CN117545783A

CN117545783A - Curable composition, method for producing cured product, film, optical element, image sensor, solid-state imaging element, image display device, and radical polymerization initiator

Info

Publication number: CN117545783A
Application number: CN202280040973.0A
Authority: CN
Inventors: 牧野雅臣
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2021-08-26
Filing date: 2022-08-15
Publication date: 2024-02-09
Also published as: WO2023026884A1; KR20240005842A; TW202309170A

Abstract

The present invention provides a curable composition which generates little outgas from the obtained cured product. The curable composition comprises a radical polymerization initiator represented by formula 1 and a radical polymerizable compound, wherein Ar in formula 1 ¹ Represents an aromatic or heteroaromatic ring, X ¹ representing-OR ¹¹ or-NR ¹² R ¹³ ，Y ¹ Represents a 2-valent linking group, R ^a Represents a hydrogen atom or a substituent, R ¹¹ ～R ¹³ Each independently represents a hydrogen atom or a substituent.

Description

Curable composition, method for producing cured product, film, optical element, image sensor, solid-state imaging element, image display device, and radical polymerization initiator

Technical Field

The present invention relates to a curable composition, a method for producing a cured product, a film, an optical element, an image sensor, a solid-state imaging element, an image display device, and a radical polymerization initiator.

Background

Filters such as color filters are manufactured using curable compositions containing colorants, photopolymerization initiators, and polymerizable compounds.

As a conventional curable composition, a composition described in patent document 1 or 2 is known.

Patent document 1 describes a polymerizable composition containing a specific α -aminoketone compound having a carbazole structure.

Patent document 2 describes an active energy ray-curable ink containing a specific α -aminoketone compound having a specific fluorene structure.

Technical literature of the prior art

Patent literature

Patent document 1: japanese patent laid-open No. 2007-163542

Patent document 2: japanese patent laid-open No. 2020-169251

Disclosure of Invention

Technical problem to be solved by the invention

The object of the present invention is to provide a curable composition which is less in outgas from the cured product obtained.

Another object of another embodiment of the present invention is to provide a method for producing a cured product of the curable composition, or a film, an optical element, an image sensor, a solid-state imaging element, or an image display device using the curable composition.

Another object of another embodiment of the present invention is to provide a novel radical polymerization initiator.

Means for solving the technical problems

The following means are included in the means for solving the above problems.

<1> a curable composition comprising a radical polymerization initiator represented by the following formula 1 and a radical polymerizable compound.

[ chemical formula 1]

Ar in formula 1 ¹ Represents an aromatic or heteroaromatic ring, X ¹ representing-OR ¹¹ or-NR ¹² R ¹³ ，Y ¹ Represents a 2-valent linking group, R ^a Represents a hydrogen atom or a substituent, R ¹¹ ～R ¹³ Each independently represents a hydrogen atom or a substituent.

<2> the curable composition according to <1>, wherein,

the radical polymerization initiator represented by the above formula 1 is a radical polymerization initiator represented by the following formula 2.

[ chemical formula 2]

Ar in formula 2 ² Represents an aromatic or heteroaromatic ring, X ² representing-OR ²⁴ or-NR ²⁵ R ²⁶ ，Y ² Represents a single bond or a 2-valent linking group, R ²¹ ～R ²⁶ Each independently represents a hydrogen atom or a substituent, R ²⁵ And R is R ²⁶ May be connected to form a ring, and n represents an integer of 1 to 3.

<3> the curable composition according to <1> or <2>, wherein,

the radical polymerization initiator represented by the above formula 1 is a radical polymerization initiator represented by the following formula 3A or formula 3B.

[ chemical formula 3]

In formula 3A or formula 3B, X ³ representing-OR ³⁴ or-NR ³⁵ R ³⁶ ，Y ³ Represents a single bond, -O-or-S-, R ³¹ Represents alkyl or aryl, R ³² ～R ³⁶ Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ³⁵ And R is R ³⁶ Can be linked to form a ring, n represents an integer of 1 to 3, R ³⁹ Each independently represents a substituent, and m represents an integer of 0 to 2.

<4> the curable composition according to any one of <1> to <3>, wherein,

the radical polymerization initiator represented by the above formula 1 is a radical polymerization initiator represented by the following formula 4.

[ chemical formula 4]

In formula 4, X ⁴ representing-OR ⁴⁴ or-NR ⁴⁵ R ⁴⁶ ，Y ⁴ Represents a single bond, -O-or-S-, R ⁴¹ Represents alkyl or aryl, R ⁴² ～R ⁴⁶ Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ⁴⁵ And R is R ⁴⁶ Can be linked to form a ring, n represents an integer of 1 to 3, L ¹ L and L ² Respectively and independently represent a single bond, -CR ⁴⁷ R ⁴⁸ -, -O-, -S-or-NR ⁴⁹ -，R ⁴⁷ ～R ⁴⁹ Each independently represents a hydrogen atom, an alkyl group or an aryl group, p represents 0 or 1, q represents an integer of 0 to 2, Z ¹ Represents alkyl, aryl, halogen, nitro, cyano, carboxyl, sulfo or-C (=O) Z ² ，Z ² Represents aryl or heteroaryl.

<5> the curable composition according to any one of <1> to <4>, further comprising a colorant.

<6> the curable composition according to any one of <1> to <5>, further comprising an oxime compound.

<7> the curable composition according to any one of <1> to <6>, wherein,

the radical polymerization initiator represented by the above formula 1 has a molar absorptivity of 1,000 L.mol with respect to light having a wavelength of 248nm in acetonitrile solution at 25 DEG C ^-1 ·cm ^-1 The above.

<8> a method for producing a cured product, comprising the step of irradiating the curable composition of any one of <1> to <7> with light having a wavelength of 150nm to 300 nm.

<9> a film obtained by curing the curable composition according to any one of <1> to <7 >.

<10> an optical element having the film of <9 >.

<11> an image sensor having the film of <9 >.

<12> a solid-state imaging element having the film of <9 >.

<13> an image display device having the film of <9 >.

<14> a radical polymerization initiator represented by the following formula 1.

[ chemical formula 5]

<15> the radical polymerization initiator according to <14>, wherein,

[ chemical formula 6]

Ar in formula 2 ² Represents an aromatic or heteroaromatic ring, X ² representing-OR ²⁴ or-NR ²⁵ R ²⁶ ，Y ² Represents a single bond or a valence of 2Linking group, R ²¹ ～R ²⁶ Each independently represents a hydrogen atom or a substituent, R ²⁵ And R is R ²⁶ May be connected to form a ring, and n represents an integer of 1 to 3.

<16> the radical polymerization initiator according to <14> or <15>, wherein,

[ chemical formula 7]

<17> the radical polymerization initiator according to any one of <14> to <16>, wherein,

[ chemical formula 8]

Effects of the invention

According to an embodiment of the present invention, there is provided a curable composition having little outgas from the obtained cured product.

Further, according to another embodiment of the present invention, there is provided a method for producing a cured product of the curable composition, or a film, an optical element, an image sensor, a solid-state imaging element, or an image display device using the curable composition.

Further, according to another embodiment of the present invention, there is provided a novel radical polymerization initiator.

Detailed Description

The following describes the present invention in detail. The following description of the constituent elements is made in accordance with the representative embodiment of the present invention, but the present invention is not limited to this embodiment.

In the present specification, "to" is used in a meaning including values described before and after the values as a lower limit value and an upper limit value.

In the labeling of groups (radicals) in the present specification, the label which is not labeled with a substituted or unsubstituted includes a group (radical) having no substituent and includes a group (radical) having a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, "exposure" includes exposure using light, and drawing using a particle beam such as an electron beam or an ion beam is also included in exposure unless otherwise specified. Examples of the light used for exposure include an open spectrum of a mercury lamp, extreme ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), active rays such as X-rays and electron beams, and radiation.

In the present specification, "(meth) acrylic acid ester" means either or both of acrylic acid ester and methacrylic acid ester, "(meth) acrylic acid" means either or both of acrylic acid and methacrylic acid, and "(meth) acryl" means either or both of acryl and methacryl.

In the present specification, me in the structural formula represents methyl, et represents ethyl, bu represents butyl, and Ph represents phenyl.

In the present specification, the weight average molecular weight and the number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).

In the present specification, the total solid component means the total mass of components from which the solvent is removed from all components of the composition.

In the present specification, the pigment means a colorant which is not easily dissolved in a solvent.

In the present specification, the term "process" includes not only an independent process but also the term if the intended function of the process is achieved even if the process cannot be clearly distinguished from other processes.

The present invention will be described in detail below.

(curable composition)

The curable composition of the present invention comprises a radical polymerization initiator represented by the following formula 1 and a radical polymerizable compound.

[ chemical formula 9]

As a result of intensive studies, the present inventors have found that by adopting the above-described structure, a curable composition having less outgas from the obtained cured product can be obtained.

The radical polymerization initiator represented by the above formula 1 is a cyclic ketone structure, and an oxygen atom or a nitrogen atom is bonded to the α -position of the above cyclic ketone structure, and therefore the bond between the carbon atom of the carbonyl group in the above cyclic ketone structure and the α -carbon atom bonded to the oxygen atom or the nitrogen atom is cleaved to generate a radical. Further, it is presumed that since the radical generated here is linked to the cyclic ketone structure and is less likely to generate volatile components, it is possible to suppress gas (outgas) discharged from a cured product obtained by curing the curable composition after curing.

The curable composition according to the present invention can be preferably used as a curable composition for an optical filter. The filter may be a color filter, an infrared transmission filter, or the like, and is preferably a color filter. That is, the curable composition according to the present invention can be preferably used as a curable composition for color filters. More specifically, the curable composition for forming a pixel can be preferably used as a color filter. Examples of the types of pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.

The infrared transmission filter may preferably be a filter that satisfies spectral characteristics such that the maximum value of the transmittance in the wavelength range of 400nm to 640nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1,100nm to 1,300nm is 70% or more (preferably 75% or more, more preferably 80% or more). The infrared transmission filter is preferably a filter satisfying any one of the spectral characteristics (1) to (5) below.

(1): a filter having a maximum value of transmittance in a wavelength range of 400nm to 640nm of 20% or less (preferably 15% or less, more preferably 10% or less) and a minimum value of transmittance in a wavelength range of 800nm to 1,500nm of 70% or more (preferably 75% or more, more preferably 80% or more).

(2): a filter having a maximum value of transmittance in a wavelength range of 400nm to 750nm of 20% or less (preferably 15% or less, more preferably 10% or less) and a minimum value of transmittance in a wavelength range of 900nm to 1,500nm of 70% or more (preferably 75% or more, more preferably 80% or more).

(3): a filter having a maximum value of transmittance in a wavelength range of 400nm to 830nm of 20% or less (preferably 15% or less, more preferably 10% or less) and a minimum value of transmittance in a wavelength range of 1,000nm to 1,500nm of 70% or more (preferably 75% or more, more preferably 80% or more).

(4): a filter having a maximum value of transmittance in a wavelength range of 400nm to 950nm of 20% or less (preferably 15% or less, more preferably 10% or less) and a minimum value of transmittance in a wavelength range of 1,100nm to 1,500nm of 70% or more (preferably 75% or more, more preferably 80% or more).

(5): a filter having a maximum value of transmittance in a wavelength range of 400nm to 1,050nm of 20% or less (preferably 15% or less, more preferably 10% or less) and a minimum value of transmittance in a wavelength range of 1,200nm to 1,500nm of 70% or more (preferably 75% or more, more preferably 80% or more).

The curable composition according to the present invention is preferably used as a solid-state imaging device. More specifically, the curable composition for a filter used for a solid-state imaging element can be preferably used, and the curable composition for a color filter used for a solid-state imaging element is more preferably used.

The solid content concentration of the curable composition according to the present invention is preferably 5 to 30% by mass. The lower limit is more preferably 7.5 mass% or more, and still more preferably 10 mass% or more. The upper limit is more preferably 25 mass% or less, and still more preferably 20 mass% or less.

< radical polymerization initiator represented by formula 1 >

The curable composition according to the present invention contains a radical polymerization initiator represented by the above formula 1.

The radical polymerization initiator represented by the above formula 1 is preferably a photo radical polymerization initiator, and more preferably a photo radical polymerization initiator that generates radicals by light having a wavelength of 150nm to 300nm.

The exposure wavelength for generating radicals by the radical initiator represented by the above formula 1 is preferably 150nm to 460nm, more preferably 150nm to 420nm, still more preferably 150nm to 380nm, and particularly preferably 150nm to 300nm.

Ar in formula 1 is from the viewpoints of the suppression of outgas generated from the obtained cured product (hereinafter, also simply referred to as "outgas suppression") and sensitivity ¹ The aromatic ring is preferably an aromatic ring having a carbazole ring structure, a fluorene ring structure, a diaryl sulfide structure, a dibenzothiophene structure, a diarylmethane structure, a triarylmethane structure, a biphenyl structure, or a naphthalene ring structure, more preferably an aromatic ring having a carbazole ring structure, a fluorene ring structure, or a diaryl sulfide structure, and particularly preferably an aromatic ring having a carbazole ring structure or a fluorene ring structure.

And Ar is as described above ¹ The aromatic or heteroaromatic ring in (2) may have a substituent. The substituent is not particularly limited, and a substituent having 0 to 100 carbon atoms is preferable, and a substituent having 0 to 50 carbon atoms is more preferable. Examples of the substituent include a halogen atom, a hydroxyl group, an amino group, an alkyl group, a cycloalkyl group, a heterocyclic group, an aryl group, a heteroaryl group, an acyl group, a nitro group, a cyano group, a sulfo group, an alkylaminocarbonyl group, an alkoxycarbonyl group, an alkylthio group, an arylthio group, a morpholino group, an alkoxyalkyl group, a carboxyl group, and a carboxyalkyl group. Further, these substituents may further have a substituent, and the substituents may bond to each other to form a ring structure.

In addition, ar is as described above ¹ The aromatic ring or heteroaromatic ring in (a) may be condensed by a ring structure such as an aliphatic ring, a heterocyclic ring, an aromatic ring, or a heteroaromatic ring.

From the standpoint of gassing inhibition and sensitivity, X in formula 1 ¹ preferably-NR ¹² R ¹³ 。

And, -OR from the viewpoint of gassing inhibition and sensitivity ¹¹ R in (a) ¹¹ Preferably a hydrogen atom, an alkyl group or an aryl group,more preferably a hydrogen atom or an alkyl group, particularly preferably an alkyl group, most preferably a methyl group.

From the standpoint of gassing inhibition and sensitivity, -NR ¹² R ¹³ R in (a) ¹² R is R ¹³ Each independently is preferably an alkyl group or an aryl group, more preferably an alkyl group, and particularly preferably a methyl group.

R is as described above ¹¹ ～R ¹³ The alkyl group and the aryl group in (a) may have a substituent. Examples of the substituent include the above substituents.

And, -NR ¹² R ¹³ R in (a) ¹² R is R ¹³ Can be bonded to each other to form a ring. The number of ring-forming atoms of the ring is not particularly limited, but is preferably a 3-to 12-membered ring, more preferably a 3-to 7-membered ring, and particularly preferably a 3-to 6-membered ring. At this time, -NR from the viewpoint of gassing inhibition and sensitivity ¹² R ¹³ Preferably aziridine, azetidine, thiomorpholine, dioxothiomorpholine, piperazine (even if considered other Zhong Huanzhuang amines), pyrrolidinyl, piperidinyl or morpholinyl, more preferably morpholinyl.

Wherein, as-NR ¹² R ¹³ From the viewpoints of gassing inhibition and sensitivity, it is preferably a dialkylamino group, a pyrrolidinyl group, a piperidinyl group or a morpholinyl group, and more preferably a dimethylamino group or a morpholinyl group.

From the standpoint of gassing inhibition, sensitivity and solubility, Y in formula 1 is contained ¹ The ring of the ring-forming atom is preferably a 5-to 8-membered ring, more preferably a 5-to 7-membered ring, particularly preferably a 5-or 6-membered ring from the viewpoint of sensitivity, and particularly preferably a 7-membered ring from the viewpoint of solubility.

From the viewpoints of gassing inhibition and sensitivity, Y in formula 1 ¹ Preferably an alkylene group, a group in which an alkylene group is bonded to an ether bond, or a group in which an alkylene group is bonded to a thioether bond, more preferably a methylene group, a vinyl group or a-CH group ₂ -O-、-CH ₂ CH ₂ -O-or-CH ₂ -S-。

And Y is ¹ Having ether or thioether linkages, inhibiting or sensitivity from gassingFrom the viewpoint, Y is preferable ¹ In which-O-or-S-is directly bonded to Ar ¹ 。

From the standpoint of gassing inhibition and sensitivity, R in formula 1 ^a Preferably alkyl or aryl, more preferably alkyl, methyl, ethyl, particularly preferably benzyl or p-methylbenzyl.

From the viewpoint of sensitivity, the radical polymerization initiator represented by formula 1 preferably has an arylcarbonyl group or a heteroarylcarbonyl group, and particularly preferably has a benzoyl group.

Further, from the viewpoint of adhesion, the radical polymerization initiator represented by formula 1 preferably has a nitro group, and more preferably has a nitro group on an aromatic ring.

The radical polymerization initiator represented by formula 1 preferably has a halogen atom, more preferably a chlorine atom or a bromine atom, and particularly preferably a chlorine atom or a bromine atom on an aromatic ring from the viewpoint of adhesion.

Further, from the viewpoint of suppressing loss in the plane direction at the bottom and end of the exposure portion (hereinafter, also simply referred to as "undercut suppressing property"), the radical polymerization initiator represented by formula 1 preferably has a sulfur atom, and more preferably has a sulfur atom directly bonded to an aromatic ring.

The preferable embodiments of the radical polymerization initiator represented by formula 1 are the same as those of formulas 2, 3A, 3B and 4.

The radical polymerization initiator represented by the above formula 1 is preferably a radical polymerization initiator represented by the following formula 2 from the viewpoints of gassing inhibition and sensitivity.

[ chemical formula 10]

Ar in formula 2 ² Represents an aromatic or heteroaromatic ring, X ² representing-OR ²⁴ or-NR ²⁵ R ²⁶ ，Y ² Represents a single bond or a 2-valent linking group, R ²¹ ～R ²⁶ Independently represent a hydrogen atom A sub or substituent, R ²⁵ And R is R ²⁶ May be connected to form a ring, and n represents an integer of 1 to 3.

