraph 0129 of Japanese Patent Publication No. 2012-137564 and paragraph 0235 of Japanese Patent Publication No. 2017-194662 can also be used as dispersants.
[0234] The resin content in the total solids of the photocurable composition is preferably 1 to 50% by mass. The upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more.
[0235] The content of the resin having an alkylene oxy group in the resin contained in the photocurable composition is preferably 10% by mass or more, more preferably 25% by mass or more, and even more preferably 50% by mass or more.
[0236] The polymerizable monomer content in the total of the resin used as a binder and the polymerizable monomer is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. The upper limit may be 100% by mass or less, or 95% by mass or less.
[0237] The photocurable composition of the present invention may contain only one type of resin, or it may contain two or more types of resins. When it contains two or more types of resins, it is preferable that their total amount is within the above range.
[0238] <<Chain Transfer Agent>> The photocurable composition of the present invention may contain a chain transfer agent. Examples of chain transfer agents include thiol compounds, thiocarbonylthio compounds, and dimers of aromatic α-methylalkenyls, with thiol compounds being preferred. Examples of chain transfer agents include those described in paragraphs 0093 to 0113 of International Publication No. 2019 / 188652.
[0239] The thiol compound used as a chain transfer agent is a compound having one or more thiol groups, and preferably a compound having two or more thiol groups. The upper limit of the number of thiol groups contained in the thiol compound is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. It is particularly preferable that the thiol compound is a compound having two thiol groups.
[0240] The thiol compound is preferably a compound represented by the following formula (SH-1). S1 - (SH) n ...Formula (SH-1) (wherein SH represents a thiol group, L 1 (This represents an n-valence base, where n is an integer greater than or equal to 1.)
[0241] L in equation (SH-1) S1 The n-valent groups represented by include hydrocarbon groups, heterocyclic groups, -O-, -S-, and -NR S1 -, -CO-, -COO-, -OCO-, -SO 2 - Or a group consisting of a combination of these. R S1The group represents a hydrogen atom, an alkyl group, or an aryl group, with a hydrogen atom being preferred. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be cyclic or acyclic. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The hydrocarbon group may have substituents or may not have substituents. The cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be monocyclic or fused rings. The heterocyclic group may be monocyclic or fused rings. A five-membered ring or a six-membered ring is preferred for the heterocyclic group. The heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. Examples of heteroatoms constituting the heterocyclic group include nitrogen atoms, oxygen atoms, and sulfur atoms. 1 The number of carbon atoms constituting the compound is preferably 3 to 100, and more preferably 6 to 50.
[0242] In formula (SH-1), n represents an integer greater than or equal to 1. The upper limit of n is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. The lower limit of n is preferably 2 or greater.
[0243] Specific examples of thiol compounds include those described in paragraphs 0100-0103 of International Publication No. 2019 / 188652. Commercially available thiol compounds include PEMP (manufactured by SC Organic Chemicals Co., Ltd.), Suncellar M (manufactured by Sanshin Chemical Industry Co., Ltd.), Karenz MTBD1, Karenz MTPE1, Karenz MTNR1, and Karenz MTTPMB (all manufactured by Resonac Co., Ltd.). As chain transfer agents, thiol compounds described in Japanese Patent Publication No. 2020-109068, ether-bonded thiol compounds described in International Publication No. 2020 / 170944, and commercially available thiol compounds such as Multiol Y-2, Y-3, and Y-4 (manufactured by Sakai Chemical Industry Co., Ltd.) can also be used.
[0244] The molecular weight of the chain transfer agent is preferably 200 or more. The upper limit is preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less, because it can increase the SH valency per unit weight.
[0245] The content of the chain transfer agent in the total solid content of the photocurable composition is preferably 0.001 to 5% by mass. The upper limit is preferably 3% by mass or less, and more preferably 1% by mass or less. The lower limit is preferably 0.05% by mass or more, and more preferably 0.01% by mass or more. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount is within the above range.
[0246] <<Polyalkyleneimines>> The photocurable composition of the present invention may contain polyalkyleneimines. Polyalkyleneimines are used, for example, as dispersing aids for pigments. Dispersing aids are materials used to improve the dispersibility of colorants such as pigments in a photocurable composition. A polyalkyleneimine is a polymer obtained by ring-opening polymerization of alkyleneimines. It is preferable that the polyalkyleneimine is a polymer having a branched structure containing primary amino groups, secondary amino groups, and tertiary amino groups. The number of carbon atoms in the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2.
[0247] The molecular weight of the polyalkyleneimine is preferably 200 or more, and more preferably 250 or more. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less. When the molecular weight of the polyalkyleneimine can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula. On the other hand, when the molecular weight of a specific amine compound cannot be calculated from the structural formula, or when it is difficult to calculate, the number-average molecular weight measured by the boiling point elevation method is used. Furthermore, when it cannot be measured by the boiling point elevation method, or when it is difficult to measure, the number-average molecular weight measured by the viscosity method is used. Furthermore, when it cannot be measured by the viscosity method, or when it is difficult to measure by the viscosity method, the number-average molecular weight in polystyrene equivalent values measured by GPC (gel permeation chromatography) is used.
[0248] The amine value of the polyalkyleneimine is preferably 5 mmol / g or more, more preferably 10 mmol / g or more, and even more preferably 15 mmol / g or more.
[0249] Specific examples of alkyleneimines include ethyleneimine, propyleneimine, 1,2-butyleneimine, and 2,3-butyleneimine, with ethyleneimine or propyleneimine being preferred, and ethyleneimine being more preferred. Polyalkyleneimines are particularly preferably polyethyleneimine. Furthermore, polyethyleneimine preferably contains 10 mol% or more of primary amino groups relative to the total of primary, secondary, and tertiary amino groups, more preferably 20 mol% or more, and even more preferably 30 mol% or more. Commercially available polyethyleneimines include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by Nippon Shokubai Co., Ltd.).
[0250] The polyalkylene imine content in the total solids of the photocurable composition is preferably 0.1 to 5% by mass. The lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. Furthermore, the polyalkylene imine content is preferably 0.5 to 20 parts by mass per 100 parts by mass of pigment. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more. The upper limit is preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less. Only one type of polyalkylene imine may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount is within the above range.