Ar in formula 2 ² Ar in formula 1 ¹ The meaning of (2) is the same, and the preferred mode is the same.

X in formula 2 ² 、-OR ²⁴ -NR ²⁵ R ²⁶ And X in formula 1 ¹ 、-OR ¹¹ -NR ¹² R ¹³ The meaning of (2) is the same as that of each other, and the preferable mode is the same as that of each other.

R in formula 2 ²¹ R in formula 1 ^a The meaning of (2) is the same, and the preferred mode is the same.

From the standpoint of gassing inhibition and sensitivity, Y in formula 2 ² Preferably a single bond, -O-or-S-, more preferably-O-or-S-.

From the standpoint of gassing inhibition and sensitivity, R in formula 2 ²² R is R ²³ Each independently is preferably a hydrogen atom, more preferably an alkyl group or an aryl group, a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

From the viewpoint of sensitivity, n in formula 2 is preferably 1 or 2.

The radical polymerization initiator represented by the above formula 1 is more preferably a radical polymerization initiator represented by the following formula 3A or 3B, and still more preferably a radical polymerization initiator represented by the following formula 3A, from the viewpoints of gassing inhibition and sensitivity.

[ chemical formula 11]

In formula 3A or formula 3B, X ³ representing-OR ³⁵ or-NR ³⁵ R ³⁶ ，Y ³ Represents a single bond, -O-or-S-, R ³¹ Represents alkyl or aryl, R ³² ～R ³⁶ Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ³⁵ And R is R ³⁶ Can be linked to form a ring, n represents an integer of 1 to 3, R ³⁹ Each independently represents a substituent, and m represents an integer of 0 to 2.

X in formula 3 ³ 、-OR ³⁴ -NR ³⁵ R ³⁶ And X in formula 1 ¹ 、-OR ¹¹ -NR ¹² R ¹³ The meaning of (2) is the same as that of each other, and the preferable mode is the same as that of each other.

R in formula 3 ³¹ R in formula 1 ^a The meaning of (2) is the same, and the preferred mode is the same.

Y in formula 3 ³ 、R ³² 、R ³³ And n and Y in formula 2 ² 、R ²² 、R ²³ And n are the same as each other, and the preferable modes are the same as each other.

M in formula 3A or formula 3B is preferably 0 or 1, more preferably 1.

R as formula 3A or formula 3B ³⁹ Examples of the substituent(s) in (a) include the above-mentioned substituents.

Wherein R is as R ³⁹ From the viewpoints of gassing inhibition and sensitivity, a halogen atom, an alkoxy group, an alkylthio group or an aryl group is preferable.

The radical polymerization initiator represented by the above formula 1 is particularly preferably a radical polymerization initiator represented by the following formula 4 from the viewpoints of gassing suppression and sensitivity.

[ chemical formula 12]

In formula 4, X ⁴ representing-OR ⁴⁴ or-NR ⁴⁵ R ⁴⁶ ，Y ⁴ Represents a single bond, -O-or-S-, R ⁴¹ Represents alkyl or aryl, R ⁴² ～R ⁴⁶ Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ⁴⁵ And R is R ⁴⁶ Can be linked to form a ring, n represents an integer of 1 to 3, L ¹ L and L ² Respectively and independently represent a single bond, -CR ⁴⁷ R ⁴⁸ -, -O-, -S-or-NR ⁴⁹ -，R ⁴⁷ ～R ⁴⁹ Each independently represents a hydrogen atom, an alkyl group or an aryl group, p represents 0 or 1, q represents an integer of 0 to 2, Z ¹ Represents alkyl, aryl,Halogen atoms, nitro groups, cyano groups, carboxyl groups, sulfo groups or-C (=o) Z ² ，Z ² Represents aryl or heteroaryl.

X in formula 4 ⁴ 、-OR ⁴⁴ -NR ⁴⁵ R ⁴⁶ And X in formula 1 ¹ 、-OR ¹¹ -NR ¹² R ¹³ The meaning of (2) is the same as that of each other, and the preferable mode is the same as that of each other.

R in formula 4 ⁴¹ R in formula 1 ^a The meaning of (2) is the same, and the preferred mode is the same.

Y in formula 4 ⁴ 、R ⁴² 、R ⁴³ And n and Y in formula 2 ² 、R ²² 、R ²³ And n are the same as each other, and the preferable modes are the same as each other.

From the standpoint of gassing inhibition and sensitivity, L in formula 4 ¹ Preferably a single bond, -S-, or-NR ⁴⁹ -, more preferably-S-or-NR ⁴⁹ -, particularly preferably-NR ⁴⁹ -。

From the standpoint of gassing inhibition and sensitivity, R in formula 4 ⁴⁷ ～R ⁴⁹ Each independently is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably an ethyl group.

And R is ⁴⁷ ～R ⁴⁹ The alkyl group and the aryl group in (a) may have a substituent. Examples of the substituent include the above substituents.

From the standpoint of gassing inhibition and sensitivity, L in formula 4 ² Preferably a single bond or-CR ⁴⁷ R ⁴⁸ -, more preferably a single bond.

From the viewpoints of gassing inhibition and sensitivity, L in formula 4 ² Preferably Y ⁴ Ortho to the bonding position of (i.e. Y) ⁴ And L is equal to ¹ And a position therebetween.

In addition, from the viewpoints of gassing inhibition and sensitivity, L in formula 4 ² Preferably L ¹ Ortho to the bonding position of (c).

From the viewpoints of gassing inhibition and sensitivity, p in formula 4 is preferably 1.

Q in formula 4 is preferably 0 or 1, more preferably 1.

From the standpoint of gassing inhibition, sensitivity and adhesion, Z in formula 4 ¹ The halogen atom, the nitro group, the cyano group, and the benzoyl group are preferable, the chlorine atom, the bromine atom, the nitro group, and the benzoyl group are more preferable, the chlorine atom, the bromine atom, and the nitro group are particularly preferable from the viewpoint of adhesion, and the benzoyl group is particularly preferable from the viewpoint of sensitivity.

From the viewpoint of sensitivity, Z in formula 4 ² Aryl is preferred, and phenyl is more preferred.

The radical polymerization initiator represented by the above formula 1 preferably has an absorption at any one of the ArF absorption region, i.e., a wavelength of 194nm, the KrF absorption region, i.e., a wavelength of 248nm, and the i-ray absorption region, i.e., a wavelength of 365 nm.

From the viewpoint of sensitivity, the molar absorptivity of the radical polymerization initiator represented by the above formula 1 at any one of the wavelengths 194nm, 248nm or 365nm is preferably 10 L.mol ^-1 ·cm ^-1 The above is more preferably 100 L.mol ^-1 ·cm ^-1 The above is particularly preferably 1,000 L.mol ^-1 ·cm ^-1 The above.

Among them, the radical polymerization initiator represented by the above formula 1 preferably has a molar absorptivity of 1,000 L.mol with respect to light having a wavelength of 248nm in acetonitrile solution at 25℃from the viewpoints of sensitivity and adhesion ^-1 ·cm ^-1 The above is more preferably 2,000 or more, and particularly preferably 3,000 or more. The upper limit is not limited, but is preferably 50,000 or less, more preferably 30,000 or less, and particularly preferably 10,000 or less. By setting the upper limit of the molar absorptivity to 10,000 or less, the transmittance of the exposure light source is improved, and the adhesion is improved.

Specific examples of the radical polymerization initiator represented by the above formula 1 include, but are not limited to, A-1 to A-112. The values in parentheses below represent the molar absorptivity (L.mol) with respect to light having a wavelength of 248nm in acetonitrile solution at 25 ℃ ^-1 ·cm ^-1 )。

Among them, at least 1 radical polymerization initiator selected from the group consisting of A-6 (23,000), A-15 (21,200), A-22 (28,500), A-32 (32,000), A-46 (31,100), A-49 (35,500), A-64 (33,000), A-68 (19,800), A-92 (3,400), A-103 (2,800) and A-109 (8,000) is preferable as the radical polymerization initiator represented by the above formula 1.

[ chemical formula 13]

[ chemical formula 14]

[ chemical formula 15]

[ chemical formula 16]

[ chemical formula 17]

The curable composition according to the present invention may contain 1 kind of radical polymerization initiator represented by the above formula 1 alone or 2 or more kinds of radical polymerization initiators. When 2 or more kinds are used, it is preferable that the total amount thereof is in the following range.

The content of the radical polymerization initiator represented by the above formula 1 is preferably 0.01 to 30% by mass, more preferably 0.05 to 20% by mass, even more preferably 0.1 to 10% by mass, and particularly preferably 1 to 8% by mass, relative to the total solid content of the curable composition, from the viewpoints of gas release inhibition and simplicity.

The radical polymerization initiator represented by the above formula 1 preferably has no absorption at a wavelength of 450nm or more, and more preferably has no absorption at a wavelength of 420nm or more. That is, the radical polymerization initiator represented by the above formula 1 is preferably white to pale yellow. The above color is preferable because it has little influence on the spectral analysis of the color filter.

Among the radical polymerization initiators represented by the above formula 1, a carbazole structure, a diphenyl sulfide structure, a biphenyl structure, or a fluorene structure is preferable as the structure having absorption at the above wavelength.

The method for producing the radical polymerization initiator represented by the above formula 1 is not particularly limited, and it may be produced by a known method or may be produced by referring to a known method.

When the radical polymerization initiator represented by the above formula 1 is an α -aminoketone compound, it can be synthesized by the same method as the known chain α -aminoketone compound, and for example, it can be synthesized by the method described in japanese patent application laid-open No. 2008-31280.

Also, it is preferable to anionize the alpha position of the cyclic ketone compound linked to the aromatic group with sodium methoxide (base) and then to react with an alkyl halide (R ^a -X) is reacted to monoalkylate, and the alpha-position halogen (bromine) is reacted with a secondary amine compound (HNR) in the presence of sodium methoxide (base) ¹² R ¹³ ) A method of carrying out the reaction.

In addition, it is also preferable to carry out monohalogenation (bromination) of the alpha-position of the cyclic ketone compound and then to carry out the reaction with a secondary amine compound (HNR ¹² R ¹³ ) The reaction is carried out and finally it is reacted with an alkyl halide (R) in the presence of sodium hydroxide (base) ^a -X) a process for alkylation by reaction.

[ chemical formula 18]

When the radical polymerization initiator represented by the above formula 1 is an α -hydroxyketone compound, a method in which the portion that reacts with the above secondary amine compound is replaced with potassium hydroxide is preferable.

As a method for synthesizing a ketone compound to be a precursor, for example, a method described in japanese patent application laid-open publication No. 2011-33793, japanese patent application laid-open publication No. 2011-209755, japanese patent application laid-open publication No. 2011-227295, international publication No. 2012/169812, international publication No. 2021/0232144, and the like can be mentioned as a method for synthesizing a cyclic ketone bonded to an aromatic group.

As the secondary amine compound used for the reaction, aliphatic secondary amine compounds such as dimethylamine, diethylamine, dipropylamine, dibutylamine, dimethanol amine, diethanolamine, piperidine, morpholine, thiomorpholine, N-methylpiperazine, N-ethylpiperazine, N-isopropylpiperazine, pyrrolidine, dihexylamine, dioctylamine, didecylamine, and ethylmethylamine, alicyclic secondary amine compounds such as aziridine, azetidine, pyrrolidine, piperidine, norbornanedimethylamine, 1, 3-bis (4-piperidyl) propane, and aromatic secondary amine compounds such as benzyl methylamine, diphenylamine, and dibenzylamine can be used.

Among them, dimethylamine or morpholine is particularly preferred.

< other radical polymerization initiator >

The curable composition according to the present invention may contain a radical polymerization initiator other than the radical polymerization initiator represented by the above formula 1.

Examples of the other radical polymerization initiator include oxime compounds, α -aminoacetophenone compounds, α -hydroxyketone compounds, and acylphosphine compounds.

Among them, oxime compounds are preferable.

By combining the radical polymerization initiator represented by the above formula 1 with another radical polymerization initiator, a pattern having a good rectangular shape and more excellent balance can be obtained.

Examples of the oxime compound include a compound described in Japanese patent application laid-open No. 2001-233836, a compound described in Japanese patent application laid-open No. 2000-080068, a compound described in J.C.S. Perkin II (1979, pages 1653-1660), a compound described in J.C.S. Perkin II (1979, pages 156-162), a compound described in Journal of Photopolymer Science and Technology (1995, pages 202-232), a compound described in Japanese patent application laid-open No. 2000-066385, a compound described in Japanese patent application laid-open No. 2004-534797, a compound described in Japanese patent application laid-open No. 2006-342166, a compound described in Japanese patent application laid-open No. 2017-019766, a compound described in International publication No. 15235, a compound described in International publication No. 2017/051680, a compound described in Japanese patent application laid-open No. 2017-198865, a compound described in International publication No. 20157-publication No. 2015, a compound described in International publication No. 20157-publication No. 2020-No. 2020, a compound described in International publication No. 2015-1675, a compound described in International publication No. 2015-No. 2015-1675, a compound described in International publication No. 2015, a publication No. 2015-publication No. 2015, and a compound described in International publication No. 2015-publication No. 2015, and a compound described in International publication, and the publication laid-publication, etc. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopenta-3-one, 2-acetoxyimino1-phenylpropan-1-one, 2-benzoyloxyimino1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino1-phenylpropan-1-one and the like, and 1- [4- (phenylthio) phenyl ] -3-cyclohexyl-propane-1, 2-dione-2- (0-acetyloxime). As commercial products, irgacure-OXE01, irgacure-OXE02, irgacure-OXE03, irgacure-OXE04 (manufactured by BASF corporation, above), TR-PBG-304, TR-PBG-327 (manufactured by TRONLY corporation), adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, japanese patent application laid-open No. 2012-014052) may be mentioned.

Furthermore, as the oxime compound, a compound which is free from coloring or a compound which is highly transparent and hardly discolored is preferably used. Examples of the commercial products include ADEKA ARKLS NCI-730, NCI-831, and NCI-930 (manufactured as ADEKA CORPORATION above).

Further, as another radical polymerization initiator, a fluorenyl aminoketone photoinitiator described in Japanese patent application laid-open No. 2020-507664 can be used.

As the oxime compound, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include a compound described in JP-A2014-137466, a compound described in JP-A6636081, and a compound described in Korean patent application No. 10-2016-0109444.

As the oxime compound, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring becomes a naphthalene ring can also be used. Specific examples of such oxime compounds include those described in international publication No. 2013/083505.

As the oxime compound, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom include a compound described in JP 2010-26261028A, compounds 24, 36 to 40 described in JP 2014-500852A, and compound (C-3) described in JP 2013-164471A.

As the oxime compound, an oxime compound having a nitro group can be used. Oxime compounds having a nitro group are also preferably dimers. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of Japanese patent application laid-open No. 2013-114249, 0008 to 0012 and 0070 to 0079 of Japanese patent application laid-open No. 2014-137466, compounds described in paragraphs 0007 to 0025 of Japanese patent application laid-open No. 4223071, and ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

As the oxime compound, an oxime compound having a benzofuran skeleton can also be used. Specific examples thereof include OE-01 to OE-75 described in International publication No. 2015/036910.

As the oxime compound, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton can also be used. Examples of such photopolymerization initiators include compounds described in International publication No. 2019/088055.

As the photo-oxime compound, an aromatic ring group Ar having an electron withdrawing group introduced into the aromatic ring can be used ^OX1 An oxime compound (hereinafter, also referred to as oxime compound OX.). Ar as the above aromatic ring group ^OX1 Has electron withdrawing group capable ofExamples of the acyl group, the nitro group, the trifluoromethyl group, the alkylsulfinyl group, the arylsulfinyl group, the alkylsulfonyl group, the arylsulfonyl group, and the cyano group are preferably an acyl group and a nitro group, and more preferably an acyl group, and further preferably a benzoyl group, from the viewpoint of easy formation of a film excellent in light resistance. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, cyano group, nitro group, hydroxyl group, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic oxy group, alkenyl group, alkylthio group, arylthio group, acyl group or amino group, more preferably an alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group or amino group, still more preferably an alkoxy group, alkylthio group or amino group.

Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of japanese patent No. 4600600.

Further, as the oxime compound, the following compounds can be particularly preferably exemplified.

[ chemical formula 19]

/>

[ chemical formula 20]

[ chemical formula 21]

The mass ratio of the radical polymerization initiator represented by the above formula 1 when used in combination with other radical polymerization initiators is not particularly limited, but from the viewpoint of gassing inhibition, the content of the radical polymerization initiator is preferably 10 mass% or more, more preferably 50 mass% or more, still more preferably 80 mass% or more, and particularly preferably 90 mass% or more, relative to the total mass of the polymerization initiator.

< radical polymerizable Compound >

The curable composition of the present invention contains a radically polymerizable compound.

Examples of the radical polymerizable compound include a compound having an ethylenically unsaturated group.

Examples of the resin type radical polymerizable compound include resins containing a repeating unit having a radical polymerizable group. The weight average molecular weight (Mw) of the resin-type polymerizable compound is preferably 2,000 ～ 2,000,000. The upper limit of the weight average molecular weight is more preferably 1,000,000 or less, and still more preferably 500,000 or less. The lower limit of the weight average molecular weight is more preferably 3,000 or more, and still more preferably 5,000 or more.

The molecular weight of the monomer-type radical polymerizable compound (polymerizable monomer) is preferably less than 2,000, more preferably 1,500 or less. The lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more, more preferably 200 or more.

The compound having an ethylenically unsaturated group as the polymerizable monomer is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound. Specific examples thereof include compounds described in paragraphs 0095 to 0108 of JP 2009-288705, 0227 of JP 2013-029760, 0254 to 0257 of JP 2008-292970, 0034 to 0038 of JP 2013-253224, 0477 of JP 2012-208494, 2017-048367, 6057891, 6031807, and 2017-194662, which are incorporated herein by reference.

Examples of the compound having an ethylenically unsaturated group include dipentaerythritol tri (meth) acrylate (commercially available as KAYARAD D-330;Nippon Kayaku Co, manufactured by ltd. And the like), dipentaerythritol tetra (meth) acrylate (commercially available as KAYARAD D-320;Nippon Kayaku Co, manufactured by ltd. And the like), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310;Nippon Kayaku Co, manufactured by ltd. And the like), dipentaerythritol hexa (commercially available as KAYARAD DPHA; nippon Kayaku co., manufactured by ltd. And the NK escer a-DPH-12e; shin-Nakamura Chemical co., manufactured by ltd. And the like), and compounds having a structure in which (meth) acryl groups of these compounds are bonded via ethylene glycol and/or propylene glycol residues (for example, SR454, SR499, commercially available by SARTOMER Company, inc. And the like). Further, as the compound having an ethylenically unsaturated group, diglycerol EO (ethylene oxide) -modified (meth) acrylate (commercially available as M-460; TOAGOSEI CO., LTD. Manufactured), pentaerythritol tetraacrylate (SHIN-NAKAMURA CHEMICAL Co., ltd., manufactured) 1, 6-hexanediol diacrylate (Nippon Kayaku Co., ltd., KAYARAD HDDA), RP-1040 (Nippon Kayaku Co., ltd., manufactured), ARONIX TO-2349 (TOAGOSEI CO., LTD., manufactured), NK Oligo UA-7200 (SHIN-NAKAMURA CHEMICAL Co., ltd., manufactured), 8UH-1006, 8UH-1012 (Taisei Fine Chemical Co., ltd., manufactured), LIGHT ACRYLATE POB-A0 (KYOEISHA CHEMICAL Co., LTD. Manufactured) and the like can also be used.

As the compound having an ethylenically unsaturated group, a 3-functional (meth) acrylate compound such as trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, ethylene isocyanatooxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, or the like is also preferably used. Examples of THE commercial products of THE 3-functional (meth) acrylate compounds include ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, M-450 (TOAGOSEI CO., LTD. Manufactured), NK ESTER A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT (SHIN-NAKAMURA CHEMICAL Co., ltd. Manufactured), YARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (Nippon Kayaku Co., manufactured by Ltd.).

The compound having an ethylenically unsaturated group may further have an acid group such as a carboxyl group, a sulfo group, or a phosphate group. Examples of commercial products of such compounds include ARONIX M-305, M-510, M-520, ARONIX T0-2349 (TOAGOSEI CO., LTD. Manufactured), and the like.

As the compound having an ethylenically unsaturated group, a compound having a caprolactone structure can also be used. For the compound having a caprolactone structure, reference can be made to paragraphs 0042 to 0045 of Japanese patent application laid-open No. 2013-253224, which is incorporated herein by reference. Examples of the compound having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, DPCA-120, which are commercially available from Nippon Kayaku Co., ltd.

As the compound having an ethylenically unsaturated group, a compound having an ethylenically unsaturated group and an alkyleneoxy group can also be used. Such a compound is preferably a compound having an ethylenically unsaturated group and an ethyleneoxy group and/or an propyleneoxy group, more preferably a compound having an ethylenically unsaturated group and an ethyleneoxy group, and still more preferably a 3-6 functional (meth) acrylate compound having 4-20 ethyleneoxy groups. Examples of the commercial products include 4-functional (meth) acrylate SR494 having 4 ethyleneoxy groups manufactured by SARTOMER Company, inc. And 3-functional (meth) acrylate KAYARAD TPA-330 having 3 isobutyleneoxy groups manufactured by Nippon Kayaku co.

As the compound having an ethylenically unsaturated group, a polymerizable compound having a fluorene skeleton can also be used. Examples of the commercial products include OGSOL FA-0200 and FA-0300 (Osaka Gas Chemicals Co., ltd. The (meth) acrylate monomer having a fluorene skeleton).

As the compound having an ethylenically unsaturated group, a compound substantially free of an environmental control substance such as toluene is also preferably used. Examples of commercial products of such compounds include KAYARAD DPHA LT, KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku co., ltd.) and the like.

As the compound having an ethylenically unsaturated group, UA-7200 (SHIN-NAKAMURA CHEMICAL Co., ltd.), DPHA-40H (Nippon Kayaku Co., ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-202UA (KYOEISHA CHEMICAL Co., LTD.), 8UH-1006, 8UH-1012 (Taisei Fine Chemical Co., ltd.), LIGHT ACRYLATE POB-A0 (KYOEISHA CHEMICAL Co., LTD.) and the like are also preferably used.

The content of the radical polymerizable compound is preferably 0.1 to 50% by mass based on the total solid content of the curable composition. The lower limit is more preferably 0.5 mass% or more, and still more preferably 1 mass% or more. The upper limit is more preferably 45 mass% or less, and still more preferably 40 mass% or less.

In the curable composition according to the present invention, only 1 kind of radical polymerizable compound may be used, or 2 or more kinds may be used. When 2 or more kinds are used, it is preferable that the total amount thereof is within the above range.

< colorant >

The curable composition according to the present invention preferably contains a colorant.

Examples of the colorant include a color colorant and a black colorant. Examples of the color colorant include colorants having a wavelength of maximum absorption in the wavelength range of 400nm to 700 nm. For example, a green colorant, a red colorant, a yellow colorant, a violet colorant, a blue colorant, an orange colorant, and the like can be cited. The other colorant is preferably a color colorant, preferably at least 1 selected from a yellow colorant and a green colorant, and more preferably a yellow colorant.

The colorant may be a pigment, or may be a dye, preferably a pigment.

The average primary particle diameter of the pigment is preferably 1nm to 200nm. The lower limit is more preferably 5nm or more, still more preferably 10nm or more. The upper limit is more preferably 180nm or less, still more preferably 150nm or less, particularly preferably 100nm or less. In the present specification, the primary particle diameter of the pigment can be obtained by observing the primary particles of the pigment with a transmission electron microscope and obtaining an image photograph. Specifically, the projected area of the primary particles of the pigment is obtained, and the equivalent circle diameter corresponding to the projected area is calculated as the primary particle diameter of the pigment. The average primary particle diameter in this specification is an arithmetic average value of primary particle diameters of primary particles for 400 pigments. The primary particles of the pigment are independent particles which are not aggregated.

The green colorant includes a phthalocyanine compound and a squaric acid compound, and is preferably a phthalocyanine compound. And, the green colorant is preferably a pigment. Specific examples of the green colorant include green pigments such as c.i. pigment green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66. Further, as the green colorant, a zinc halide phthalocyanine pigment having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule can be used. Specific examples thereof include compounds described in International publication No. 2015/118720. Further, as the green colorant, a compound described in the specification of chinese patent application No. 106909027, a phthalocyanine compound having a phosphate as a ligand described in international publication No. 2012/102395, a phthalocyanine compound described in japanese patent application laid-open No. 2019-008014, a phthalocyanine compound described in japanese patent application laid-open No. 2018-180023, a compound described in japanese patent application laid-open No. 2019-038958, an aluminum phthalocyanine compound described in japanese patent application laid-open No. 2020-070426, a core-shell type pigment described in japanese patent application laid-open No. 2020-076995, a diarylmethane compound described in japanese patent application laid-open No. 2020-504758, and the like can be used.

The green colorant is preferably c.i. pigment green 7, 36, 58, 59, 62, 63, more preferably c.i. pigment green 7, 36, 58, 59.

Examples of the red colorant include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, thioindigo compounds, preferably diketopyrrolopyrrole compounds, anthraquinone compounds, and azo compounds, more preferably diketopyrrolopyrrole compounds. And, the red colorant is preferably a pigment. Specific examples of the red colorant 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, 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, 255, 264, 269, 270, 272, 279, 294, 295, 297, etc. Further, as the red colorant, a diketopyrrolopyrrole compound having a structure in which at least 1 bromine atom is substituted as described in japanese patent application laid-open No. 2017-201384, a diketopyrrolopyrrole compound described in paragraphs 0016 to 0022 of japanese patent application laid-open No. 6248838, a diketopyrrolopyrrole compound described in international publication No. 2012/102399, a diketopyrrolopyrrole compound described in international publication No. 2012/117965, a diketopyrrolopyrrole bromide compound described in japanese patent application laid-open No. 2020-085947, a naphthol azo compound described in japanese patent application laid-open No. 2012-229344, a red colorant described in japanese patent application laid-open No. 6516119, a red colorant described in japanese patent application laid-open No. 6525101, a diketopyrrolopyrrole bromide compound described in japanese patent application laid-open No. 0229, an anthraquinone compound described in japanese patent application laid-open No. 10-2019-0741, a diketopyrrolopyrrole compound described in korean patent application laid-open No. 2012-2019-01444, a perylene compound described in japanese patent application laid-open No. 2020-00296, a perylene compound described in japanese patent application laid-open No. 2020-5, a perylene compound described in japanese patent application laid-open No. 2020-5, and a red colorant can be used. As the red colorant, a compound having the following structure can be used: and a structure in which an aromatic ring group having a group having an oxygen atom, a sulfur atom or a nitrogen atom bonded thereto is bonded to a diketopyrrolopyrrole skeleton. As the red colorant, lumogen F Orange 240 (manufactured by BASF corporation, red pigment, perylene pigment) can also be used.

The red colorant is preferably c.i. pigment red 122, 177, 179, 254, 255, 264, 269, 272, 291, more preferably c.i. pigment red 254, 264, 272.

Examples of the yellow colorant include azo compounds, azomethine compounds, isoindoline compounds, pteridinyl compounds, quinophthalone compounds, and perylene compounds. The yellow colorant is preferably a pigment, more preferably an azo pigment, an azomethine pigment, an isoindoline pigment, a pteridine-based pigment, a quinophthalone pigment or a perylene pigment, and still more preferably an azo pigment or an azomethine pigment. Specific examples of the yellow colorant 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, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 1 68, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 215, 213, 232, 236, 232, and the like.

The yellow colorant may be an azo barbiturate nickel complex having the following structure.

[ chemical formula 22]

And, as a yellow colorant, the compounds described in Japanese patent application laid-open No. 2017-201003, the compounds described in Japanese patent application laid-open No. 2017-197719, the compounds described in paragraphs 0011 to 0062, 0137 to 0276, the compounds described in Japanese patent application laid-open No. 2017-171913, the compounds described in paragraphs 0010 to 0062, 0138 to 0295, the compounds described in paragraphs 0011 to 0062, 0139 to 0190, the compounds described in paragraphs 0010 to 0065, 0142 to 0222, the compounds described in paragraphs 0013 to 054339, the quinophthalone compounds described in paragraphs 0011 to 0034, the compounds described in paragraphs 0013 to 0018, and the isoindoline compounds described in Japanese patent application laid-open No. 2018-062644; quinophthalone compound described in japanese patent application laid-open publication No. 2018-203798, quinophthalone compound described in japanese patent application laid-open publication No. 2018-062578, quinophthalone compound described in japanese patent application No. 6432076, quinophthalone compound described in japanese patent application laid-open publication No. 2018-155881, quinophthalone compound described in japanese patent application laid-open publication No. 2018-111757, quinophthalone compound described in japanese patent application laid-open publication No. 2018-040835, quinophthalone compound described in japanese patent application laid-open publication No. 2017-197640, quinophthalone compound described in japanese patent application laid-open publication No. 2016-145282, quinophthalone compound described in japanese patent application laid-open publication No. 2014-085565, quinophthalone compound described in japanese patent application laid-open publication No. 2014-021139, quinophthalone compound described in japanese patent application laid-open publication No. 2013-2093-614, quinophthalone compound described in japanese patent application laid-open publication No. 2013-435, the compounds of quinophthalone described in japanese laid-open patent publication No. 2013-181015, quinophthalone described in japanese laid-open patent publication No. 2013-061622, quinophthalone described in japanese laid-open patent publication No. 2013-032586, quinophthalone described in japanese laid-open patent publication No. 2012-226110, quinophthalone described in japanese laid-open patent publication No. 2008-074987, quinophthalone described in japanese laid-open patent publication No. 2008-081565, quinophthalone described in japanese laid-open patent publication No. 2008-07565 6, quinophthalone described in japanese laid-open patent publication No. 2008-07354985, quinophthalone described in japanese laid-open patent publication No. 2008-050420, quinophthalone described in japanese laid-open patent publication No. 2008-031281, quinophthalone described in japanese laid-open patent publication No. 48-032765, quinophthalone described in japanese laid-open patent publication No. 2019-004, quinophthalone described in japanese laid-open patent publication No. 2008-081565, quinophthalone described in japanese laid-open patent publication No. 2008-3562, japanese patent publication No. 3521, japanese patent publication No. 3525, japanese patent publication No. 20122-top-032020, no. 2020, no. 20125, no. 20122-2020, no. 2020, and No. 032020, no. 2020, no. 20125, no. 2020, and 5, and so forth The compound described in International publication No. 2020/045197, the azo compound described in Japanese patent application laid-open No. 2020-093994, the perylene compound described in International publication No. 2020/105346, the quinophthalone compound described in Japanese patent application laid-open No. 2020-517791, the compound represented by the following formula (QP 1), and the compound represented by the following formula (QP 2). Further, from the viewpoint of improving the color value, it is also preferable to use a compound obtained by multimerizing these compounds.

[ chemical formula 23]

In the formula (QP 1), X ¹ ～X ¹⁶ Each independently represents a hydrogen atom or a halogen atom, Z ¹ An alkylene group having 1 to 3 carbon atoms. Specific examples of the compound represented by the formula (QP 1) include a compound described in paragraph 0016 of japanese patent No. 6443711.

[ chemical formula 24]

In the formula (QP 2), Y ¹ ～Y ³ Each independently represents a halogen atom. n and m represent integers of 0 to 6, and p represents an integer of 0 to 5. (n+m) is 1 or more. Specific examples of the compound represented by the formula (QP 2) include compounds described in paragraphs 0047 to 0048 of Japanese patent application publication No. 6432077.

The yellow colorant is preferably c.i. pigment yellow 117, 129, 138, 139, 150, 185.

Examples of the orange colorant include orange pigments such as 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, 73, and the like.

Examples of the violet colorant include violet pigments such as c.i. pigment violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.

Examples of the blue colorant include 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, 88, and the like. Further, as the blue colorant, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples thereof include compounds described in paragraphs 0022 to 0030 of Japanese patent application laid-open No. 2012-247591 and paragraph 0047 of Japanese patent application laid-open No. 2011-157478.

Color colorants can also use dyes. The dye is not particularly limited, and known dyes can be used. Examples thereof include dyes such as pyrazole azo dyes, anilinoazo 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 pyrrole methylene dyes.

Pigment polymers can also be used as color colorants. The dye multimer is preferably a dye that is dissolved in an organic solvent. Further, the pigment multimer may form particles. When the pigment polymer is a particle, it is usually used in a state of being dispersed in a solvent. The pigment polymer in a particulate state can be obtained by emulsion polymerization, and a specific example thereof is a compound and a production method described in JP-A2015-214682. The dye multimer is a compound having 2 or more dye structures in one molecule, preferably 3 or more dye structures. The upper limit is not particularly limited, and may be 100 or less. The plurality of dye structures in one molecule may have the same dye structure or may have different dye 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 still more preferably 6000 or more. The upper limit is more preferably 30000 or less, and still more preferably 20000 or less. As the dye multimer, a compound described in Japanese patent application laid-open No. 2011-213925, japanese patent application laid-open No. 2013-042097, japanese patent application laid-open No. 2015-028144, japanese patent application laid-open No. 2015-030742, international publication No. 2016/031442, and the like can be used.

The color colorant may be a diarylmethane compound described in japanese patent application laid-open No. 2020-504758, a triarylmethane dye polymer described in japanese patent application laid-open No. 10-2020-0028160, a xanthene compound described in japanese patent application laid-open No. 2020-117638, a phthalocyanine compound described in international patent application laid-open No. 2020/174991, an isoindoline compound or a salt thereof described in japanese patent application laid-open No. 2020-160279, a compound represented by formula 1 described in korean patent application laid-open No. 10-2020-0069442, a compound represented by formula 1 described in korean patent application laid-open No. 10-2020-0069730, a compound represented by formula 1 described in korean patent application laid-open No. 10-2020-0069070, a compound represented by formula 1 described in korean patent application laid-open No. 10-2020-0069067, a compound represented by formula 1 described in korean patent application laid-open No. 2020-160279, a compound represented by formula 1, a zinc halide dye described in korean patent application laid-open No. 6809649, or a zinc halide dye described in japanese patent application laid-open No. 180176. The color coloring agent can be rotaxane, and the pigment skeleton can be used for a cyclic structure of the rotaxane, a rod-shaped structure or two structures.

The color colorant may be used in combination of 2 or more. When 2 or more color colorants are used in combination, black can be formed by a combination of 2 or more color colorants.

The black colorant is not particularly limited, and a known colorant can be used. Examples of the inorganic black colorant include carbon black, titanium black, and graphite, and carbon black or titanium black is preferable, and titanium black is more preferable. Titanium black is black particles containing titanium atoms, preferably titanium suboxide or titanium oxynitride. The titanium black may be surface-modified as needed for the purpose of improving dispersibility, suppressing aggregation, and the like. For example, the surface of the titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, a treatment using a water repellent substance as described in japanese patent laid-open No. 2007-302836 can also be performed. As black colorants, pigment black 1, 7 can also be used with color index (c.i.). The titanium black preferably has a small primary particle diameter and a small average primary particle diameter. Specifically, the average primary particle diameter is preferably 10 to 45nm. Titanium black can also be used as a dispersion. For example, the following dispersions are mentioned: and a dispersion in which the content ratio of Si atoms to Ti atoms in the dispersion is adjusted to be in the range of 0.20 to 0.50. The above-mentioned dispersion can be described in paragraphs 0020 to 0105 of Japanese patent application laid-open No. 2012-169556, incorporated herein by reference. Examples of the commercial products of titanium black include titanium black 10S, 12S, 13R, 13M-C, 13R-N, 13M-T (manufactured by product name: mitsubishi Materials Corporation), and Tilack D (manufactured by product name: ako Kasei Co., ltd.). Examples of the organic black colorant include bis-benzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, and bis-benzofuranone compounds and perylene compounds are preferable. Examples of the bis-benzofuranone compound include compounds described in Japanese patent application laid-open No. 2010-534726, japanese patent application laid-open No. 2012-515233, japanese patent application laid-open No. 2012-515234, international publication No. 2014/208348, japanese patent application laid-open No. 2015-525260, and the like, and are available as "Irgaphor Black" by BASF corporation. Examples of the perylene compound include c.i. pigment blacks 31 and 32. Examples of azomethine compounds include compounds described in JP-A-01-170601 and JP-A-02-034664, and are available as, for example, "CHROMO FINE BLACK A1103" from Ltd. Furthermore, perylene Black (Lumogen Black FK4280, etc.) described in paragraphs 0016 to 0020 of japanese unexamined patent publication No. 2017-226821 may also be used as the organic Black colorant.