[0251] <<Compounds Having Cyclic Ether Groups>> The photocurable composition of the present invention may contain compounds having cyclic ether groups. Examples of cyclic ether groups include epoxy groups and oxetanyl groups. The epoxy group may be an alicyclic epoxy group. An alicyclic epoxy group refers to a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are fused. The compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound). Examples of epoxy compounds include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferred. The epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups contained in the epoxy compound can be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups contained in the epoxy compound is preferably 2 or more.
[0252] As compounds having a cyclic ether group, you can use the compounds described in paragraphs 0034 to 0036 of Japanese Patent Publication No. 2013-011869, paragraphs 0147 to 0156 of Japanese Patent Publication No. 2014-043556, paragraphs 0085 to 0092 of Japanese Patent Publication No. 2014-089408, the compounds described in Japanese Patent Publication No. 2017-179172, the xanthene type epoxy resin described in Japanese Patent Publication No. 2021-195421, and the xanthene type epoxy resin described in Japanese Patent Publication No. 2021-195422.
[0253] The compound having a cyclic ether group may be a low molecular weight compound (for example, with a molecular weight of less than 2000, and even less than 1000) or a high molecular weight compound (macromolecule) (for example, with a molecular weight of 1000 or more, or in the case of a polymer, with a weight-average molecular weight of 1000 or more). The weight-average molecular weight of the compound having a cyclic ether group is preferably 200 to 100000, and more preferably 500 to 50000. The upper limit of the weight-average molecular weight is preferably 10000 or less, more preferably 5000 or less, and even more preferably 3000 or less.
[0254] Examples of commercially available compounds containing cyclic ether groups include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (all manufactured by NOF Corporation, epoxy group-containing polymers).
[0255] The content of compounds having cyclic ether groups in the total solid content of the photocurable composition is preferably 0.1 to 20% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. Only one compound having a cyclic ether group may be used, or two or more compounds may be used. When two or more compounds are used, it is preferable that their total amount is within the above range.
[0256] <<Ultraviolet Absorbers>> The photocurable composition of the present invention may contain ultraviolet absorbers. Examples of ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, and dibenzoyl compounds. As ultraviolet absorbers, compounds described in paragraph 0179 of International Publication No. 2022 / 085485, reactive triazine ultraviolet absorbers described in Japanese Patent Application Publication No. 2021-178918, ultraviolet absorbers described in Japanese Patent Application Publication No. 2022-007884, compounds described in Korean Patent Publication No. 10-2022-0014454, compounds described in Japanese Patent Application Publication No. 2023-013321, compounds described in Japanese Patent Application Publication No. 2023-178225, and compounds represented by formula (1) described in Japanese Patent Application Publication No. 2024-140703 may also be used. The content of ultraviolet absorbers in the total solid content of the photocurable composition is preferably 0.01 to 10% by mass, and more preferably 0.01 to 5% by mass. Only one type of ultraviolet absorber may be used, or two or more types may be used. If two or more types are used, it is preferable that their total amount falls within the above range.
[0257] <<Polymerization Inhibitor>> The photocurable composition of the present invention may contain a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salts, cerium salts, etc.). Among these, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the photocurable composition is preferably 0.0001 to 5% by mass. There may be only one type of polymerization inhibitor, or there may be two or more types. If there are two or more types, it is preferable that the total amount is within the above range.
[0258] <<Silane Coupling Agent>> The photocurable composition of the present invention may contain a silane coupling agent. Examples of silane coupling agents include silane compounds having a hydrolyzable group, and it is preferable that the silane compound has a hydrolyzable group and other functional groups. A hydrolyzable group is a substituent that is directly bonded to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, and acyloxy groups, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, thiol groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, isocyanate groups, and phenyl groups, with amino groups, (meth)acryloyl groups, and epoxy groups being preferred. Specific examples of silane coupling agents include the compounds described in paragraph 0177 of International Publication No. 2022 / 085485 and the compounds described in Japanese Patent Publication No. 2019-183020. The content of the silane coupling agent in the total solid content of the photocurable composition is preferably 0.1 to 15% by mass. The upper limit is preferably 10% by mass or less, and more preferably 5% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. There may be only one type of silane coupling agent, or there may be two or more types. If there are two or more types, it is preferable that the total amount is within the above range.
[0259] <<Surfactants>> The photocurable composition of the present invention may contain a surfactant. Various surfactants can be used, such as fluorinated surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants. The surfactant is preferably a silicone surfactant or a fluorinated surfactant, and more preferably a silicone surfactant. For surfactants, refer to the surfactants described in paragraphs 0238 to 0245 of International Publication No. 2015 / 166779, which are incorporated herein by reference.
[0260] As fluorinated surfactants, compounds described in paragraphs 0167-0173 of International Publication No. 2022 / 085485 can be used.
[0261] Examples of nonionic surfactants include the compounds described in paragraph 0174 of International Publication No. 2022 / 085485.
[0262] Examples of silicone-based surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, and SF 8419. Examples include OIL (manufactured by Dow Toray Industries, Inc.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (manufactured by Bic Chemie, Inc.), etc. Furthermore, compounds with the following structure can also be used as silicone-based surfactants.
[0263] As surfactants, polymers described in International Publication No. 2021 / 131726, silicone-containing copolymers described in International Publication No. 2024 / 024440, and silicone-containing copolymers described in International Publication No. 2024 / 024441 can also be used.
[0264] The surfactant content in the total solids of the photocurable composition is preferably 0.001% to 5.0% by mass, and more preferably 0.005% to 3.0% by mass. The surfactant may be one type or two or more types. If two or more types are used, the total amount is preferably within the above range.
[0265] <<Antioxidants>> The photocurable composition of the present invention may contain antioxidants. Examples of antioxidants include phenolic antioxidants, amine antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Examples of phenolic antioxidants include hindered phenol compounds. Phenolic antioxidants are preferably compounds having a substituent at the ortho position adjacent to the phenolic hydroxyl group. As for the substituents, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Antioxidants are also preferably compounds having a phenolic group and a phosphite ester group in the same molecule. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosfepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosfepin-2-yl)oxy]ethyl]amine, ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphate, and tris(2,4-di-tert-butylphenyl) phosphite. Examples of commercially available antioxidants include ADEKA stab AO-20, ADEKA stab AO-30, ADEKA stab AO-40, ADEKA stab AO-50, ADEKA stab AO-50F, ADEKA stab AO-60, ADEKA stab AO-60G, ADEKA stab AO-80, and ADEKA stab AO-330 (all manufactured by ADEKA Corporation), and JP-650 (manufactured by Johoku Chemical Industry Co., Ltd.). The antioxidants can also be compounds described in paragraphs 0023-0048 of Japanese Patent No. 6268967, compounds described in International Publication No. 2017 / 006600, compounds described in International Publication No. 2017 / 164024, and compounds described in Korean Published Patent No. 10-2019-0059371. The antioxidant content in the total solids of the photocurable composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. Only one type of antioxidant may be used, or two or more types may be used. If two or more types are used, it is preferable that their total amount falls within the above range.