The curable composition according to the present invention may contain a colorant alone or 2 or more kinds of the composition. When 2 or more kinds are used, it is preferable that the total amount thereof is in the following range.

The content of the colorant is preferably 10 to 75% by mass based on the total solid content of the curable composition. The upper limit is more preferably 70 mass% or less, and still more preferably 65 mass% or less. The lower limit is more preferably 20 mass% or more, and still more preferably 30 mass% or more.

< resin >

The curable composition of the present invention preferably contains a resin.

The curable composition of the present invention can use a resin as the radical polymerizable compound. The radical polymerizable compound preferably contains at least a resin. For example, the resin is blended for applications such as dispersing pigments in a curable composition and for applications of adhesives. In addition, a resin mainly used for dispersing a pigment in a curable composition or the like is also referred to as a dispersant. However, such uses of the resin are examples, and the resin may be used for purposes other than such uses.

In addition, resins having radically polymerizable groups are also radically polymerizable compounds.

The weight average molecular weight of the resin is preferably 3000 to 2000000. The upper limit is preferably 1000000 or less, more preferably 500000 or less. The lower limit is preferably 4000 or more, more preferably 5000 or more.

Examples of the resin include (meth) acrylic resin, epoxy resin, alkene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polystyrene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamide resin, polyamideimide resin, polyolefin resin, cycloolefin resin, polyester resin, styrene resin, vinyl acetate resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyurethane resin, polyurea resin, and the like. Among these resins, 1 kind may be used alone, or 2 or more kinds may be used in combination. The cycloolefin resin is preferably a norbornene resin from the viewpoint of improving heat resistance. Examples of the commercially available norbornene resin include ARTON series (for example, ARTON F4520) manufactured by JSR Corporation. As the resin, a resin described in the examples of international publication No. 2016/088645, a resin described in japanese patent application laid-open publication No. 2017-057265, a resin described in japanese patent application laid-open publication No. 2017-032585, a resin described in japanese patent application laid-open publication No. 2017-075248, a resin described in japanese patent application laid-open publication No. 2017-066240, a resin described in japanese patent application laid-open publication No. 2017-167513, a resin described in japanese patent application laid-open publication No. 2017-173787, a resin described in paragraphs 0041 to 0060 of japanese patent application laid-open publication No. 2017-206689, a blocked polyisocyanate resin described in japanese patent application laid-open publication No. 2018-010856, a resin described in japanese patent application laid-open publication No. 2012-222891, a resin described in japanese patent application laid-open publication No. 2020-122052, a resin described in japanese patent application laid-open publication No. 2020-111656, a resin described in japanese patent application laid-open publication No. 2017-167513, a resin described in japanese patent application laid-open publication No. 2017-20668513, a resin described in japanese patent application laid-open publication No. 2017-5-6-fig. 2019, a resin having a structure containing a side chain unit in which has a phenyl group in its side chain unit. As the resin, a resin having a fluorene skeleton can be preferably used. For the resin having a fluorene skeleton, reference can be made to the description of U.S. patent application publication No. 2017/0102610, which is incorporated herein. The resin may be any of the resins described in paragraphs 0199 to 0233 of Japanese unexamined patent application publication No. 2020-186373, the alkali soluble resins described in Japanese unexamined patent application publication No. 2020-186325, and the resins represented by formula 1 described in Korean laid-open patent application No. 10-2020-007839.

As the resin, a resin having an acid group is preferably used. Examples of the acid group include a carboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxyl group. These acid groups may be 1 or 2 or more. For example, a resin having an acid group can be used as the alkali-soluble resin. The acid value of the resin having an acid group is preferably 30 to 500mgKOH/g. The lower limit is preferably 50mgKOH/g or more, more preferably 70mgKOH/g or more. The upper limit is preferably 400mgKOH/g or less, more preferably 200mgKOH/g or less, still more preferably 150mgKOH/g or less, and most preferably 120mgKOH/g or less.

As the resin, a resin including a repeating unit derived from a compound represented by the formula (ED 1) and/or a compound represented by the formula (ED 2) (hereinafter, these compounds may also be referred to as "ether dimers") is also preferable.

[ chemical formula 25]

In the formula (ED 1), R ¹ R is R ² Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

[ chemical formula 26]

In the formula (ED 2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the formula (ED 2), reference can be made to the description of japanese patent laid-open No. 2010-16889.

For a specific example of the ether dimer, reference can be made to paragraph 0317 of Japanese patent application laid-open No. 2013-029760, which is incorporated herein.

As the resin, a resin having a polymerizable group is also preferably used. Examples of the polymerizable group include an ethylenically unsaturated group and a cyclic ether group.

As the resin, a resin having at least 1 kind of repeating unit (hereinafter, also referred to as repeating unit Ep) selected from the repeating unit represented by formula (Ep-1) and the repeating unit represented by formula (Ep-2) (hereinafter, also referred to as resin Ep) can be used. The resin Ep may contain only any one of the repeating unit represented by the formula (Ep-1) and the repeating unit represented by the formula (Ep-2), or may contain the repeating unit represented by the formula (Ep-1) and the repeating unit represented by the formula (Ep-2), respectively. When two kinds of repeating units are contained, the ratio of the repeating unit represented by the formula (Ep-1) to the repeating unit represented by the formula (Ep-2) is preferably the repeating unit represented by the formula (Ep-1) in terms of a molar ratio: the repeating unit represented by the formula (Ep-2) =5:95 to 95:5, more preferably 10:90 to 90:10, still more preferably 20:80 to 80:20.

[ chemical formula 27]

In the formula (Ep-1), (Ep-2), L ¹ Represents a single bond or a 2-valent linking group, R ¹ Represents a hydrogen atom or a substituent. As R ¹ Examples of the substituent include an alkyl group and an aryl group, and an alkyl group is preferable. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.R is R ¹ Preferably a hydrogen atom or a methyl group. As L ¹ Examples of the 2-valent linking group include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO ₂ -, -CO-, -O-; -COO-, -OCO-, S-and a group formed by combining 2 or more of these. The alkylene group may be any of linear, branched and cyclic, and is preferably linear or branched. The alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxyl group and an alkoxy group.

The content of the above-mentioned repeating unit Ep in the resin Ep is preferably 1 mol% to 100 mol% in all the repeating units of the resin Ep. The upper limit is preferably 90 mol% or less, more preferably 80 mol% or less. The lower limit is preferably 2 mol% or more, more preferably 3 mol% or more.

The resin Ep may contain repeating units other than the repeating unit Ep described above. Examples of the other repeating unit include a repeating unit having an acid group, a repeating unit having an ethylenically unsaturated group, and the like.

Examples of the acid group include a phenolic hydroxyl group, a carboxyl group, a sulfo group, and a phosphate group, and the phenolic hydroxyl group or the carboxyl group is preferable, and the carboxyl group is more preferable.

Examples of the ethylenically unsaturated group include vinyl, styryl, (meth) allyl, and (meth) acryl.

When the resin Ep contains a repeating unit having an acid group, the content of the repeating unit having an acid group in the resin Ep is preferably 5 mol% to 85 mol% in all the repeating units of the resin Ep. The upper limit is preferably 60 mol% or less, more preferably 40 mol% or less. The lower limit is preferably 8 mol% or more, more preferably 10 mol% or more.

When the resin Ep contains a repeating unit having an ethylenically unsaturated group, the content of the repeating unit having an ethylenically unsaturated group in the resin Ep is preferably 1 mol% to 65 mol% in all the repeating units of the resin Ep. The upper limit is preferably 45 mol% or less, more preferably 30 mol% or less. The lower limit is preferably 2 mol% or more, more preferably 3 mol% or more.

The resin Ep preferably further comprises a repeating unit having an aromatic hydrocarbon ring. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, and preferably a benzene ring. The aromatic hydrocarbon ring may have a substituent. Examples of the substituent include an alkyl group and the like. When the resin having a cyclic ether group contains a repeating unit having an aromatic hydrocarbon ring, the content of the repeating unit having an aromatic hydrocarbon ring is preferably 1 mol% to 65 mol% of all the repeating units of the resin having a cyclic ether group. The upper limit is 45 mol% or less, more preferably 30 mol% or less, still more preferably. The lower limit is more preferably 2 mol% or more, and still more preferably 3 mol% or more. Examples of the repeating unit having an aromatic hydrocarbon ring include repeating units derived from monofunctional polymerizable compounds having an aromatic hydrocarbon ring such as vinyltoluene and benzyl (meth) acrylate.

As the resin, a resin containing a repeating unit derived from the compound represented by formula (X) is also preferably used.

[ chemical formula 28]

Wherein R is ¹ Represents a hydrogen atom or a methyl group, R ²¹ R is R ²² Each independently represents an alkylene group, and n represents an integer of 0 to 15. R is R ²¹ R is R ²² The number of carbon atoms of the alkylene group represented is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, particularly preferably 2 or 3.n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and even more preferably an integer of 0 to 3.

Examples of the compound represented by the formula (X) include ethylene oxide or propylene oxide modified (meth) acrylate of p-cumylphenol (para-cumylphenol). Examples of the commercial products include aromix M-110 (manufactured by TOAGOSEI co., ltd.) and the like.

As the resin, a resin having an aromatic carboxyl group (hereinafter, also referred to as a resin Ac) is also preferably used. The aromatic carboxyl group in the resin Ac may be contained in the main chain of the repeating unit or may be contained in the side chain of the repeating unit. The aromatic carboxyl group is preferably contained in the main chain of the repeating unit. In the present specification, the aromatic carboxyl group means a group in which 1 or more carboxyl groups are bonded to an aromatic ring structure. Among the aromatic carboxyl groups, the number of carboxyl groups bonded to the aromatic ring is preferably 1 to 4, more preferably 1 to 2.

The resin Ac is preferably a resin comprising at least 1 repeating unit selected from the repeating units represented by the formula (Ac-1) and the repeating units represented by the formula (Ac-2).

[ chemical formula 29]

Ar in formula (Ac-1) ¹ Represents a group containing an aromatic carboxyl group, L ¹ represents-C00-or-CONH-, L ² Represents a 2-valent linking group.

Ar in formula (Ac-2) ¹⁰ Represents a group containing an aromatic carboxyl group, L ¹¹ represents-COO-or-CONH-, L ¹² Represents a 3-valent linking group, P ¹⁰ Representing a polymer chain.

In the formula (Ac-1), as Ar ¹ Examples of the group containing an aromatic carboxyl group include a structure derived from an aromatic tricarboxylic anhydride, a structure derived from an aromatic tetracarboxylic anhydride, and the like. Examples of the aromatic tricarboxylic acid anhydride and the aromatic tetracarboxylic acid anhydride include compounds having the following structures.

[ chemical formula 30]

In the above, Q ¹ Represents a single bond, -O-, -CO-, -COOCH ₂ CH ₂ OCO-、-SO ₂ -、-C(CF ₃ ) ₂ -, a group represented by the following formula (Q-1) or a group represented by the following formula (Q-2).

[ chemical formula 31]

Ar ¹ The group containing an aromatic carboxyl group represented may have a polymerizable group. The polymerizable group is preferably an ethylenically unsaturated group or a cyclic ether group, and more preferably an ethylenically unsaturated group.

As Ar ¹ Specific examples of the group containing an aromatic carboxyl group represented by the formula (Ar-11), the group represented by the formula (Ar-12), the group represented by the formula (Ar-13), and the like are given.

[ chemical formula 32]

In the formula (Ar-11), n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2.

In the formula (Ar-12), n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and further preferably 2.

In the formula (Ar-13), n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, and still more preferably 1. Wherein at least one of n3 and n4 is an integer of 1 or more.

In the formula (Ar-13), Q ¹ Represents a single bond, -O-, -CO-, -COOCH ₂ CH ₂ OCO-、-SO ₂ -、-C(CF ₃ ) ₂ -, a group represented by the above formula (Q-1) or a group represented by the above formula (Q-2).

In the formulae (Ar-11) to (Ar-13), 1 represents a group represented by formula L ¹ Is used for the bonding position of the substrate.

In the formula (Ac-1), L ¹ represents-COO-or CONH-, preferably-COO-.

As L in formula (Ac-1) ² Examples of the 2-valent linking group include an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-and a combination of 2 or more of these groups. The number of carbon atoms of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The alkylene group may be any of linear, branched, and cyclic. The number of carbon atoms of the arylene group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. The alkylene group and arylene group may have a substituent. Examples of the substituent include a hydroxyl group and the like. L (L) ² The 2-valent linking group represented is preferably represented by-L ^2a -a group represented by O-. L (L) ^2a An alkylene group; arylene groups; a group formed by combining an alkylene group and an arylene group; at least 1 selected from alkylene and arylene groups and at least one selected from-O- -CO-, -COO-, -OCO-, -NH-and-S-, and the like, alkylene groups are preferred. The number of carbon atoms of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The alkylene group may be any of linear, branched, and cyclic. The alkylene group and arylene group may have a substituent. Examples of the substituent include a hydroxyl group and the like.

Ar in formula (Ac-2) ¹⁰ A group containing an aromatic carboxyl group represented by the formula (Ac-1) and Ar ¹ The meaning of (2) is the same, and the preferred mode is the same.

In the formula (Ac-2), L ¹¹ represents-COO-or CONH-, preferably-COO-.

As L in formula (Ac-2) ¹² Examples of the 3-valent linking group include a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-and a group in which 2 or more of these groups are combined. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The aliphatic hydrocarbon group may be any of straight chain, branched chain, and cyclic. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxyl group and the like. L (L) ¹² The 3-valent linking group represented by formula (Li 2-1) is preferable, and the group represented by formula (L12-2) is more preferable.

[ chemical formula 33]

In the formula (L12-1), L ^12b Represents a 3-valent linking group, X ¹ Represents S, 1 represents L of formula (Ac-2) ¹¹ Is represented by the formula (Ac-2) ¹⁰ Is used for the bonding position of the substrate. As L ^12b Examples of the 3-valent linking group include a hydrocarbon group; hydrocarbyl radicals and are selected from the group consisting of-O-, -CO-, -COO-, -OCO-, at least 1 of-NH-and-S-and the like, preferably a hydrocarbyl group or a combination of a hydrocarbyl and-0-.

In the formula (L12-2), L ^12c Represents a 3-valent linking group, X ¹ Represents S, 1 represents L of formula (Ac-2) ¹¹ Is represented by the formula (Ac-2) ¹⁰ Is used for the bonding position of the substrate. As L ^12c Examples of the 3-valent linking group include a hydrocarbon group; hydrocarbyl radicals and are selected from the group consisting of-O-, -CO-, -COO-, -OCO-, at least 1 of-NH-and-S-and the like, preferably a hydrocarbon group.

In the formula (Ac-2), P ¹⁰ Representing a polymer chain. P (P) ¹⁰ The polymer chain represented preferably has at least 1 repeating unit selected from the group consisting of poly (meth) acrylic acid repeating units, polyether repeating units, polyester repeating units and polyol repeating units. Polymer chain P ¹⁰ The weight average molecular weight of (2) is preferably 500 to 20,000. The lower limit is more preferably 1,000 or more. The upper limit is more preferably 10,000 or less, still more preferably 5,000 or less, and particularly preferably 3,000 or less. As long as P ¹⁰ When the weight average molecular weight of (b) is within the above range, the dispersibility of the pigment in the composition is good. When the resin having an aromatic carboxyl group is a resin having a repeating unit represented by the formula (Ac-2), the resin can be preferably used as a dispersant.

P ¹⁰ The indicated polymer chain may comprise a polymerizable group. As the polymerizable group, there may be mentioned ethylenically unsaturated groupsA group.

The curable composition of the present invention preferably contains a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and an alkaline dispersant (alkaline resin). Here, the acidic dispersant (acidic resin) means a resin having an amount of acid groups larger than an amount of base groups. When the total amount of the acid groups and the base groups is 100 mol% as the acid dispersant (acid resin), a resin having 70 mol% or more of the acid groups is preferable. The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10mgKOH/g to 105mgKOH/g. The basic dispersant (basic resin) is a resin having a larger amount of base than acid groups. As the basic dispersant (basic resin), a resin having an amount of base exceeding 50 mol% is preferable, when the total amount of the amount of acid groups and the amount of base is set to 100 mol%.

The basic group of the basic dispersant is preferably an amino group.

The resin used as the dispersant is also preferably a graft resin. For details of the graft resin, refer to paragraphs 0025 to 0094 of Japanese patent application laid-open No. 2012-255128, which is incorporated herein by reference.

The resin used as the dispersant is also preferably a polyimide-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The polyimide-based dispersant is preferably a resin having a main chain and a side chain, at least one of the main chain and the side chain having a basic nitrogen atom, the main chain having a partial structure having a functional group with pKa14 or less, and the number of atoms of the side chain being 40 to 10000. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. The polyimide-based dispersant can be described in paragraphs 0102 to 0166 of Japanese patent application laid-open No. 2012-255128, incorporated herein by reference.

The resin used as the dispersant is also preferably a resin having a structure in which a plurality of polymer chains are bonded to the core. Examples of such resins include dendrimers (including star polymers). Specific examples of the dendrimer include the polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A2013-043962.

The resin used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated group in a side chain. The content of the repeating unit having an ethylenically unsaturated group in the side chain is preferably 10 mol% or more, more preferably 10 mol% to 80 mol%, and still more preferably 20 mol% to 70 mol% based on the total repeating units of the resin.

The resin used as the dispersant is preferably a resin having an oxetanyl group in the side chain, and more preferably a resin having a repeating unit having an oxetanyl group in the side chain.

In addition, the resin having an oxetanyl group in the side chain is preferably a graft polymer.

The oxetanyl group-containing resin in the side chain is preferably a resin described in examples described below. The content of the repeating unit having an oxetanyl group in the side chain in the resin is preferably 10 mol% or more, more preferably 10 mol% to 80 mol%, and still more preferably 20 mol% to 70 mol% based on the total repeating units in the resin.

The dispersing agent may be a resin described in Japanese patent application laid-open No. 2018-087939, block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese patent application laid-open No. 6432077, polyethyleneimine having a polyester side chain described in International publication No. 2016/104803, a block copolymer described in International publication No. 2019/125940, a block polymer having an acrylamide structural unit described in Japanese patent application laid-open No. 2020-066687, a block polymer having an acrylamide structural unit described in Japanese patent application laid-open No. 2020-066688, or a dispersing agent described in International publication No. 2016/104803.