[0266] <<Other Components>> The photocurable composition of the present invention may contain, if necessary, a sensitizer, a plasticizer, and other auxiliaries (for example, conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, fragrances, surface tension adjusters, chain transfer agents, etc.). By appropriately containing these components, properties such as film physical properties can be adjusted. These components can be compounds described in paragraph 0182 of WO 2022 / 085485, compounds having two or more triethoxysilyl groups described in JP 2023-180607 A, metal compounds described in JP 2024-129722 A, metal compounds described in JP 2024-129724 A, metal compounds described in JP 2024-128802 A, metal compounds described in JP 2024-128809 A, metal compounds described in JP 2024-129723 A, etc.
[0267] The photocurable composition of the present invention may contain a metal oxide to adjust the refractive index of the resulting film. Examples of the metal oxide include TiO 2 , ZrO 2 , Al 2 O 3 , SiO 2 etc. The primary particle diameter of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, and even more preferably 5 to 50 nm. The metal oxide may have a core-shell structure. In this case, the core part may be hollow.
[0268] The photocurable composition of the present invention may contain a light resistance improver. Examples of the light resistance improver include the compounds described in paragraph 0183 of WO 2022 / 085485.
[0269] The photocurable composition of the present invention may contain a compound derived from a biomass raw material, a compound containing a radioactive carbon atom, or a compound having 50% or more of percent modern carbon. The compound derived from a biomass raw material may be 20% by mass or more based on all the compounds.
[0270] It is also preferable that the photocurable composition of the present invention substantially does not contain terephthalic acid ester. Here, "substantially does not contain" means that the content of terephthalic acid ester is 1000 mass ppm or less in the total amount of the photocurable composition, more preferably 100 mass ppm or less, and particularly preferably zero.
[0271] From the perspective of environmental regulations, it is preferable that the content of melamine in the photocurable composition of the present invention is 10000 mass ppm or less.
[0272] It is preferable that the free metal content of the photocurable composition of the present invention is 100 ppm or less, and more preferably 50 ppm or less. Also, the free halogen content is preferably 100 ppm or less, and more preferably 50 ppm or less. Examples of methods for reducing free metals and halogens in the photocurable composition include washing with ion-exchanged water, filtration, ultrafiltration, purification with ion-exchange resins, and the like.
[0273] From an environmental perspective, the use of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts may be restricted. In the photocurable composition of the present invention, when the content of the above-mentioned compounds is reduced, the content of perfluoroalkyl sulfonic acid (particularly perfluoroalkyl sulfonic acid with 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts, and perfluoroalkyl carboxylic acid (particularly perfluoroalkyl carboxylic acid with 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts is preferably in the range of 0.01 ppb to 1000 ppb, more preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb, relative to the total solid content of the photocurable composition. The photocurable composition of the present invention may substantially not contain perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts. For example, a photocurable composition substantially free of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts, may be selected by using compounds that can substitute for perfluoroalkyl sulfonic acid and its salts, and compounds that can substitute for perfluoroalkyl carboxylic acid and its salts. Examples of compounds that can substitute for regulated compounds include compounds that have been excluded from regulation due to differences in the number of carbon atoms in the perfluoroalkyl group. However, the above does not preclude the use of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts. The photocurable composition of the present invention may contain perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts, to the maximum permissible extent.
[0274] The water content of the photocurable composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably in the range of 0.1 to 1.0% by mass. The water content can be measured by the Karl Fischer method.
[0275] The photocurable composition of the present invention can be used by adjusting its viscosity for purposes such as adjusting the film surface (flatness, etc.) and adjusting the film thickness. The viscosity value can be appropriately selected as needed, but for example, 0.3 mPa·s to 50 mPa·s is preferred at 25°C, and 0.5 mPa·s to 20 mPa·s is more preferred. As a method for measuring viscosity, for example, a cone-plate type viscometer can be used and the measurement can be taken while the temperature has been adjusted to 25°C.
[0276] <<Container>> There are no particular limitations on the container used to contain the photocurable composition, and any known container can be used. Alternatively, the container described in paragraph 0187 of International Publication No. 2022 / 085485 can be used as the container.
[0277] <Method for preparing the photocurable composition> The photocurable composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the photocurable composition, all components may be dissolved and / or dispersed simultaneously in a solvent to prepare the photocurable composition, or, if necessary, each component may be prepared as two or more solutions or dispersions and mixed at the time of use (coating) to prepare the photocurable composition.
[0278] The preparation of a photocurable composition preferably includes a process for dispersing the pigment. Examples of mechanical forces used for pigment dispersion include compression, squeezing, impact, shearing, and cavitation. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, and ultrasonic dispersion. Furthermore, in the grinding of pigments using a sand mill (bead mill), it is preferable to process the material under conditions that enhance grinding efficiency, such as by using small-diameter beads or increasing the bead packing density. It is also preferable to remove coarse particles after the grinding process by filtration or centrifugation. Furthermore, the processes and dispersers for dispersing the pigments can suitably be those described in "Complete Collection of Dispersion Technologies, published by Joho Kiko Co., Ltd., July 15, 2005," "Comprehensive Data Collection on Dispersion Technologies and Industrial Applications Focusing on Suspensions (Solid / Liquid Dispersion Systems), published by Keiei Kaihatsu Center Publishing Department, October 10, 1978," and paragraph 0022 of Japanese Patent Publication No. 2015-157893. In addition, in the process of dispersing the pigments, particle refinement treatment may be performed in a salt milling step. For materials, equipment, and processing conditions used in the salt milling step, for example, refer to the descriptions in Japanese Patent Publication No. 2015-194521 and Japanese Patent Publication No. 2012-046629. Examples of bead materials used for dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, and glass. Furthermore, inorganic compounds with a Mohs hardness of 2 or higher can be used as beads. The photocurable composition may contain 1 to 10,000 ppm of the above-mentioned beads.