The dispersant is commercially available, and specific examples thereof include the Disperbyk series (e.g., disperbyk-111, 161, 2001, etc.) manufactured by BYK-Chemie GmbH, the solsprse series (e.g., solsprse 20000, 76500, etc.) manufactured by Japan Lubrizol Corporation, the Ajinomoto Fine-Techno co., inc. Further, as the dispersant, a product described in 0129 of japanese patent application laid-open No. 2012-137564 or a product described in 0235 of japanese patent application laid-open No. 2017-194662 may be used.

When the curable composition of the present invention contains a resin as the radical polymerizable compound, the content of the resin is preferably 1 to 70% by mass based on the total solid content of the curable composition. The lower limit is more preferably 2% by mass or more, still more preferably 3% by mass or more, and particularly preferably 5% by mass or more. The upper limit is more preferably 65 mass% or less, and still more preferably 60 mass% or less.

The content of the resin having an acid group is preferably 1 to 70% by mass based on the total solid content of the curable composition. The lower limit is more preferably 2% by mass or more, still more preferably 3% by mass or more, and particularly preferably 5% by mass or more. The upper limit is more preferably 65 mass% or less, and still more preferably 60 mass% or less.

The content of the alkali-soluble resin is preferably 1 to 70% by mass based on the total solid content of the curable composition. The lower limit is more preferably 2% by mass or more, still more preferably 3% by mass or more, and particularly preferably 5% by mass or more. The upper limit is more preferably 65 mass% or less, and still more preferably 60 mass% or less.

When the curable composition of the present invention contains a resin as a dispersant, the content of the resin as a dispersant is preferably 0.1 to 30% by mass based on the total solid content of the curable composition. The upper limit is more preferably 25 mass% or less, and still more preferably 20 mass% or less. The lower limit is more preferably 0.5 mass% or more, and still more preferably 1 mass% or more. The content of the resin as the dispersant is preferably 1 to 100 parts by mass based on 100 parts by mass of the colorant. The upper limit is more preferably 80 parts by mass or less, still more preferably 70 parts by mass or less, and particularly preferably 60 parts by mass or less. The lower limit is more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, and particularly preferably 20 parts by mass or more.

The curable composition according to the present invention may contain only 1 resin or 2 or more resins. When 2 or more resins are contained, it is preferable that their total amount is within the above range.

< solvent >

The curable composition of the present invention preferably contains a solvent. As the solvent, an organic solvent can be mentioned. The type of the solvent is not particularly limited as long as the solubility of each component and the coatability of the composition are satisfied. Examples of the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For details of these, reference can be made to paragraph 0223 of International publication No. 2015/166779, which is incorporated herein. Also, a cyclic alkyl-substituted ester solvent or a cyclic alkyl-substituted ketone solvent can be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, methylene chloride, methyl 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 acetate, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, γ -butyrolactone, sulfolane, anisole, 1, 4-diacetoxybutane, diethylene glycol monoacetate, 1, 3-butanediol diacetate, dipropylene glycol methyl ether acetate, dipropylene glycol (also referred to as 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, and the like. However, for environmental reasons, it is preferable to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as the organic solvent (for example, 50 mass ppm (parts per million: parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less relative to the total amount of the organic solvent).

In the present invention, an organic solvent having a small metal content is preferably used. The metal content of the organic solvent is preferably 10 ppb by mass (parts per billion:parts per billion) or less, for example. Organic solvents of the order of ppt (parts per trillion: megafraction) can be used as desired, such as provided by Toyo Gosei co., ltd (chemical industry journal, 2015, 11, 13).

Examples of the method for removing impurities such as metals from the organic solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

The organic solvent may contain isomers (compounds having the same number of atoms but different structures). The isomer may be contained in 1 or more kinds.

The content of the peroxide in the organic solvent is preferably 0.8mmol/L or less, and more preferably substantially no peroxide is contained.

The content of the solvent in the curable composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 90% by mass.

The curable composition of the present invention preferably contains substantially no environmental control substance from the viewpoint of environmental protection. In the present invention, the fact that the curable composition does not substantially contain an environmental control substance means that the content of the environmental control substance in the curable composition is 50 mass ppm or less, preferably 30 mass ppm or less, more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. For example, the environmental control materials include benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene, etc. These are based on REACH (for chemical registration, assessment, approval and limitation; registration Evaluation Authorization and Restriction of CHemicals) act, PRTR (contaminant release transport declaration; pollutant Release and Transfer Register) act, VOC (volatile organic compound; volatile Organic Compounds) regulations and the like, registered as environmental regulatory substances, and strictly regulate the amount of use and the method of operation. These compounds are sometimes used as solvents in the production of components and the like used in the curable composition, and may be mixed into the curable composition as residual solvents. From the viewpoints of safety to humans and environmental protection, it is preferable to reduce these substances as much as possible. As a method for reducing the environmental controlled substance, there is a method in which the inside of the system is heated and depressurized to a temperature equal to or higher than the boiling point of the environmental controlled substance, whereby the environmental controlled substance is distilled off from the inside of the system and reduced. In addition, when a small amount of an environmental control substance is distilled off, it is useful to azeotropically remove the substance with a solvent having the same boiling point as the solvent in order to improve efficiency. In addition, when a compound having radical polymerizability is contained, a polymerization inhibitor or the like may be added to carry out reduced pressure distillation to prevent intermolecular crosslinking due to radical polymerization during reduced pressure distillation. These distillation removal methods can be carried out at any stage, such as a stage of starting materials, a stage of reacting starting materials (for example, a resin solution after polymerization, a polyfunctional monomer solution), or a stage of a curable composition produced by mixing these compounds.

< pigment derivative >

The curable composition according to the present invention may contain a pigment derivative. Pigment derivatives are useful, for example, as dispersing aids. Examples of the pigment derivative include a compound having a structure in which an acid group or a base is bonded to a pigment skeleton.

Examples of the pigment skeleton constituting the pigment derivative include a quinoline pigment skeleton, a benzimidazolone pigment skeleton, a benzindole pigment skeleton, a benzothiazole pigment skeleton, an ammonium (iminium) pigment skeleton, a squaric acid pigment skeleton, a Ketone onium pigment skeleton, an oxonol pigment skeleton, a pyrrolopyrrole pigment skeleton, a diketopyrrolopyrrole pigment skeleton, an azo pigment skeleton, an azomethine pigment skeleton, a phthalocyanine pigment skeleton, a naphthalocyanine pigment skeleton, an anthraquinone pigment skeleton, a quinacridone pigment skeleton, a dioxazine pigment skeleton, a cyclic ketone pigment skeleton, a perylene pigment skeleton, a thioindigo pigment skeleton, an isoindoline pigment skeleton, an isoindolinone pigment skeleton, a quinophthalone pigment skeleton, an ammonium pigment skeleton, a dithiol pigment skeleton, a triarylmethane pigment skeleton, and a pyrrole methylene pigment skeleton.

Examples of the acid group include a carboxyl group, a sulfo group, a phosphate group, a borate group, a carboxylic acid amide group, a sulfonic acid amide group, an imide group, and salts thereof. Examples of the atoms or groups of atoms constituting the salt include alkali metal ions (Li ⁺ 、Na ⁺ 、K ⁺ Etc.), alkaline earth metal ions (Ca) ²⁺ 、Mg ²⁺ Etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ions, etc. As the carboxylic acid amide group, those composed of-NHCOR are preferable ^X1 A group represented by the formula (I). As the sulfonic acid amide group, those composed of-NHSO are preferable ₂ R ^X2 A group represented by the formula (I). As imide groups, preference is given to those derived from-SO ₂ NHSO ₂ R ^X3 、-CONHSO ₂ R ^X4 、-CONHCOR ^X5 or-SO ₂ NHCOR ^X6 Represented groups, more preferably-SO ₂ NHSO ₂ R ^X3 。R ^X1 ～R ^X6 Each independently represents an alkyl group or an aryl group. R is R ^X1 ～R ^X6 The alkyl group and the aryl group may have a substituent. The substituent is preferably a halogen atom, more preferably a fluorine atom.

Examples of the base include an amino group, a pyridyl group and salts thereof, and salts of an ammonium group, and a phthalimidomethyl group. Examples of the atoms or groups of atoms constituting the salt include hydroxide ions, halogen ions, carboxylic acid ions, sulfonic acid ions, phenoxide ions, and the like.

Pigment derivatives having excellent visible transparency (hereinafter, also referred to as transparent pigment derivatives) can also be used as pigment derivatives. The maximum value (. Epsilon.max) of the molar absorptivity of the transparent pigment derivative in the wavelength region of 400nm to 700nm is preferably 3,000L. Mu. Mol ^-1 ·cm ^-1 Hereinafter, more preferably 1,000 L.mol ¹ ·cm ^-1 Hereinafter, it is more preferably 100 L.mol ^-1 ·cm ^-1 The following is given. The lower limit of εmax is, for example, 1L mol ^-1 ·cm ^-1 Above, it may be 10 L.mol ^-1 ·cm ^-1 The above.

As a specific example of the pigment derivative, there is provided, examples thereof include a compound described in Japanese patent application laid-open No. 56-118462, a compound described in Japanese patent application laid-open No. 63-264674, a compound described in Japanese patent application laid-open No. 01-217077, a compound described in Japanese patent application laid-open No. 03-009961, a compound described in Japanese patent application laid-open No. 03-026767, a compound described in Japanese patent application laid-open No. 03-153780, a compound described in Japanese patent application laid-open No. 03-045662, a compound described in Japanese patent application laid-open No. 04-285669, a compound described in Japanese patent application laid-open No. 06-145546, a compound described in Japanese patent application laid-open No. 06-212088, a compound described in Japanese patent application laid-open No. 06-240158, a compound described in Japanese patent application laid-open No. 10-030063 the compound described in JP-A10-195326, the compound described in paragraphs 0086 to 0098 of International publication No. 2011/024896, the compound described in paragraphs 0063 to 0094 of International publication No. 2012/102399, the compound described in paragraph 0082 of International publication No. 2017/038252, the compound described in paragraph 0171 of JP-A2015-151530, the compound described in paragraphs 0162 to 0183 of JP-A2011-252065, the compound described in JP-A2003-081972, the compound described in JP-A5299151, the compound described in JP-A2015-172732, the compound described in JP-A2014-199308, the compound described in JP-A2014-085562, the compound described in JP-A2014-035351, the compound described in JP-A, the compound described in JP-A2008-081565, the compound described in JP-A2019-109512, the compound described in JP-A2019-133154, the diketopyrrolopyrrole compound having a thiol-linking group described in International publication No. 2020/002106, the benzimidazolone compound described in JP-A2018-168418, or a salt thereof.

The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, based on 100 parts by mass of the colorant. The total content of the pigment derivative and the colorant is preferably 35% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, and particularly preferably 50% by mass or more, based on the total solid content of the curable composition. The upper limit is preferably 70 mass% or less, more preferably 65 mass% or less. The pigment derivative may be used alone or in combination of 2 or more.

< polyalkyleneimine >

The curable composition of the present invention may contain a polyalkyleneimine. The polyalkyleneimines are useful, for example, as dispersing assistants for pigments. The dispersion aid is a material for improving the dispersibility of the pigment in the curable composition. The polyalkyleneimine means a polymer obtained by ring-opening polymerization of an alkyleneimine and having at least a secondary amino group. The polyalkyleneimines may contain, in addition to secondary amino groups, primary or tertiary amino groups. The polyalkyleneimine is preferably a polymer having a branched structure containing a primary amino group, a secondary amino group and a tertiary amino group, respectively. The number of carbon atoms of the alkylene imine is preferably 2 to 6, more preferably 2 to 4, further preferably 2 or 3, particularly preferably 2.

The molecular weight of the polyalkyleneimine is preferably 200 or more, more preferably 250 or more. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, still more preferably 10,000 or less, and particularly preferably 2,000 or less. In addition, when the molecular weight of the polyalkyleneimine is calculated from the structural formula, the molecular weight of the polyalkyleneimine can be 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 is not easy to calculate, a value of the number average molecular weight measured by the boiling point increase method is used. When the measurement is impossible or difficult by the boiling point increase method, the value of the number average molecular weight measured by the viscosity method is used. Further, when the measurement by the viscosity method is not possible or is not easy, a value of the number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) is used.

The amine value of the polyalkyl amine is preferably 5mmol/g or more, more preferably 10mmol/g or more, and still more preferably 15mmol/g or more.

Specific examples of the alkylene imine include ethylene imine, propylene imine, 1, 2-butene imine, and 2, 3-butene imine, and ethylene imine and propylene imine are preferable, and ethylene imine is more preferable. The polyalkyleneimine is particularly preferably polyethyleneimine. The polyethyleneimine preferably contains 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more of the primary amino groups, the secondary amino groups, and the tertiary amino groups in total. Examples of commercially available polyethylenimine include EPOMIN SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (manufactured by NIPPON SHOKUBIAI CO., LTD. Above).

The content of the polyalkyleneimine in the total solid content of the curable composition is preferably 0.1 to 5% by mass. The lower limit is more preferably 0.2 mass% or more, still more preferably 0.5 mass% or more, and particularly preferably 1 mass% or more. The upper limit is more preferably 4.5 mass% or less, still more preferably 4 mass% or less, and particularly preferably 3 mass% or less. The content of the polyalkyleneimine is preferably 0.5 to 20 parts by mass based on 100 parts by mass of the pigment. The lower limit is more preferably 0.6 parts by mass or more, still more preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more. The upper limit is more preferably 10 parts by mass or less, and still more preferably 8 parts by mass or less. The polyalkyleneimine may be used in an amount of 1 or 2 or more. When 2 or more kinds are used, it is preferable that the total amount thereof is within the above range.

< curing accelerator >

The curable composition of the present invention may contain a curing accelerator. Examples of the curing accelerator include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, base generating agents, isocyanate compounds, alkoxysilane compounds, and onium salt compounds. Specific examples of the curing accelerator include a compound described in paragraph 0094 to 0097 of Japanese patent application laid-open No. 2018/056189, a compound described in paragraph 0246 to 0253 of Japanese patent application laid-open No. 2015-034963, a compound described in paragraph 0186 to 0251 of Japanese patent application laid-open No. 2013-041115, an ionic compound described in Japanese patent application laid-open No. 2014-055114, a compound described in paragraph 0071 to 0080 of Japanese patent application laid-open No. 2012-150180, an alkoxysilane compound having an epoxy group described in Japanese patent application laid-open No. 2011-253054, a compound described in paragraph 0085 to 0092 of Japanese patent application laid-open No. 5765059, and an epoxy curing agent containing a carboxyl group described in Japanese patent application laid-open No. 2017-036379. The content of the curing accelerator in the total solid content of the curable composition is preferably 0.3 to 8.9 mass%, more preferably 0.8 to 6.4 mass%.

< Infrared absorber >

The curable composition of the present invention may contain an infrared absorber. For example, when an infrared transmission filter is formed using the curable composition according to the present invention, the wavelength of transmitted light can be shifted to the longer wavelength side with respect to a film obtained by including an infrared absorber in the curable composition. The infrared absorber is preferably a compound having a maximum absorption wavelength on the longer wavelength side than the wavelength of 700 nm. The infrared absorber is preferably a compound having a maximum absorption wavelength in a range exceeding 700nm and 1800nm or less. And the absorbance A of the infrared absorbent at a wavelength of 500nm ¹ And absorbance A at maximum absorption wavelength ² Ratio A of (2) ¹ /A ² Preferably 0.08 or less, more preferably 0.04 or less.

Examples of the infrared absorbing agent include pyrrolopyrrole compounds, cyanine compounds, squaric acid compounds, phthalocyanine compounds, naphthalocyanine compounds, quaternium compounds, merocyanine compounds, ketone onium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyrrole methylene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiol metal complexes, metal oxides, and metal borides. Examples of the pyrrolopyrrole compound include compounds described in paragraphs 0016 to 0058 of JP 2009-263614, compounds described in paragraphs 0037 to 0052 of JP 2011-068731, and compounds described in paragraphs 0010 to 0033 of International publication No. 2015/166873. As the squaric acid compound, japanese patent application laid-open No. 2011-20810 may be mentioned The compounds described in paragraphs 0044 to 0049 of publication No. 1, the compounds described in paragraphs 0060 to 0061 of publication No. 6065169, the compounds described in paragraph 0040 of International publication No. 2016/181987, the compounds described in publication No. 2015-176046, the compounds described in paragraph 0072 of International publication No. 2016/190162, the compounds described in paragraphs 0196 to 0228 of publication No. 2016-074649, the compounds described in paragraph 0124 of publication No. 2017-067963, the compounds described in International publication No. 2017/135359, the compounds described in publication No. 2017-114956, the compounds described in publication No. 6197940, the compounds described in publication No. 120166, and the like. Examples of the cyanine compound include a compound described in paragraphs 0044 to 0045 of JP-A2009-108267, a compound described in paragraphs 0026 to 0030 of JP-A2002-194040, a compound described in JP-A2015-17204, a compound described in JP-A2015-172102, a compound described in JP-A2008-088426, a compound described in 0090 of International publication 2016/190162, and a compound described in JP-A2017-031394. Examples of the Ketone onium compound include those described in Japanese patent application laid-open No. 2017-081029. Examples of the ammonium compound include a compound described in japanese patent application laid-open publication No. 2008-528706, a compound described in japanese patent application laid-open publication No. 2012-012999, a compound described in japanese patent application laid-open publication No. 2007-092060, and a compound described in paragraphs 0048 to 0063 of international publication No. 2018/043564. Examples of the phthalocyanine compound include a compound described in paragraph 0093 of JP 2012-077153, oxytitanium phthalocyanine described in JP 2006-343631, a compound described in paragraphs 0013 to 0029 of JP 2013-195480, a vanadium phthalocyanine compound described in JP 6081771, a vanadium phthalocyanine compound described in International publication No. 2020/071486, and a phthalocyanine compound described in International publication No. 2020/071470. Examples of the naphthalocyanine compound include a compound described in paragraph 0093 of Japanese patent application laid-open No. 2012-077153. As a metal complex of the dithiolene, Examples of the compounds include those described in Japanese patent publication No. 5733804. Examples of the metal oxide include indium tin oxide, antimony tin oxide, zinc oxide, A1-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, and tungsten oxide. For the details of tungsten oxide, refer to paragraph 0080 of Japanese patent application laid-open No. 2016-006476, which is incorporated herein by reference. Examples of the metal boride include lanthanum boride. As the lanthanum boride commercial product, there can be mentioned LaB ₆ F (Japan New Metals Co., ltd.) and the like. Further, as the metal boride, a compound described in international publication No. 2017/119394 can be used. As a commercially available product of indium tin oxide, F-ITO (DOWA HIGHTECH CO., LTD. Manufactured) and the like can be mentioned.

And, as an infrared ray absorber, the squaric acid compound described in Japanese patent application laid-open No. 2017-197437, the squaric acid compound described in Japanese patent application laid-open No. 2017-025311, the squaric acid compound described in International publication No. 2016/154782, the squaric acid compound described in Japanese patent application laid-open No. 5884953, the squaric acid compound described in Japanese patent application laid-open No. 6036689, the squaric acid compound described in Japanese patent application laid-open No. 5810604, the squaric acid compound described in paragraphs 0090 to 0107 of International publication No. 2017/213047, the pyrrole-containing compound described in paragraphs 0019 to 0075 of Japanese patent application laid-open No. 2018-054760, the pyrrole-containing compound described in paragraphs 0078 to 0082 of Japanese patent application laid-open No. 2018-040955, the pyrrole-containing compound described in paragraphs 0043 to 0069 of Japanese patent application laid-open No. 2018-002773, the pyrrole-containing compound a squaric acid compound having an aromatic ring at the α -position of an amide described in paragraphs 0024 to 0086 of JP-A2018-0411, an amide-linked squaric acid compound described in JP-A2017-179131, a compound having a pyrrole-bis-squaric acid skeleton or a Ketone onium skeleton described in JP-A2017-141215, a dihydrocarbazole-bis-squaric acid compound described in JP-A2017-081029, an asymmetric compound described in paragraphs 0027 to 0114 of JP-A2017-068120, a pyrrole-containing ring compound (carbazole type) described in JP-A2017-067963, a phthalocyanine compound described in JP-A6251530, a compound described in paragraphs 0144 to 0146 of International publication No. 2021/049441, and the like.

The content of the infrared absorber in the total solid content of the curable composition is preferably 1 to 40 mass%. The lower limit is more preferably 2% by mass or more, still more preferably 5% by mass or more, and particularly preferably 10% by mass or more. The upper limit is more preferably 30 mass% or less, and still more preferably 25 mass% or less. The curable composition according to the present invention may contain only 1 kind of infrared absorber or 2 or more kinds of infrared absorbers. When the infrared absorbing agent is contained in an amount of 2 or more, it is preferable that the total amount thereof is within the above range.

< ultraviolet absorber >

The curable composition of the present invention may contain an ultraviolet absorber. Examples of the ultraviolet absorber include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyl triazine compounds, indole compounds, and triazine compounds. Specific examples of such compounds include compounds described in paragraphs 0038 to 0052 of JP 2009-2174221, paragraphs 0052 to 0072 of JP 2012-208374, paragraphs 0317 to 0334 of JP 2013-068814, and paragraphs 0061 to 0080 of JP 2016-162946, which are incorporated herein by reference. Examples of the commercial products of the ultraviolet absorber include UV-503 (DAITO CHEMICAL CO., LTD.), tinuvin series manufactured by BASF corporation, uvinul series manufactured by Sumika Chemtex Company Sumisorb series, and the like. Examples of the benzotriazole compound include MIYOSHI OIL & FAT co, ltd, and the system of MYUA (journal of chemical industry, year 2016, month 2, and day 1). The ultraviolet absorber may be any of those described in paragraphs 0049 to 0059 of Japanese patent application laid-open No. 6268967, those described in paragraphs 0059 to 0076 of International publication No. 2016/181987, and those described in International publication No. 2020/137819. The content of the ultraviolet absorber in the total solid content of the curable composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. The ultraviolet absorber may be used in an amount of 1 or 2 or more. When 2 or more kinds are used, it is preferable that the total amount thereof is within the above range.

< polymerization inhibitor >

The curable composition of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4 '-thiobis (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), and N-nitrophenyl hydroxylamine salts (ammonium salts, cerium salts, and the like). Among them, p-methoxyphenol is preferable. The content of the polymerization inhibitor in the total solid content of the curable composition is preferably 0.0001 to 5% by mass. The polymerization inhibitor may be 1 or 2 or more. When the number is 2 or more, the total amount thereof is preferably within the above range.

< silane coupling agent >

The curable composition of the present invention may contain a silane coupling agent. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and a functional group other than the hydrolyzable group. The hydrolyzable group is a substituent that is directly bonded to a silicon atom and can generate a siloxane bond by at least one of hydrolysis reaction and condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of the functional group other than the hydrolyzable group include a vinyl group, a (meth) allyl group, a (meth) acryl group, a mercapto group, an epoxy group, an oxetanyl group, a amino group, a urea group, a thioether group, an isocyanate group, a phenyl group, and the like, and amino groups, a (meth) acryl group, and an epoxy group are preferable. Specific examples of the silane coupling agent include N- β -aminoethyl- γ -aminopropyl methyldimethoxysilane (Shin-Etsu Chemical Co., ltd. Manufactured under the product name KBM-602), N- β -aminoethyl- γ -aminopropyl trimethoxysilane (Shin-Etsu Chemical Co., ltd. Manufactured under the product name KBM-603), N- β -aminoethyl- γ -aminopropyl triethoxysilane (Shin-Etsu Chemical Co., ltd. Manufactured under the product name KBE-602), γ -aminopropyl trimethoxysilane (Shin-Etsu Chemical Co., ltd. Manufactured under the product name KBM-903), γ -aminopropyl triethoxysilane (Shin-Etsu Chemical Co., ltd. Manufactured under the product name KBE-903), 3-methacryloxypropyl methyldimethoxysilane (Shin-Etsu Chemical Co., ltd. Manufactured under the product name KBM-502), and 3-methacryloxypropyl trimethoxysilane (Tsu Chemical Co., ltd. Manufactured under the product name KBM-502). Specific examples of the silane coupling agent include compounds described in paragraphs 0018 to 0036 of JP-A2009-288703 and compounds described in paragraphs 0056 to 0066 of JP-A2009-242604, which are incorporated herein by reference. The content of the silane coupling agent in the total solid content of the curable composition is preferably 0.01 to 15.0 mass%, more preferably 0.05 to 10.0 mass%.

The number of silane coupling agents may be 1 or 2 or more. When the number is 2 or more, the total amount thereof is preferably within the above range.

< surfactant >

The curable composition of the present invention may contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used. The surfactant is preferably a silicone surfactant or a fluorine surfactant. The surfactant may be any surfactant described in paragraphs 0238 to 0245 of International publication No. 2015/166779, incorporated herein by reference.

The fluorine content of the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. The fluorine-containing surfactant having a fluorine content within this range is effective in uniformity of thickness of the coating film and liquid saving property, and has good solubility in the curable composition.

Examples of the fluorine-based surfactant include surfactants described in paragraphs 0060 to 0064 of JP 2014-04318 (corresponding to paragraphs 0060 to 0064 of International publication No. 2014/017669), surfactants described in paragraphs 0117 to 0132 of JP 2011-132503, and surfactants described in JP 2020-008634, the contents of which are incorporated herein by reference. As a commercial product of the fluorine-based surfactant, for example, examples thereof include MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-01, R-40-LM, R-41-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (manufactured by DIC Corporation above) FLUORAD FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited above), SURFLON S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC INC above), polyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA SOLUTIONS INC above), futurent 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 710FS, FTX-218 (manufactured by NEOS COMPANY LIMITED above), and the like.

The fluorine-based surfactant may preferably be an acrylic compound having a molecular structure including a functional group containing a fluorine atom, and the fluorine atom may be volatilized by cutting a portion of the functional group containing a fluorine atom when heated. Examples of such fluorine-based surfactants include MEGAFACE DS series (chemical industry journal of the year 2016, month 22, and daily industrial news (year 2016, month 2, and month 23)), manufactured by DIC Corporation, and MEGAFACE DS-21.

The fluorine-containing surfactant is also preferably a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Examples of such a fluorine-based surfactant include those disclosed in JP 2016-216602A, the contents of which are incorporated herein by reference.

The fluorine-based surfactant may be a block polymer. The fluorine-containing surfactant may preferably be a fluorine-containing polymer compound comprising: repeating units derived from a (meth) acrylate compound having a fluorine atom; and a repeating unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group, propyleneoxy group). The fluorosurfactant described in paragraphs 0016 to 0037 of JP-A2010-032698 and the following compounds are also exemplified as the fluorosurfactant used in the present invention.

[ chemical formula 34]

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000. In the above-mentioned compounds, the% representing the proportion of the repeating unit is mol%.

The fluorine-based surfactant may be a fluorine-containing polymer having an ethylenically unsaturated group in a side chain. Specific examples thereof include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A2010-164965, and MEGAFACE RS-101, RS-102 and RS-718K, RS-72-K manufactured by DIC Corporation. The fluorine-based surfactant may be a compound described in paragraphs 0015 to 0158 of JP-A2015-117327.

In addition, from the viewpoint of environmental protection, it is also preferable to use a surfactant described in International publication No. 2020/084854 instead of the surfactant having a perfluoroalkyl group having 6 or more carbon atoms.

Furthermore, a fluoroimide salt compound represented by the formula (fi-1) is also preferably used as the surfactant.

[ chemical formula 35]

In the formula (fi-1), m represents 1 or 2, n represents an integer of 1 to 4, a represents 1 or 2, X ^a+ Represents a valence metal ion, primary ammonium ion, secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ionAmmonium ion or NH ₄ ⁺ 。

Examples of the nonionic surfactant include glycerol (glycerol), trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, and the like), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, pluronic Li0, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF corporation), tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF corporation), SOLSPERSE 20000 (manufactured by Japan Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), piomin D-6112, D-6112-W, D-6315 (manufactured by tamoto & Fat, ltd.), OLFIN 1010, sunk 104, and ltd 440, and the like.

Examples of silicone surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67Additive, 74Additive, M Additive, SF 8419 OIL (manufactured by Ltd.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc. above), 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 BYK-Chemie GmbH) and the like.

The silicone surfactant may also be a compound having the following structure.

[ chemical formula 36]

The content of the surfactant in the total solid content of the curable composition is preferably 0.001 to 5.0% by mass, more preferably 0.005 to 3.0% by mass. The number of surfactants may be 1 or 2 or more. When the number is 2 or more, the total amount thereof is preferably within the above range.

< antioxidant >

The curable composition of the present invention may contain an antioxidant. Examples of the antioxidant include phenol compounds, phosphite compounds, and thioether compounds. As the phenol compound, any phenol compound that has been a conventional phenol-based antioxidant can be used. Preferred examples of the phenol compound include hindered phenol compounds. Compounds having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position) are preferred. The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. The antioxidant is preferably a compound having a phenol group and a phosphite group in the same molecule. In addition, a phosphorus antioxidant can be preferably used as the antioxidant. Examples of the phosphorus antioxidant include tris [2- [ [2,4,8, 10-tetrakis (1, 1-dimethylethyl) dibenzo [ d, f ] [1,3,2] dioxaphosph-6-yl ] oxy ] ethyl ] amine, tris [2- [ (4, 6,9, 11-tetra-t-butyldibenzo [ d, f ] [1,3,2] dioxaphosph-2-yl) oxy ] ethyl ] amine, and bis (2, 4-di-t-butyl-6-methylphenyl) ethyl phosphite. Examples of the commercially available antioxidants include ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50F, ADEKA STAB AO-60G, ADEKA STAB AO-80, and ADEKA STAB AO-330 (manufactured as ADEKA CORPORATION). The antioxidant may be a compound described in paragraphs 0023 to 0048 of Japanese patent application publication No. 6268967, a compound described in International publication No. 2017/006600, a compound described in International publication No. 2017/164024, or a compound described in Korean patent application publication No. 10-2019-0059371. The content of the antioxidant in the total solid content of the curable composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. The antioxidant may be used in an amount of 1 or 2 or more. When 2 or more kinds are used, it is preferable that the total amount thereof is within the above range.

< other ingredients >

The curable composition according to the present invention may contain a sensitizer, a curing accelerator, a filler, a heat curing accelerator, a plasticizer, and other auxiliary agents (for example, conductive particles, an antifoaming agent, a flame retardant, a leveling agent, a peeling accelerator, a perfume, a surface tension regulator, a chain transfer agent, and the like) as necessary. By properly containing these components, properties such as film physical properties can be adjusted. For these components, for example, reference can be made to the descriptions of paragraphs 0183 and later of Japanese patent application laid-open No. 2012-003225 (paragraph 0237 of the specification of corresponding U.S. patent application publication No. 2013/0034812), and the descriptions of paragraphs 0101 to 0104 and 0107 to 0109 of Japanese patent application laid-open No. 2008-250074, and the like, which are incorporated herein by reference. The curable composition of the present invention may contain a latent antioxidant as needed. As potential antioxidants, the following compounds may be mentioned: the site functioning as an antioxidant is protected by a protecting group and the protecting group is detached by heating at 100 to 250 ℃ or heating at 80 to 200 ℃ in the presence of an acid/base catalyst and functions as an antioxidant. Examples of the latent antioxidant include compounds described in Japanese patent laid-open publication Nos. 2014/021023 and 2017/030005, and Japanese patent laid-open publication No. 2017-008219. Examples of commercial products of the latent antioxidant include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION).

The curable composition according to the present invention may contain a metal oxide to adjust the refractive index of the obtained 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 1nm to 100nm, more preferably 3nm to 70nm, and still more preferably 5nm to 50nm. The metal oxide may have a core-shell structure. In this case, the core may be hollow.

The curable composition according to the present invention may contain a light resistance improver. As an agent for improving the light resistance, examples thereof include the compounds described in paragraphs 0036 to 0037 of Japanese patent application laid-open No. 2017-198787, the compounds described in paragraphs 0029 to 0034 of Japanese patent application laid-open No. 2017-146350, the compounds described in paragraphs 0036 to 0037 and 0049 to 0052 of Japanese patent application laid-open No. 2017-129774, the compounds described in paragraphs 0031 to 0034 and 0058 to 0059 of Japanese patent application laid-open No. 2017-129674, the compounds described in paragraphs 0036 to 0037 and 0051 to 0054 of Japanese patent application laid-open No. 2017-122803, the compounds described in paragraphs 0025 to 0039 of International publication No. 2017/164127, the compounds described in paragraphs 0034 to 0047 of Japanese patent application laid-open No. 2017-186546, and the like the compounds described in paragraphs 0019 to 0041 of Japanese patent application laid-open No. 2015-025116, the compounds described in paragraphs 0101 to 0125 of Japanese patent application laid-open No. 2012-145604, the compounds described in paragraphs 0018 to 0021 of Japanese patent application laid-open No. 2012-1034975, the compounds described in paragraphs 0015 to 0018 of Japanese patent application laid-open No. 2011-257591, the compounds described in paragraphs 0017 to 0021 of Japanese patent application laid-open No. 2011-191483, the compounds described in paragraphs 0108 to 0116 of Japanese patent application laid-open No. 2011-145668, and the compounds described in paragraphs 0103 to 0153 of Japanese patent application laid-open No. 2011-253174.

The curable composition of the present invention preferably also contains substantially no terephthalate. The term "substantially free" as used herein means that the content of terephthalic acid ester in the total amount of the curable composition is 1000 ppb by mass or less, more preferably 100 ppb by mass or less, and particularly preferably zero.

From the viewpoint of environmental protection, the use of perfluoroalkylsulfonic acids and salts thereof, and perfluoroalkylcarboxylic acids and salts thereof may be regulated. In the curable composition according to the present invention, when the content of the above-mentioned compound is reduced, the content of the perfluoroalkylsulfonic acid (particularly, the perfluoroalkyl sulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt, and the perfluoroalkyl carboxylic acid (particularly, the perfluoroalkyl carboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt are preferably in the range of 0.01ppb to 1,000ppb, more preferably in the range of 0.05ppb to 500ppb, and even more preferably in the range of 0.1ppb to 300ppb, relative to the total solid content of the curable composition. The curable composition of the present invention may contain substantially no perfluoroalkylsulfonic acid or salt thereof, or no perfluoroalkylcarboxylic acid or salt thereof. For example, by using a compound capable of substituting for the perfluoroalkyl sulfonic acid and its salt and a compound capable of substituting for the perfluoroalkyl carboxylic acid and its salt, a curable composition substantially free of the perfluoroalkyl sulfonic acid and its salt and the perfluoroalkyl carboxylic acid and its salt can be selected. Examples of the compound that can be substituted for the controlled compound include compounds that are excluded from the controlled object according to the difference in the number of carbon atoms of the perfluoroalkyl group. However, the use of perfluoroalkylsulfonic acids and salts thereof, and perfluoroalkylcarboxylic acids and salts thereof is not hindered by the foregoing. The curable composition according to the present invention may contain a perfluoroalkylsulfonic acid or a salt thereof and a perfluoroalkylcarboxylic acid or a salt thereof within a maximum allowable range.

The water content of the curable composition according to the present invention is preferably 3% by mass or less, more preferably 0.01% by mass to 1.5% by mass, and still more preferably 0.1% by mass to 1.0% by mass. The water content can be measured by the karl fischer method.

The curable composition of the present invention can be used with the purpose of adjusting the film surface (flatness, etc.), adjusting the film thickness, etc., and adjusting the viscosity. The viscosity value can be appropriately selected as required, and is preferably 0.3 to 50 mPas, more preferably 0.5 to 20 mPas, at 25 ℃. As a method for measuring the viscosity, for example, a cone-plate viscometer can be used, and the temperature can be adjusted to 25 ℃.

In the curable composition according to the present invention, the amount of chloride ions in the curable composition is preferably 10,000ppm or less, more preferably 1000ppm or less, from the viewpoints of environmental protection, suppression of generation of foreign matters, suppression of device contamination, and the like. In order to make the chloride ion in the curable composition fall within the above range, a method of using a raw material having a small chloride ion content, a method of removing chloride ions by water washing, ion exchange resin, filter filtration, or the like, and the like are exemplified. As a method for measuring chloride ions, known methods can be used, and examples thereof include ion chromatography and combustion ion chromatography.