[0279] In preparing a photocurable composition, it is preferable to filter the photocurable composition with a filter for purposes such as removing foreign matter and reducing defects. Examples of filters and filtration methods used for filtration include those described in paragraphs 0196 to 0199 of International Publication No. 2022 / 085485.
[0280] <Membrane> The membrane of the present invention is obtained by curing the photocurable composition of the present invention described above. The membrane of the present invention can be used in optical filters such as color filters, infrared transmission filters and infrared cut filters.
[0281] The film thickness of the film of the present invention can be appropriately adjusted depending on the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.
[0282] When the film of the present invention is used as a color filter, it is preferable that the film has a hue of green, red, blue, cyan, magenta, or yellow. Furthermore, the film of the present invention can be preferably used as a colored pixel of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.
[0283] <Method for Manufacturing Pixels> A method for manufacturing pixels using the photocurable composition of the present invention will now be described. The method for manufacturing pixels includes the steps of forming a composition layer on a support using the photocurable composition of the present invention, exposing the composition layer in a pattern, and developing and removing the unexposed parts of the composition layer. If necessary, a step of drying the composition layer (pre-bake step) and a step of heat-treating the developed pattern (pixel) (post-bake step) may be provided.
[0284] In the step of forming the composition layer, the photocurable composition of the present invention is used to form the composition layer on a support. The support is not particularly limited and can be appropriately selected depending on the application. Examples include glass substrates and silicon substrates, with silicon substrates being preferred. A charge-coupled device (CCD), complementary metal-oxide-semiconductor (CMOS), transparent conductive film, etc., may be formed on the silicon substrate. A black matrix that isolates each pixel may also be formed on the silicon substrate. Furthermore, a base layer may be provided on the silicon substrate to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the substrate surface. The surface contact angle of the base layer is preferably 20 to 70° when measured with diiodomethane. It is also preferably 30 to 80° when measured with water.
[0285] Known methods can be used for coating the photocurable composition. For example, drop casting; slit coating; spray coating; roll coating; spin coating; casting; slit and spin coating; pre-wetting (for example, the method described in Japanese Patent Application Publication No. 2009-145395); various printing methods such as inkjet (for example, on-demand, piezo, and thermal), nozzle jet printing, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing; transfer methods using molds, etc.; and nanoimprint methods. In addition, the coating method described in paragraph 0207 of International Publication No. 2022 / 085485 can also be used.
[0286] The composition layer formed on the support may be dried (pre-baked). Pre-baking is not necessary when manufacturing the film by a low-temperature process. If pre-baking is performed, the pre-baking temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. The lower limit can be, for example, 50°C or higher, and also 80°C or higher. The pre-baking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Pre-baking can be performed using a hot plate, oven, etc.
[0287] Next, the composition layer is exposed in a pattern (exposure step). For example, the composition layer can be exposed in a pattern by using a stepper exposure machine or a scanner exposure machine to expose it through a mask having a predetermined mask pattern. This allows the exposed areas to be cured.
[0288] Examples of radiation (light) that can be used for exposure include g-rays and i-rays. Light with a wavelength of 150 to 300 nm can also be used. Examples of light with a wavelength of 150 to 300 nm include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm), with KrF rays (wavelength 248 nm) being preferred. The light with a wavelength of 150 to 300 nm is preferably excimer laser light with a wavelength of 150 to 300 nm. In addition, long-wavelength light sources of 300 nm or more can also be used for exposure.
[0289] During exposure, the light may be irradiated continuously or pulsed (pulsed exposure). Pulsed exposure is an exposure method in which light irradiation and pauses are repeated in short cycles (for example, at the millisecond level or less).
[0290] The irradiation dose (exposure dose) is, for example, 0.03 to 2.5 J / cm². 2 Preferably, 0.05 to 1.0 J / cm 2 This is more preferable. The oxygen concentration during exposure can be appropriately selected. In addition to exposure in air, exposure may be carried out in a low-oxygen atmosphere with an oxygen concentration of 19 volume% or less (e.g., 15 volume%, 5 volume%, or substantially oxygen-free), or in a high-oxygen atmosphere with an oxygen concentration exceeding 21 volume% (e.g., 22 volume%, 30 volume%, or 50 volume%). Furthermore, the exposure intensity can be appropriately set, usually 1000 W / m². 2 ~100000W / m 2 (For example, 5000 W / m 2 , 15000 W / m 2 , or 35,000 W / m 2 ) can be selected from the range. The oxygen concentration and exposure illuminance can be combined as appropriate; for example, an oxygen concentration of 10 vol% and an illuminance of 10,000 W / m². 2At an oxygen concentration of 35% by volume, the illuminance is 20,000 W / m². 2 This can be done as follows.
[0291] Next, the unexposed areas of the composition layer are developed and removed to form a pattern (pixels). The unexposed areas of the composition layer can be developed and removed using a developer. This causes the unexposed areas of the composition layer in the exposure process to dissolve in the developer, leaving only the photocured parts. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. In addition, to improve the ability to remove residue, the developer may be emptied every 60 seconds, and the process of supplying fresh developer may be repeated several times.
[0292] Examples of developing solutions include organic solvents and alkaline developers, with alkaline developers being preferred. For the developing solution and the rinsing method after development, the developing solution and rinsing method described in paragraph 0214 of International Publication No. 2022 / 085485 may be used.
[0293] After development and drying, it is preferable to perform additional exposure or heat treatment (post-bake). Additional exposure and post-bake are curing treatments after development to ensure complete hardening. The heating temperature in post-bake is preferably 100 to 300°C, and more preferably 200 to 270°C. Post-bake can be performed continuously or in batches using heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to achieve the above conditions. When performing additional exposure, it is preferable that the light used for exposure has a wavelength of 400 nm or less. The additional exposure may also be performed by the method described in Korean Published Patent No. 10-2017-0122130.
[0294] <Optical Filter> The optical filter of the present invention includes the film of the present invention described above. Examples of types of optical filters include color filters, infrared cut filters, and infrared transmission filters, with color filters being preferred. The color filter preferably has the film of the present invention as its pixels, and more preferably has the film of the present invention as its colored pixels.