< storage Container >

The container for the curable composition is not particularly limited, and a known container can be used. In addition, as the storage container, a multilayer bottle having 6 types of 6-layer resins constituting the inner wall of the container and a bottle having 6 types of resins in a 7-layer structure are preferably used in order to prevent impurities from being mixed into the raw material and the curable composition. Examples of such a container include those described in Japanese patent application laid-open No. 2015-123351. The inner wall of the container is preferably made of glass, stainless steel, or the like for the purpose of preventing elution of metal from the inner wall of the container, improving the storage stability of the curable composition, suppressing deterioration of components, or the like.

< method for producing curable composition >

The curable composition according to the present invention can be prepared by mixing the above-described components. In the preparation of the curable composition, all the components may be dissolved and/or dispersed in a solvent at the same time to prepare the curable composition, or the components may be appropriately divided into 2 parts or more of solutions or dispersions as required, and these may be mixed at the time of use (at the time of coating) to prepare the curable composition.

In addition, in the preparation of the curable composition, a process of dispersing the pigment is preferably included. In the process of dispersing the pigment, as the mechanical force for dispersing the pigment, compression, extrusion, impact, shearing, cavitation, and the like are mentioned. Specific examples of these processes include bead milling, sand milling, roll milling, ball milling, paint stirring, micro-jet, high-speed impeller, sand mixing, jet mixing, high-pressure wet micronization, and ultrasonic dispersion. In addition, in grinding a pigment in a sand mill (bead mill), it is preferable to perform a treatment under a condition that the grinding efficiency is improved by using microbeads having a small diameter, increasing the filling rate of the microbeads, or the like. Further, it is preferable to remove coarse particles by filtration, centrifugal separation, or the like after the pulverization treatment. The process and the disperser for dispersing the pigment can be preferably used as the "general collection of dispersing techniques, JOHOKIKO co., ltd. Release, 7.15 th year in 2005" or "integrated data set of dispersion techniques and practical applications in industry, release by the department of business development center, 10.10 th year in 1978, and the process and disperser described in paragraph 0022 of japanese patent application laid-open No. 2015-157893. In the process of dispersing the pigment, the fine particle treatment may be performed by a salt milling process. For example, materials, apparatuses, processing conditions, and the like used in the salt milling step can be described in Japanese patent application laid-open No. 2015-194521 and Japanese patent application laid-open No. 2012-046629. As the beads for dispersion, zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, glass, or a combination thereof can be used. Further, an inorganic compound having a mohs hardness of 2 or more can be used. The beads may be contained in the composition in an amount of 1 to 10000 ppm.

In preparing the curable composition, it is preferable to filter the curable composition with a filter in order to remove foreign matters, reduce defects, and the like. The filter is not particularly limited as long as it is a filter conventionally used for filtration and the like. Examples of the filter include filters using a material such as a fluororesin such as Polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVDF), a polyamide resin such as nylon (for example, nylon-6 or nylon-6, 6), a polyolefin resin such as polyethylene or polypropylene (PP) (including a high-density and ultrahigh-molecular-weight polyolefin resin). Among these materials, polypropylene (including high density polypropylene) and nylon are preferred.

The pore diameter of the filter is preferably 0.01 μm to 7.0. Mu.m, more preferably 0.01 μm to 3.0. Mu.m, still more preferably 0.05 μm to 0.5. Mu.m. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. As regards the pore size value of the filter, reference can be made to the nominal value of the filter manufacturer. As the filter, various filters provided by Nihon Pall ltd (DFA 4201NIEY, DFA4201NAEY, DFA4201J006P, etc.), advantec Toyo Kaisha, ltd, nihon Entegris k.k. (Formerly Nippon Mykrolis Corporation), KITZ MICROFILTER Corporation, etc. can be used.

Also, as the filter, a fibrous filter material is preferably used. Examples of the fibrous filter material include polypropylene fibers, nylon fibers, and glass fibers. Examples of commercial products include ROKITECHNO CO, LTD. SBP type series (SBP 008, etc.), TPR type series (TPR 002, TPR005, etc.), SHPX type series (SHPX 003, etc.).

When filters are used, different filters (e.g., filter 1 and filter 2, etc.) may be combined. In this case, the filtration using each filter may be performed only 1 time, or may be performed 2 times or more. Also, filters of different pore diameters may be combined within the above range. The filtration using the 1 st filter is performed only on the dispersion, and the filtration using the 2 nd filter may be performed after mixing other components. And, the filter can be appropriately selected according to the hydrophilicity and hydrophobicity of the composition.

(cured product and film)

The cured product according to the present invention is a cured product obtained by curing the curable composition according to the present invention.

The film according to the present invention is a film obtained from the curable composition according to the present invention, preferably a film obtained by curing the curable composition according to the present invention. The film according to the present invention can be used for filters such as color filters and infrared transmission filters. In particular, a colored pixel which is used as a color filter can be preferable. Examples of the coloring pixel include a red pixel, a green pixel, a blue pixel, a magenta pixel, a cyan pixel, a yellow pixel, and the like, preferably a green pixel and a blue pixel, and more preferably a green pixel.

The film thickness of the film according to the present invention can be appropriately adjusted according to the purpose, and is preferably 0.1 μm to 20. Mu.m. The upper limit of the film thickness is more preferably 10 μm or less, still more preferably 5 μm or less, particularly preferably 3 μm or less, and most preferably 1.5 μm or less. The lower limit of the film thickness is more preferably 0.2 μm or more, and still more preferably 0.3 μm or more.

(method for producing cured product and method for producing film)

The method for producing a cured product according to the present invention and the method for producing a film according to the present invention are not particularly limited, and the method preferably includes a step of irradiating the curable composition according to the present invention with light having a wavelength of 150nm to 380nm, and more preferably includes a step of irradiating the curable composition with light having a wavelength of 150nm to 300 nm.

Examples of the light having a wavelength of 150nm to 380nm include i-rays (365 nm), krF rays (248 nm), arF rays (193 nm), and the like.

The shape of the obtained cured product is not particularly limited, and is preferably film-like.

The film according to the present invention can be produced by a process of applying the curable composition according to the present invention to a support. The method for producing a film preferably further includes a step of forming a pattern (pixel). As a method for forming a pattern (pixel), photolithography and dry etching are mentioned, and photolithography is preferable.

The patterning by photolithography preferably includes the steps of: the curable composition layer is formed on the support using the curable composition of the present invention, the curable composition layer is exposed in a pattern, and the unexposed portion of the curable composition layer is removed by development to form a pattern (pixel). A step of baking the curable composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided as needed.

In the step of forming the curable composition layer, the curable composition according to the present invention is used to form the curable composition layer on the support. The support is not particularly limited, and may be appropriately selected according to the application. For example, a glass substrate, a silicon substrate, or the like is given, and a silicon substrate is preferable. Further, a Charge Coupled Device (CCD), a Complementary Metal Oxide Semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate. Further, a black matrix (black matrix) may be formed on the silicon substrate to isolate each pixel. In order to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the substrate surface, a base layer may be provided on the silicon substrate. The underlayer can be formed using a composition obtained by removing a colorant from the curable composition described in the present specification, a composition containing a resin, a polymerizable compound, a surfactant, or the like described in the present specification, or the like. The surface contact angle of the underlayer is preferably 20 ° to 70 ° when measured with diiodomethane. And, when measured with water, it is preferably 30 to 80 °.

As a method for applying the curable composition, a known method can be used. For example, a drop casting method (drop casting); a slit coating method; spraying; roll coating; spin coating (spin coating); a casting coating method; slit spin coating; prewet (for example, a method described in japanese patent application laid-open No. 2009-145395); inkjet (e.g., on-demand, piezo, thermal), jet printing such as nozzle jetting, flexography, screen printing, gravure, reverse offset printing, metal mask printing, and the like; a transfer method using a mold or the like; nanoimprint method, and the like. The method of application in inkjet is not particularly limited, and examples thereof include a method shown in "unlimited possibility in inkjet development and use-patent, release 2 in 2005, sumitbe Techon Research co., ltd." (especially page 115 to page 133), a method described in japanese patent application laid-open publication nos. 2003-262626716, 2003-185831, 2003-261827, 2012-126830, 2006-169325, and the like. The method of applying the curable composition can be described in international publication nos. 2017/030174 and 2017/018419, which are incorporated herein by reference.

The curable composition layer formed on the support may be dried (prebaked). When the film is manufactured by a low temperature process, the pre-baking may not be performed. In the case of performing the prebaking, the prebaking temperature is preferably 150℃or less, more preferably 120℃or less, and further preferably 110℃or less. The lower limit may be, for example, 50℃or higher, or 80℃or higher. The pre-baking time is preferably 10 seconds to 300 seconds, more preferably 40 seconds to 250 seconds, still more preferably 80 seconds to 220 seconds. The pre-baking can be performed using a hot plate, an oven, or the like.

Next, the curable composition layer is exposed in a pattern (exposure step). For example, the curable composition layer can be exposed in a pattern by exposing the curable composition layer through a mask having a predetermined mask pattern using a stepper, a scanner, or the like. Thereby, the exposed portion can be cured.

Examples of radiation (light) that can be used for exposure include g-rays and i-rays. Light having a wavelength of 300nm or less (preferably, light having a wavelength of 150nm to 300 nm) can also be used. Examples of light having a wavelength of 300nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm) are preferable. Further, a long wavelength light source of 300nm or more can be used.

In the exposure, light may be continuously irradiated to perform exposure, or pulse irradiation may be performed to perform exposure (pulse exposure). The pulse exposure is an exposure method in which exposure is performed by repeating irradiation and suspension of light in a short period of time (for example, in the order of milliseconds or less).

The irradiation amount (exposure amount) is preferably, for example, 0.03J/cm ² ～2.5J/cm ² More preferably 0.05J/cm ² ～1.0J/cm ² . The oxygen concentration at the time of exposure can be appropriately selected, and in addition to the exposure to the atmosphere, for example, exposure may be performed in a low oxygen atmosphere (for example, 15 vol%, 5 vol%, or substantially no oxygen) having an oxygen concentration of 19 vol% or less, or exposure may be performed in a high oxygen atmosphere (for example, 22 vol%, 30 vol%, or 50 vol%) having an oxygen concentration of more than 21 vol%. The exposure illuminance can be set appropriately, and can be generally selected from 1000W/m ² ～100000W/m ² (e.g., 5000W/m ² 、15000W/m ² Or 35000W/m ² ) Is not limited in terms of the range of (a). The conditions of the oxygen concentration and the exposure illuminance may be appropriately combined, and for example, the oxygen concentration may be 10% by volume and the illuminance 10000W/m ² Oxygen concentration is 35% by volume and illuminance is 20000W/m ² Etc.

Then, the unexposed portions of the curable composition layer are removed by development to form a pattern (pixel). The development and removal of the unexposed portion of the curable composition layer can be performed using a developer. Thus, the curable composition layer in the unexposed portion in the exposure step dissolves into the developer, leaving only the photo-cured portion. For example, the temperature of the developer is preferably 20 to 30 ℃. The development time is preferably 20 seconds to 180 seconds. In order to improve the residue removal performance, the following steps may be repeated several times: and a step of throwing away the developer every 60 seconds and re-supplying a new developer.

The developer may be an organic solvent, an alkaline developer, or the like, and an alkaline developer is preferably used. As the alkaline developer, an alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water is preferable. Examples of the alkaline agent include organic alkaline compounds such as ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1, 8-diazabicyclo [5.4.0] -7-undecene, and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, and sodium metasilicate. The alkaline agent is preferably a compound having a large molecular weight from the viewpoint of environmental aspects and safety aspects. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The developer may further contain a surfactant. From the standpoint of convenience in transportation, storage, and the like, the developer may be first prepared as a concentrated solution and diluted to a desired concentration at the time of use. The dilution ratio is not particularly limited, and can be set in a range of 1.5 to 100 times, for example. Further, it is also preferable to perform cleaning (rinsing) with pure water after development. And, the following flushing is preferably performed: the rinse solution is supplied to the developed curable composition layer while rotating the support on which the developed curable composition layer is formed. Further, it is also preferable that the cleaning liquid is discharged by moving the nozzle from the center portion of the support body to the peripheral portion of the support body. In this case, when the nozzle is moved from the center portion to the peripheral portion of the support body, the nozzle can be moved while gradually reducing the moving speed. By performing the flushing in this manner, in-plane unevenness of flushing can be suppressed. The same effect can be obtained by gradually decreasing the rotation speed of the support body while moving the nozzle from the center portion to the peripheral portion of the support body.

After development, it is preferable to perform additional exposure treatment and heat treatment (post baking) after drying. The additional exposure treatment and post baking are curing treatments after development for producing a fully cured curable composition. The heating temperature in the post baking is, for example, preferably 100 to 240 ℃, more preferably 200 to 240 ℃. The film after development can be post-baked continuously or batchwise using a heating mechanism such as a hot plate, a convection oven (heated air circulation dryer), or a high-frequency heater so as to satisfy the above conditions. In the case of performing the additional exposure treatment, the light used for exposure is preferably light having a wavelength of 400nm or less. The additional exposure treatment may be performed by the method described in korean laid-open patent No. 10-2017-012130.

The patterning by the dry etching method preferably includes the steps of: the method for producing a cured product of the curable composition of the present invention comprises the steps of forming a curable composition layer on a support using the curable composition of the present invention, curing the entire curable composition layer to form a cured product layer, forming a resist layer on the cured product layer, exposing the resist layer in a pattern, developing the exposed resist layer to form a resist pattern, and dry etching the cured product layer using an etching gas with the resist pattern as a mask. When forming the resist layer, it is preferable to further perform a pre-bake treatment. In particular, as a process for forming the resist layer, a method of performing a post-exposure heat treatment and a post-development heat treatment (post-baking treatment) is preferable. For the patterning by the dry etching method, reference can be made to the descriptions in paragraphs 0010 to 0067 of Japanese patent application laid-open No. 2013-064993, which is incorporated herein by reference.

(optical element)

The optical element according to the present invention has the film according to the present invention.

Examples of the optical element include a filter, a lens, a prism, a mirror, and a diffraction grating. Among them, a filter may be preferable.

Examples of the type of the filter include a color filter and an infrared transmission filter, and a color filter is preferable. The color filter preferably has the film according to the present invention as its coloring pixel.

In the optical filter, the film thickness of the film according to the present invention can be appropriately adjusted according to the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, and still 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 still more preferably 0.3 μm or more.

The width of the pixels included in the filter is preferably 0.4 μm to 10.0 μm. The lower limit is more preferably 0.4 μm or more, still more preferably 0.5 μm or more, and particularly preferably 0.6 μm or more. The upper limit is more preferably 5.0 μm or less, still more preferably 2.0 μm or less, particularly preferably 1.0 μm or less, and most preferably 0.8 μm or less. The Young's modulus of the pixel is preferably 0.5GPa to 20GPa, more preferably 2.5GPa to 15GPa.

Each pixel included in the filter preferably has high flatness. Specifically, the surface roughness Ra of the pixel is preferably 100nm or less, more preferably 40nm or less, and further preferably 15nm or less. The lower limit is not limited, but is preferably 0.1nm or more, for example. The surface roughness of the pixel can be measured by using, for example, AFM (atomic force microscope) Dimension3100 manufactured by Veeco corporation. The water contact angle at the pixel can be set to an appropriate preferable value, and is usually in the range of 50 ° to 110 °. For example, the contact angle can be measured using a contact angle meter CV-dt·a type (Kyowa Interface Science co., ltd.). Further, the volume resistance value of the pixel is preferably high. Specifically, the volume resistance value of the pixel is preferably 10 ⁹ Omega cm or more, more preferably 10 ¹¹ Omega cm or more. The upper limit is not specified, and is preferably 10 ¹⁴ Q.cm or less. For example, the volume resistance value of the pixel can be measured using the ultra-high resistance meter 5410 (manufactured by ADVANTEST CORPORATION).

In the optical filter, a protective layer may be provided on the surface of the film according to the present invention. By providing the protective layer, various functions such as oxidation resistance, low reflection, hydrophilic and hydrophobic properties, and shielding of light of a specific wavelength (ultraviolet rays, near infrared rays, and the like) can be imparted. The thickness of the protective layer is preferably 0.01 μm to 10. Mu.m, more preferably 0.1 μm to 5. Mu.m. Examples of the method for forming the protective layer include a method of forming a protective layer by applying a protective layer forming product, a chemical vapor deposition method, and a method of adhering a molded resin with an adhesive material. Examples of the component constituting the protective layer include (meth) acrylic resin, alkene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfoneResins, polyethersulfone resins, polystyrene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, polyol resins, polyvinylidene chloride resins, melamine resins, polyurethane resins, aromatic polyamide resins, alkyd resins, epoxy resins, modified silicone resins, fluorine resins, polycarbonate resins, polyacrylonitrile resins, cellulose resins, si, C, W, al ₂ O ₃ 、M _o 、SiO ₂ 、Si ₂ N ₄ And the like, two or more of these components may be contained. For example, in the case of a protective layer for the purpose of oxidation resistance, the protective layer preferably contains a polyol resin, siO ₂ Si (Si) ₂ N ₄ . In the case of a protective layer for the purpose of low reflection, the protective layer preferably contains a (meth) acrylic resin and a fluororesin.

The protective layer may contain organic/inorganic particles, an absorber of light of a specific wavelength (for example, ultraviolet rays, near infrared rays, or the like), a refractive index adjuster, an antioxidant, a thickener, a surfactant, or other additives as necessary. Examples of the organic/inorganic particles include polymer particles (for example, silicone resin particles, polystyrene particles, and melamine resin particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, calcium carbonate, and barium sulfate. The absorber for light of a specific wavelength can be a known absorber. The content of these additives can be appropriately adjusted, and is preferably 0.1 to 70 mass%, more preferably 1 to 60 mass%, relative to the total mass of the protective layer.

Further, as the protective layer, the protective layers described in paragraphs 0073 to 0092 of Japanese patent application laid-open No. 2017-151176 can be used.

The filter may also have the following structure: for example, each pixel is embedded in a space divided into a square by a partition wall.

(image sensor)

The image sensor according to the present invention has the film according to the present invention.

Examples of the image sensor include a solid-state imaging element, an X-ray imaging element, and an organic thin film imaging element. Among them, the present invention can be preferably used for a solid-state imaging element.

The solid-state imaging device according to the present invention includes the film according to the present invention. The configuration of the solid-state imaging device is not particularly limited as long as it functions as a solid-state imaging device, and examples thereof include the following.