[0295] The optical filter may have a protective layer on the surface of the film of the present invention. By providing a protective layer, various functions such as oxygen barrier, low reflectivity, hydrophilicity, and shielding of light of specific wavelengths (ultraviolet rays, infrared rays, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, and more preferably 0.1 to 5 μm. Methods for forming the protective layer include applying a resin composition for forming the protective layer, chemical vapor deposition, and attaching molded resin with an adhesive. The components that make up the protective layer include (meth)acrylic resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene etherphosphine oxide resin, polyimide resin, polyamide-imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluororesin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al 2 O 3 Mo, SiO 2 Si 2 N 4 These are some examples, and two or more of these components may be included. For example, in the case of a protective layer intended for oxygen barrier, the protective layer may be made of polyol resin and SiO 2 And, Si 2 N 4 It is preferable that it contains [a specific component]. Furthermore, in the case of a protective layer intended for low reflectivity, it is preferable that the protective layer contains (meth)acrylic resin and fluororesin.
[0296] When forming a protective layer by coating a resin composition, known methods such as spin coating, casting, screen printing, and inkjet printing can be used as the coating method for the resin composition. The organic solvent contained in the resin composition can be a known organic solvent (for example, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.). When forming the protective layer by chemical vapor deposition, known chemical vapor deposition methods (thermochemical vapor deposition, plasma chemical vapor deposition, photochemical vapor deposition) can be used.
[0297] The protective layer may contain additives such as organic and inorganic fine particles, light absorbers of specific wavelengths (e.g., ultraviolet, infrared, etc.), refractive index adjusters, antioxidants, adhesives, and surfactants, as needed. Examples of organic and inorganic fine particles include polymer fine particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium dioxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silica, calcium carbonate, and barium sulfate. Known light absorbers can be used for light absorbers of specific wavelengths. The content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by mass and more preferably 1 to 60% by mass relative to the total mass of the protective layer.
[0298] As a protective layer, the protective layer described in paragraphs 0073 to 0092 of Japanese Patent Publication No. 2017-151176 can also be used.
[0299] The optical filter may have a structure in which each pixel is embedded in a space partitioned, for example, in a grid pattern by a partition wall.
[0300] <Solid-State Image Sensor> The solid-state image sensor of the present invention has the film of the present invention described above. The configuration of the solid-state image sensor is not particularly limited as long as it has the film of the present invention and functions as a solid-state image sensor, but for example, the following configuration can be given.
[0301] The device has a substrate on which multiple photodiodes and transfer electrodes made of polysilicon or the like constitute the light-receiving area of a solid-state image sensor (such as a CCD (charge-coupled device) image sensor or a CMOS (complementary metal-oxide-semiconductor) image sensor), a light-shielding film with an opening only for the light-receiving portion of the photodiode is placed on the photodiode and transfer electrodes, a device protection film made of silicon nitride or the like is formed on the light-shielding film to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode, and a color filter is placed on the device protection film. Furthermore, the device may have a configuration in which a light-gathering means (for example, a microlens; the same applies hereinafter) is placed on the device protection film and below the color filter (on the side closer to the substrate), or a configuration in which the light-gathering means is placed on the color filter. The color filter may also have a structure in which each colored pixel is embedded in a space partitioned by partitions, for example in a grid pattern. In this case, it is preferable that the partitions have a lower refractive index than each colored pixel. Examples of imaging devices having such a structure include those described in Japanese Patent Publication No. 2012-227478, Japanese Patent Publication No. 2014-179577, and International Publication No. 2018 / 043654. Furthermore, as shown in Japanese Patent Publication No. 2019-211559, the light resistance may be improved by providing an ultraviolet absorption layer within the structure of the solid-state image sensor. The imaging device equipped with the solid-state image sensor of the present invention can be used not only in digital cameras and electronic devices with imaging functions (such as mobile phones), but also in in-vehicle cameras and surveillance cameras.
[0302] <Image Display Device> The image display device of the present invention has the film of the present invention described above. Examples of image display devices include liquid crystal display devices and organic electroluminescent display devices. For definitions of image display devices and details of each image display device, see, for example, "Electronic Display Devices" (by Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990) and "Display Devices" (by Yoshiaki Ibuki, Sangyo Tosho Co., Ltd., published in 1989). Liquid crystal display devices are described, for example, in "Next-Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994). There are no particular restrictions on the liquid crystal display devices to which the present invention can be applied; for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "Next-Generation Liquid Crystal Display Technology".
[0303] The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the structural formulas shown below, iPr represents an isopropyl group, and Ph represents a phenyl group.
[0304] <Synthesis Example> (Synthesis Example 1)15.0 g (0.0350 mol) of trimethylolpropane EO-modified triacrylate (manufactured by Toagosei Co., Ltd., Aronix M-350) and 4.52 g (0.0350 mol) of dibutylamine (manufactured by Fujifilm Wako Pure Chemical Corporation) were added to a 100 ml three-necked flask, and the mixture was heated and stirred at 50 °C for 24 hours. After confirming by NMR (nuclear magnetic resonance) that dibutylamine had disappeared, 45.56 g of propylene glycol monomethyl ether acetate (PGMEA) was added to obtain a 30% by mass solution of amine monomer M6 in PGMEA. Amine monomers M7 to M9, M14 to M23, and M34 to M40 were also synthesized in the same manner.
[0305] (Synthesis Example 2) 15.0 g (0.0757 mol) of 1,4-butanediol diacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.98 g (0.0378 mol) of 2-(2-aminoethoxy)ethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 100 ml three-necked flask, and the mixture was heated and stirred at 70 °C for 48 hours. After confirming by NMR that 2-(2-aminoethoxy)ethanol had disappeared, 44.3 g of PGMEA was added to obtain a 30% by mass solution of amine monomer M1 in PGMEA. Amine monomers M2 to M5, M10 to M13, M24 to M33, and M41 to M52 were also synthesized in the same manner.
[0306] The molecular weight, alkylene oxy group count, amino group count, C=C group count (ethylenically unsaturated bond count), amine value, C=C value (ethylenically unsaturated bond count), and hydroxyl value of amine monomers M1 to M52 are as follows. The amine value, C=C value, and hydroxyl value of amine monomers M1 to M52 are theoretical values calculated from the raw materials used in the synthesis.
[0307] <Manufacturing of Pigment Dispersions> The mixture of materials listed in the table below is mixed and dispersed for 3 hours using a bead mill (using zirconia beads with a diameter of 0.1 mm). Then, it is dispersed again using a high-pressure disperser with a vacuum mechanism, NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.), at a pressure of 2000 MPa and a flow rate of 500 g / min. This dispersion process is repeated 10 times to obtain each pigment dispersion. The average particle size (nm) and viscosity (mPa·s) of the pigment in each pigment dispersion are recorded together. The average particle size of the pigment is measured by dynamic light scattering using a particle size analyzer (nanoSAQLA, manufactured by Otsuka Electronics Co., Ltd.). The viscosity of the pigment dispersion is measured using a viscometer (RE-85L, manufactured by Toki Sangyo Co., Ltd.) with the temperature of the pigment dispersion adjusted to 25°C.
[0308]
[0309]
[0310] The details of the materials listed in the abbreviations in the table above are as follows: (Colorants) PR254: C.I. Pigment Red 254 (diketopyrrolopyrrole compound, red pigment) PR272: C.I. Pigment Red 272 (diketopyrrolopyrrole compound, red pigment) PY139: C.I. Pigment Yellow 139 (isoindoline compound, yellow pigment) PY150: C.I. Pigment Yellow 150 (azobarbiturate compound, yellow pigment) PY185: C.I. Pigment Yellow 150 (isoindoline compound, yellow pigment) PG36: C.I. Pigment Green 36 (phthalocyanine compound, green pigment) PG58: C.I. Pigment Green 58 (phthalocyanine compound, green pigment) PB15:6: C.I. Pigment Blue 15:6 (phthalocyanine compound, blue pigment) PV23: C.I. Pigment Violet 23 (dioxazine compound, purple pigment) PBk32: C.I. Pigment Black 32 (perylene compound, organic black pigment) CB1: Carbon Black (black pigment, manufactured by Mitsubishi Chemical Corporation, #2300) TB1: Titanium Black (black pigment, manufactured by Mitsubishi Materials Corporation, Titanium Black 10S) TB2: Titanium Black (black pigment, manufactured by Akaho Chemicals Co., Ltd., Tilak D) IR Colorant 1: Compound with the following structure (infrared absorbing pigment)
[0311] Derivative 1: Compound with the following structure Derivative 2: Compound with the following structure Derivative 3: Compound with the following structure Derivative 4: Compound with the following structure Derivative 5: Compound with the following structure Derivative 6: Compound with the following structure Derivative 7: Compound with the following structure Derivative 8: Compound with the following structure Derivative 9: Compound with the following structure Derivative 10: A compound with the following structure (n=1) Derivative 11: Compound with the following structure Derivative 12: Compound with the following structure
[0312] (Resin) P1: Prysurf A212C (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., resin having a phosphate group (pKa = approximately 2) and an alkylene oxy group, terminal acid group type) P2: Resin with the following structure (resin having a sulfo group (pKa = approximately 2) and an alkylene oxy group, terminal acid group type) P3: Resin with the following structure (the values appended to the main chain represent the mass ratio of repeating units, and the values appended to the side chain represent the number of repeating units. Weight-average molecular weight 20,000, acid value 130.4 mg KOH / g) P4: Jeffermin M-2070 (manufactured by Tomoe Engineering Co., Ltd., methoxypoly(oxyethylene / oxypropylene)-2-propylamine, a resin having an amino group and an alkylene oxy group)
[0313] (Solvents) Solvent 1: Propylene glycol monomethyl ether acetate Solvent 2: Cyclopentanone Solvent 3: 1-Methoxy-2-propanol
[0314] <Manufacturing of Photocurable Composition> The materials are mixed in the proportions shown in the formulation below, and the mixture is filtered through a nylon filter with a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to produce the photocurable composition. In the table below, the value of the polymerizable monomer content in the total solids of the photocurable composition is indicated in the "Monomer Concentration" column, and the value of the photopolymerization initiator content in the total solids of the photocurable composition is indicated in the "Initiator Concentration" column.
[0315]
[0316]
[0317]
[0318]
[0319]
[0320] The details of the materials listed in the abbreviations in the table above are as follows: (Pigment dispersion) R1-R9, Y1, Y2, G1-G11, B1-B9, Cy1, Cy2, IR1, IR2, Bk1-Bk4: The aforementioned pigment dispersions R1-R9, Y1, Y2, G1-G11, B1-B9, Cy1, Cy2, IR1, IR2, Bk1-Bk4
[0321] (Polymerizable monomers) M1-M52: The amine monomers M1-M52 mentioned above m-1: OGSOL EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd.) m-2: Trimethylolpropane triacrylate m-3: Pentaerythritol tetraacrylate m-4: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) CM1: Compound with the following structure (comparative compound)
[0322] (Binder) b-1: Resin with the following structure (the values appended to the main chain are the molar ratio of repeating units. Weight-average molecular weight 11000, acid value 70 mgKOH / g, C=C value 1.1 mmol / g) b-2: Resin with the following structure (the values attached to the main chain are the molar ratio of repeating units, and the values attached to the side chain are the number of repeating units. Weight-average molecular weight 18000, acid value 61.8 mgKOH / g, C=C value 0.525 mmol / g)
[0323] (Photopolymerization initiators) I-1 to I-10: Compounds with the following structure (oxime compounds)
[0324] (Surfactant) W-1: KF-6000 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone-based surfactant)
[0325] (Polymerization inhibitor) A-1: p-methoxyphenol
[0326] (Thermal crosslinking agent) T-1: Compound with the following structure
[0327] (Additive) X-1: Compound with the following structure
[0328] (Chain transfer agent) S-1: Compound with the following structure
[0329] (Dye) Dye 1: Compound with the following structure (xanthene dye, m=3, n=3, weight-average molecular weight 7000)
[0330] (Solvents) Solvent 1: Propylene glycol monomethyl ether acetate (PGMEA) Solvent 2: Cyclopentanone Solvent 3: 1-Methoxy-2-propanol
[0331] <Evaluation> (Sensitivity evaluation) CT-4000L (manufactured by Fujifilm Electronic Materials Co., Ltd.) is applied to an 8-inch (20.32 cm) silicon wafer using a spin coater to a thickness of 0.1 μm after post-baking. A base coat layer is formed by heating at 220°C for 300 seconds using a hot plate to obtain a silicon wafer with a base coat layer (support). Next, a photocurable composition is applied by spin coating to a film thickness of 0.5 μm after post-baking. Next, it is heated at 90°C for 2 minutes using a hot plate (pre-baking). Next, using an i-line stepper exposure system FPA-3000i5+ (manufactured by Canon Inc.), light with a wavelength of 365 nm is exposed at a specific exposure amount through a 1.0 μm square Bayer pattern mask. Next, the exposed composition layer is developed using a developing device (Act8, manufactured by Tokyo Electron). A 0.20% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) is used as the developer, and shower development is performed at 23°C for 90 seconds. Afterward, rinsing is performed with a spin shower using pure water, followed by spin drying, and then heating (post-bake) on a 200°C hot plate for 5 minutes to form a pattern (pixel). The silicon wafer with the formed pixels is divided, platinum deposition is performed, and a scanning electron microscope (SEM) image of the pixels in cross-section is obtained using a scanning electron microscope. While varying the specific exposure amount described above, the obtained pattern is observed, and the minimum exposure amount that resolves a square pattern with sides of 1.0 μm is determined. The sensitivity is then evaluated according to the following evaluation criteria: -Evaluation Criteria- A: The minimum exposure amount is 100 mJ / cm² 2 B: The minimum exposure dose was less than 100 mJ / cm². 2 More than 200mJ / cm 2C: The minimum exposure dose was less than 200 mJ / cm². 2 More than 500mJ / cm 2 D: The minimum exposure dose was less than 500 mJ / cm². 2 More than 1000mJ / cm 2 E: The minimum exposure dose was less than 1000 mJ / cm². 2 That was all.
[0332] (Evaluation of Adhesion) A photocurable composition is applied to an 8-inch (20.32 cm) silicon wafer by spin coating so that the post-baking film thickness is 0.5 μm. Then, it is heated on a hot plate at 90°C for 2 minutes (pre-baking). Next, using an i-line stepper exposure system FPA-3000i5+ (manufactured by Canon Inc.), exposure is performed at 200 mJ / cm² through a mask having a Bayer pattern that forms a predetermined pixel (pattern) size. 2Exposure is performed with the specified exposure amount. The mask used has a Bayer pattern formed by pixel patterns of 0.7 μm square, 0.8 μm square, 0.9 μm square, 1.0 μm square, 1.1 μm square, 1.2 μm square, 1.3 μm square, 1.4 μm square, 1.5 μm square, 1.6 μm square, 1.7 μm square, 2.0 μm square, 3.0 μm square, 5.0 μm square, and 10.0 μm square. Next, paddle development is performed at 23°C for 90 seconds using a 0.4 mass% aqueous solution of tetramethylammonium hydroxide (TMAH). After that, rinsing is performed with pure water using a spin shower. Next, the pattern (pixels) is formed by heating (post-baking) at 200°C for 5 minutes using a hot plate. Using a high-resolution FEB measuring device (HITACHI CD-SEM) S9380II (manufactured by Hitachi High-Tech Corporation), patterns of 0.7 μm square, 0.8 μm square, 0.9 μm square, 1.0 μm square, 1.1 μm square, 1.2 μm square, 1.3 μm square, 1.4 μm square, 1.5 μm square, 1.6 μm square, 1.7 μm square, 2.0 μm square, 3.0 μm square, 5.0 μm square, and 10.0 μm square were observed, and the smallest pattern size (minimum contact line width) in which the pattern was formed without peeling was determined. The adhesion was then evaluated according to the following criteria. A smaller minimum contact line width indicates better adhesion. -Evaluation Criteria- A: Minimum contact line width is 1.2 μm square or less B: Minimum contact line width is greater than 1.2 μm square and 1.3 μm square or less C: Minimum contact line width is greater than 1.3 μm square and 1.4 μm square or less D: Minimum contact line width is greater than 1.4 μm square and 1.6 μm square or less E: Minimum contact line width is greater than 1.6 μm square
[0333] <Evaluation of chipping suppression> An 8-inch (20.32 cm) silicon wafer is coated with CT-4000L (manufactured by Fujifilm Electronic Materials Co., Ltd.) using a spin coater to a thickness of 0.1 μm after post-baking. A base coat layer is formed by heating at 220°C for 300 seconds using a hot plate, obtaining a silicon wafer (support) with a base coat layer. Next, a photocurable composition is applied by spin coating to a post-baking film thickness of 0.5 μm. Then, it is heated at 90°C for 2 minutes using a hot plate (pre-baking). Finally, using an i-line stepper exposure system FPA-3000i5+ (manufactured by Canon Inc.), light with a wavelength of 365 nm is applied at a rate of 200 mJ / cm². 2 The material is exposed to light through a mask having a 1.0 μm square Bayer pattern at the specified exposure level. Next, the exposed composition layer is developed using a developer (Act8, manufactured by Tokyo Electron). A 0.20 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) is used as the developer, and shower development is performed at 23°C for 90 seconds. After that, the material is rinsed with a spin shower using pure water, then spin-dried, and then heated on a hot plate at 200°C for 5 minutes (post-bake) to form the pattern (pixels). The silicon wafer on which the pixels have been formed is observed at 100 points in the pixel area (pattern) using a high-resolution FEB (Field Emission Beam) measuring device (HITACHI CD-SEM) S9380II (manufactured by Hitachi High-Tech Corporation), and the number of missing pixels is calculated. A pixel with a defect is defined as a pixel with a defect in the rectangular area at the top of the pattern. -Evaluation Criteria- A: 0 missing pixels B: 1 missing pixel C: 2 missing pixels D: 3 or 4 missing pixels E: 5 or more missing pixels
[0334]
[0335]
[0336] As shown in the table above, the examples demonstrate excellent evaluation of sensitivity, adhesion, and chipping suppression.
[0337] Films obtained from the photocurable compositions described in the examples can be suitably used in optical filters, solid-state image sensors, and image display devices.
[0338] In Example 1, even if the resin P1 in the pigment dispersion R1 is replaced with resins P5 to P9, the same effect as in Example 1 can be obtained. Resin P5: Prysurf A208F (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., resin having a phosphate group (pKa = approximately 2) and an alkylene oxy group, terminal acid group type) Resin P6: Prysurf A215C (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., resin having a phosphate group (pKa = approximately 2) and an alkylene oxy group, terminal acid group type) Resin P7: Prysurf A219B (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., resin having a phosphate group (pKa = approximately 2) and an alkylene oxy group, terminal acid group type) Resin P8: Prysurf H-3606 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., resin having a carboxyl group (pKa = approximately 4.5) and an alkylene oxy group, terminal acid group type) Resin P9: Hosmer PP (manufactured by Unichemical Co., Ltd., resin having a phosphate group (pKa = approximately 2), an ethylenically unsaturated bond-containing group and an alkylene oxy group, terminal acid group type)
[0339] In Example 9, even if resin P4 is replaced with resins P10 to P13 as the pigment dispersion R9, the same effect as in Example 9 can be obtained. Resin P10: Jeffermin M-1000 (manufactured by Tomoe Engineering Co., Ltd., methoxypoly(oxyethylene / oxypropylene)-2-propylamine, a resin having an amino group and an alkylene oxy group) Resin P11: Jeffermin M-3085 (manufactured by Tomoe Engineering Co., Ltd., methoxypoly(oxyethylene / oxypropylene)-2-propylamine, a resin having an amino group and an alkylene oxy group) Resin P12: A resin obtained by reacting 7.4 parts by mass of polyethyleneimine (molecular weight 300), 83.3 parts by mass of compound pp12a having the following structure, and 9.2 parts by mass of compound pp12b having the following structure (acid value 44.6 mg KOH / g, amine value 38.9 mg KOH / g, molecular weight 4032). Resin P12 is a resin having a structure represented by formula pp12. Resin P13: A resin obtained by reacting 6.8 parts by mass of polyethyleneimine (molecular weight 300), 84.8 parts by mass of compound pp13a having the structure shown below, and 8.4 parts by mass of compound pp13b having the structure shown below (acid value 40.6 mg KOH / g, amine value 35.7 mg KOH / g, molecular weight 4412). Resin P13 is a resin having the structure represented by formula pp13.
[0340] In Example 1, even if derivative 1 is replaced with derivatives 13 to 18 (compounds with the structure described below) as the pigment dispersion R1, the same effect as in Example 1 can be obtained.
[0341] In Example 9, even if derivative 2 is replaced with derivatives 19 to 28 (compounds with the structure described below) as the pigment dispersion R9, the same effect as in Example 9 can be obtained.
[0342] In Example 1, even if binder b-1 is replaced with binder b-2 described above or a resin synthesized according to the method described in synthesis example P-1 in paragraph 0291 of International Publication No. 2018 / 037812, the same effects as in Example 1 can be obtained.
[0343] In Example 13, even if the thermal crosslinking agent T-1 is changed to thermal crosslinking agent T-2 or T-3 (a compound with the structure shown below), the same effect as in Example 13 can be obtained.
[0344] In Example 1, the same effect can be obtained even if surfactant W-1 is changed to surfactant W-2 or surfactant W-3. Surfactant W-2: A compound with the structure shown below (weight-average molecular weight = 14000, the % value indicating the proportion of repeating units is in mole percent, fluorine-based surfactant) Surfactant W-3: PolyFox PF6320 (manufactured by OMNOVA, a fluorine-based surfactant)
[0345] In Example 1, the same effect can be obtained even if polymerization inhibitor A-1 is changed to polymerization inhibitor A-2 or polymerization inhibitor A-3 (a compound with the structure shown below).
[0346] In Example 75, the same effect can be obtained even if additive X-1 is changed to additive X-2 (a compound with the structure shown below).
[0347] In Example 76, the same effect can be obtained even if dye Dey1 is changed to dye Dey2 (a compound with the structure shown below).
[0348] In Example 154, the same effect can be obtained even if the chain transfer agent S-1 is changed to the chain transfer agent S-2 (a compound with the structure shown below).
Claims
1. A photocurable composition comprising a polymerizable monomer and a photopolymerization initiator, wherein the polymerizable monomer comprises polymerizable monomer a having an amino group, an alkylene oxy group, and an ethylenically unsaturated bond-containing group, and the photopolymerization initiator comprises an oxime compound.
2. The photocurable composition according to claim 1, wherein the alkylene oxy group of the polymerizable monomer a is an ethylene oxy group.
3. The photocurable composition according to claim 1 or 2, wherein the hydroxyl value of the polymerizable monomer a is 100 mg KOH / g or less.
4. The photocurable composition according to claim 1 or 2, wherein the amine value of the polymerizable monomer a is 80 mg KOH / g or less.
5. The photocurable composition according to claim 1 or 2, wherein the ethylenically unsaturated bond content value of the polymerizable monomer a is 1.5 mmol / g or more.
6. The photocurable composition according to claim 1 or 2, wherein the polymerizable monomer a comprises polymerizable monomer a1 having an amino group, an alkylene oxy group, and six or more ethylenically unsaturated bond-containing groups.
7. The photocurable composition according to claim 6, wherein the polymerizable monomer a further comprises polymerizable monomer a2 having an amino group, an alkylene oxy group, and 1 to 5 ethylenically unsaturated bond-containing groups.
8. The photocurable composition according to claim 1 or 2, wherein the polymerizable monomer further comprises polymerizable monomer b other than polymerizable monomer a, and either polymerizable monomer a or polymerizable monomer b comprises a compound having six or more ethylenically unsaturated bond-containing groups, and the other comprises a compound having one to five ethylenically unsaturated bond-containing groups.
9. The oxime compound-containing photocurable composition according to claim 1 or 2, wherein the oxime compound contains a compound represented by formula (OX-1); In formula (OX-1), X 1a represents a divalent linking group containing at least one selected from the group consisting of an aromatic ring and a heterocyclic ring, R 1a represents a hydrogen atom or an acyl group, R 2a represents an alkyl group or an aryl group, R 3a and R 4a each independently represent a hydrogen atom or an alkyl group, Alk 1 and Alk 2 each independently represent an alkyl group, R 3a and R 4a may combine to form a ring, Alk 1 and Alk 2 may combine to form a ring, and n represents 0 or 1.
10. The photocurable composition according to claim 1 or 2, comprising a resin having an alkylene oxy group.
11. The photocurable composition according to claim 1 or 2, comprising a resin having a phosphate group and an alkylene oxy group.
12. The photocurable composition according to claim 1 or 2, further comprising a colorant.
13. A film obtained using the photocurable composition according to claim 1 or 2.
14. An optical filter having the film described in claim 13.
15. A solid-state image sensor having the film described in claim 13.
16. An image display device having the film described in claim 13.