That is, a transfer electrode formed of a plurality of photodiodes and polysilicon or the like constituting a light receiving region of a solid-state imaging element (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide film semiconductor) image sensor or the like) is provided on a substrate, a light shielding film having only a light receiving portion opening of the photodiode is provided on the photodiodes and the transfer electrode, an element protection film formed of silicon nitride or the like is provided on the light shielding film so as to cover the entire surface of the light shielding film and the light receiving portion of the photodiode, and a color filter is provided on the element protection film. The device protection film may have a light condensing means (for example, a microlens, etc. hereinafter, the same applies) below the color filter (on the side close to the substrate), or the color filter may have a light condensing means.

The color filter may have the following structure: for example, each colored pixel is embedded in a space divided into a square by a partition wall. The refractive index of the partition wall at this time is preferably lower than that of each colored pixel. Examples of imaging devices having such a structure include those described in japanese patent application laid-open publication No. 2012-227478, japanese patent application laid-open publication No. 2014-179577, and international publication No. 2018/043654. Further, as shown in japanese patent application laid-open No. 2019-211559, an ultraviolet absorbing layer may be provided in the structure of the solid-state imaging element to improve light resistance. An imaging device including a solid-state imaging element according to the present invention can be used as a digital camera, an electronic device (such as a mobile phone) having an imaging function, a vehicle camera, and a monitoring camera.

(image display device)

The image display device according to the present invention includes the film according to the present invention. Examples of the image display device include a liquid crystal display device and an organic electroluminescent display device. The definition of the image display device and the details of each image display device are described in, for example, "electronic display device (zozuo zhaofu, kogyo Chosakai Publishing co., ltd., release in 1990)", "display device (isb, chapter Sangyo Tosho Publishing co., ltd., release in 1989)", and the like. The liquid crystal display device is described in, for example, "next-generation liquid crystal display technology (edited in Tian Longnan, kogyo Chosakai Publishing co., ltd., release 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the "next-generation liquid crystal display technology" described above.

(radical polymerization initiator represented by formula 1)

The radical polymerization initiator according to the present invention is a radical polymerization initiator represented by the following formula 1.

The radical polymerization initiator according to the present invention is preferably a photo radical polymerization initiator, more preferably a photo radical polymerization initiator that generates radicals by light having a wavelength of 150nm to 300 nm.

[ chemical formula 37]

The preferred mode of the radical polymerization initiator represented by the formula 1 in the radical polymerization initiator according to the present invention is the same as the preferred mode of the radical polymerization initiator represented by the formula 1 in the curable composition.

(Compound represented by formula 2)

The compound according to the present invention is a novel compound represented by the following formula 2.

[ chemical formula 38]

The preferable mode of the compound represented by formula 2 among the compounds according to the present invention is the same as the preferable mode of the radical polymerization initiator represented by formula 2 in the curable composition.

The compound represented by the above formula 2 is preferably a compound represented by the following formula 3A or formula 3B.

[ chemical formula 39]

The preferable mode of the compound represented by the formula 3A or 3B among the compounds according to the present invention is the same as the preferable mode of the radical polymerization initiator represented by the formula 3A or 3B in the curable composition.

The compound represented by the above formula 2 is particularly preferably a compound represented by the following formula 4.

[ chemical formula 40]

The preferable mode of the compound represented by formula 4 among the compounds according to the present invention is the same as the preferable mode of the radical polymerization initiator represented by formula 4 in the curable composition.

Examples

The present invention will be described in further detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment order, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. Me in the structural formula shown below represents methyl, et represents ethyl, and Ph represents phenyl. In this example, "%" and "parts" represent "% by mass" and "parts by mass", respectively, unless otherwise specified.

The photo radical polymerization initiators A-1 to A-112 used in the examples were the same as the above specifically described examples of the radical polymerization initiator represented by formula 1, respectively, A-1 to A-112.

Synthesis example 1: synthesis method of photo radical polymerization initiator A-1

14.6g of α -tetralone was added to a three-necked flask, and dissolved in 300mL of tetrahydrofuran. After cooling to 5 ℃, 19.3g of sodium methoxide 28% methanol solution was slowly added dropwise and stirred for further 30 minutes. 14.1g of methyl iodide was slowly added dropwise to the reaction solution, and the mixture was stirred at 5℃for 5 hours. The obtained reaction solution was extracted with ethyl acetate, washed with water, and the organic phase was dried over magnesium sulfate and concentrated. The obtained mixture was purified by column chromatography (hexane/ethyl acetate=10/1), whereby 12.3g (77% yield) of 2-methyl- α -tetralone was obtained.

12.3g of 2-methyl- α -tetralone obtained above was dissolved in 200mL of acetic acid, and 12.3g of bromine was added dropwise over 1 hour at room temperature (25 ℃ C., the same applies below), followed by stirring at room temperature for 5 hours. The obtained reaction solution was extracted with ethyl acetate, washed with an aqueous sodium thiosulfate solution and with water, and the organic phase was dried over magnesium sulfate and concentrated. The obtained mixture was purified by column chromatography (hexane/ethyl acetate=10/1), whereby 13.6g (74% yield) of 2-bromo-2-methyl- α -tetralone was obtained.

13.6g of 2-bromo-2-methyl- α -tetralone was dissolved in 120mL of tetrahydrofuran, 10.9g of 28% methanol solution of sodium methoxide was added thereto, and the mixture was stirred at 60℃for 2 hours, followed by distillation to remove volatile components of the reaction solution. After the obtained residue was dissolved in 100mL of toluene and washed with water. The organic phase was dried over sodium sulfate and distilled to remove the solvent. To the obtained residue was added 100mL of a 10% tetrahydrofuran solution of dimethylamine, 10.5g of lithium perchlorate was added thereto while stirring, and the temperature was raised to 60 ℃. The mixture was stirred under nitrogen at 60℃for a further 6 hours. The obtained reaction solution was extracted with ethyl acetate, washed with water, and the organic phase was dried over magnesium sulfate and concentrated. The obtained mixture was purified by column chromatography (hexane/ethyl acetate=4/1), whereby 7.5g of a photo radical polymerization initiator a-1 was obtained (yield of 64%).

1HNMR(400MHz)δ＝1.58(s，3H)，1.8(m，2H)，2.26(s，6H)，2.8(m，2H)，7.1-7.5(m，3H)，7.83(d，1H)

< synthetic example 2: synthesis method of photo radical polymerization initiator A-6

A photo radical polymerization initiator A-6 was synthesized in the same manner as in Synthesis example 1 except that 2-methyl- α -tetralone was changed to 6-chloro-3-methylsulfanyl-gram -4-one and dimethylamine was changed to morpholine.

¹ HNMR(400MHz)6＝1.63(s，3H)，2.7(m，4H)，2.85(d，1H)，3.10(d，1H)，3.6(m，4H)，7.1-7.5(m，2H)，7.78(s，1H)

< synthesis example 3: synthesis method of photo radical polymerization initiator A-15

To a three-necked flask, 19.8g of 6-chloro-sulfur-necked- -4-ketone was added and dissolved in 300mL of acetic acid, followed by dropwise addition of 16.3g of bromine at room temperature over 1 hour and further stirring at room temperature over 5 hours. The obtained reaction solution was extracted with ethyl acetate, washed with an aqueous sodium thiosulfate solution and with water, and the organic phase was dried over magnesium sulfate and concentrated. The obtained mixture was purified by column chromatography (hexane/ethyl acetate=8/1), whereby 23.4g (85% yield) of 3-bromo-6-chlorothiokout g -4-one was obtained

23.4g of 3-bromo-6-chlorothiokout- -4-one obtained above was dissolved in 200mL of tetrahydrofuran and cooled to 0 ℃. 50mL of a 10% tetrahydrofuran solution of dimethylamine was added thereto over 30 minutes, and the mixture was stirred at 0℃for 4 hours. The obtained reaction solution was extracted with ethyl acetate, washed with water, and the organic phase was dried over magnesium sulfate and concentrated. The obtained mixture was recrystallized from methanol and purified to thereby obtain 14.2g (69% yield) of 6-chloro-3- (dimethylamino) thioxo- -4-one.

14.2g of 6-chloro-3- (dimethylamino) thiokou- -4-one obtained above was dissolved in 200mL of N, N-dimethylformamide and heated to 50 ℃. To this was added 3.5g of sodium hydroxide, followed by 13.0g of p-methylbenzyl bromide, and the mixture was heated and stirred at 50℃for 6 hours. The obtained reaction liquid was added to 1L of pure water, crystallized and filtered, whereby a white solid was obtained. It was recrystallized and purified from 200mL of methanol, whereby 10.3g of photo radical polymerization initiator A-15 was obtained (yield of 51%).

¹ HNMR(400MHz)δ＝2.19(s，3H)，2.26(s，6H)，2.85(d，1H)，2.95(dd，4H)，3.10(d，1H)，3.6(m，4H)，7.00(d，2H)，7.06(d，2H)，7.38(d，1H)，7.54(d，1H)，7.78(s，1H)

< synthetic example 4: synthesis method of photo radical polymerization initiator A-22

A photo radical polymerization initiator A-22 was synthesized in the same manner as in Synthesis example 3 except that 6-chloro-thiokout- -4-ketone was changed to 2, 3-dihydro-1H-benzo [ f ] thiokout- -1-ketone.

¹ HNMR(400MHz)δ＝2.21(s，3H)，2.29(s，6H)，2.85(d，1H)，2.95(dd，4H)，3.10(d，1H)，3.6(m，4H)，7.05(d，2H)，7.11(d，2H)，7.2-7.8(m，5H)，8.75(d，1H)

< synthetic example 5: synthesis method of photo radical polymerization initiator A-32

A photo radical polymerization initiator A-32 was synthesized in the same manner as in Synthesis example 2 except that 6-chloro-3-methylsulfanyl- -one was changed to 5- ((4-benzoylphenyl) thio) -2, 3-dihydro-1H-inden-1-one.

¹ HNMR(400MHz)δ＝1.59(s，3H)，2.7(m，5H)，2.87(d，1H)，3.6(m，4H)，7.1-7.9(m，12H)

< synthetic example 6: synthesis method of photo radical polymerization initiator A-46

A photo radical polymerization initiator A-46 was synthesized in the same manner as in Synthesis example 1 except that 2-methyl- α -tetralone was changed to N-ethyl-9- (2-methylbenzoyl) -1, 6-dihydro-cyclopenta [ c ] carbazole-3 (2H) -one and methyl iodide was changed to ethyl iodide.

¹ HNMR(400MHz)δ＝0.89(t，3H)，1.37(t，3H)，1.52(q，2H)，2.26(s，6H)，2.48(s，3H)，2.62(d，1H)，2.80(d，1H)，4.33(q，2H)，7.1-7.9(m，6H)，8.17(d，1H)，8.32(d，1H)，8.49(s，1H)

< synthetic example 7: synthesis method of photo radical polymerization initiator A-49

A photo radical polymerization initiator A-49 was synthesized in the same manner as in Synthesis example 2 except that 6-chloro-3-methylsulfanyl- -one was changed to N-ethyl-9- (2-methylbenzoyl) -1, 6-dihydro-cyclopenta [ c ] carbazole-3 (2H) -one.

¹ HNMR(400MHz)6＝1.37(t，3H)，1.59(s，3H)，2.48(s，3H)，2.62(d，1H)，2.7(m，4H)，2.80(d，1H)，3.6(m，4H)，4.33(q，2H)，7.1-7.9(m，6H)，8.18(d，1H)，8.34(d，1H)，8.51(s，1H)

< synthesis example 8: synthesis method of photo radical polymerization initiator A-64

A photo radical polymerization initiator A-64 was synthesized in the same manner as in Synthesis example 1 except that 2-methyl- α -tetralone was changed to N-ethyl-11- (2-methylbenzoyl) -3, 4-dihydro-2H-oxa [3,2-c ] carbazol-5 (8H) -one and methyl iodide was changed to ethyl iodide.

¹ HNMR(400MHz)δ＝0.87(t，3H)，1.37(t，3H)，1.51(q，2H)，2.28(s，6H)，2.48(s，3H)，3.7-4.1(m，4H)，4.38(q，2H)，7.1-7.9(m，6H)，8.15(d，1H)，8.33(d，1H)，8.47(s，1H)

< synthetic example 9: synthesis method of photo radical polymerization initiator A-68

A photo radical polymerization initiator A-68 was synthesized in the same manner as in Synthesis example 8 except that N-ethyl-11- (2-methylbenzoyl) -3, 4-dihydro-2H-oxazol [3,2-c ] carbazol-5 (8H) -one was changed to N-ethyl-11-nitro-3, 4-dihydro-2H-oxazol [3,2-c ] carbazol-5 (8H) -one.

¹ HNMR(400MHz)δ＝0.88(t，3H)，1.38(t，3H)，1.49(q，2H)，2.31(s，6H)，2.42(s，3H)，3.7-4.1(m，4H)，4.35(q，2H)，7.49(d，1H)，7.97(d，1H)，8.2(m，2H)，8.99(s，1H)

< synthetic example 10: synthesis method of photo radical polymerization initiator A-92

A photo radical polymerization initiator A-92 was synthesized in the same manner as in Synthesis example 8 except that N-ethyl-11- (2-methylbenzoyl) -3, 4-dihydro-2H-oxazepine [3,2-c ] carbazol-5 (8H) -one was changed to 7- (4- (2-methylbenzoyl) phenyl) -3, 4-dihydrobenzo [ b ] oxazepin-5 (2H) -one.

¹ HNMR(400MHz)δ＝0.88(t，3H)，1.49(q，2H)，2.31(s，6H)，2.42(s，3H)，3.7-4.1(m，4H)，7.1-7.8(m，9H)，8.32(d，1H)，8.54(s，1H)

< synthesis example 11: synthesis method of photo radical polymerization initiator A-103

A photo radical polymerization initiator A-103 was synthesized in the same manner as in Synthesis example 2 except that 6-chloro-3-methylsulfanyl- -one was changed to 7-bromo-9, 9-dipropyl-3, 9-dihydropyran [ b ] fluoren-1 (2H) -one.

¹ HNMR(400MHz)δ＝0.89(t，6H)，1.35(m，4H)，1.63(s，3H)，1.83(t，4H)，2.7(m，4H)，2.85(d，1H)，3.10(d，1H)，3.6(m，4H)，7.5-7.8(m，3H)，7.79(s，1H)，8.18(s，1H)

< synthetic example 12: synthesis method of photo radical polymerization initiator A-109-

A photo radical polymerization initiator A-109 was synthesized in the same manner as in Synthesis example 6 except that N-ethyl-9- (2-methylbenzoyl) -1, 6-dihydro-cyclopenta [ c ] carbazole-3 (2H) -one was changed to 9, 9-dimethyl-7-nitro-3, 9-dihydro-cyclopenta [ b ] fluorene-1 (2H) -one.

¹ HNMR(400MHz)δ＝0.89(t，3H)，1.52(q，2H)，1.69(s，6H)，2.26(s，6H)，2.62(d，1H)，2.80(d，1H)，7.84(s，1H)，8.2-8.4(m，3H)，8.48(s，1H)

< synthesis examples 12 to 112: synthesis method of the photo radical polymerization initiator other than the above

Photo radical polymerization initiators A-2 to A-5, A-7 to A-14, A-16 to A-21, A-23 to A-31, A-33 to A-45, A-47, A-48, A-50 to A-63, A-65 to A-67, A-69 to A-91, A-93 to A-102, A-104 to A-108 and A-110 to A-112 were obtained in a similar manner to Synthesis example 1 except that the raw materials and the like were changed.

< preparation of Dispersion liquid >

The mixed solution obtained by mixing the raw materials shown in Table 1 was mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.1mm in diameter). Next, a high-pressure dispenser NANO-3000-10 (manufactured by Nippon BEE Co., ltd.) with a pressure reducing mechanism was used at a pressure of 2,000kg/cm ² And a dispersion treatment was carried out at a flow rate of 500 g/min. The dispersion treatment was repeated 10 times in total to obtain a dispersion. The numerical values showing the blending amounts described in table 1 below are parts by mass. The amount of the dispersant blended is a value calculated by solid content conversion.

Details of materials expressed by abbreviations in table 1 indicating the formulation of the above dispersion are as follows.

< colorant >

PR264: C.I. pigment Red 264[ diketopyrrolopyrrole Compound, red pigment (R pigment) ]

PR254: C.I. pigment Red 254[ diketopyrrolopyrrole Compound, red pigment (R pigment) ]

PR291: C.I. pigment Red 291[ brominated diketopyrrolopyrrole Compound, red pigment (R pigment) ]

PO71: C.I. pigment orange 71[ diketopyrrolopyrrole Compound, orange pigment (0 pigment) ]

PG36: C.I. pigment Green 36[ copper phthalocyanine complex, green pigment (G pigment) ]

PG58: C.I. pigment Green 58[ Zinc phthalocyanine Complex, green pigment (G pigment) ]

PY129: C.I. pigment yellow 129[ copper azomethine complex, yellow pigment (Y pigment) ]

PY185: C.I. pigment yellow 185[ isoindoline Compound, yellow pigment (Y pigment) ]

PY215: C.I. pigment yellow 215[ pteridine compounds, yellow pigment (Y pigment) ]

PB16: C.I. pigment blue 16[ no metal phthalocyanine compound, blue pigment (B pigment) ]

PB15:6: C.I. pigment blue 15:6[ copper phthalocyanine complex, blue pigment (B pigment) ]

IR pigment: compounds of the following structure (near infrared ray absorbing pigment, wherein Me represents methyl group, ph represents phenyl group.)

[ chemical formula 41]

TiBk: titanium black [ black pigment (Bk pigment) ]

Oxynitriding Zr: zirconium oxynitride (black pigment (Bk pigment))

< pigment derivative >

PD-1: the following compounds

PD-2: the following compounds

[ chemical formula 42]

< dispersant >

P-1: 30 mass% Propylene Glycol Monomethyl Ether Acrylate (PGMEA) solution of the resin of the following structure. The numbers noted in the main chain are molar ratios, and the numbers noted in the side chains are the numbers of repeating units. Mw:20,000.

[ chemical formula 43]

P-2: 30 mass% PGMEA solution of the resin of the following structure. The numbers noted in the main chain are molar ratios, and the numbers noted in the side chains are the numbers of repeating units. Mw:28,000. Where r=15, s=63, t=5, u=17, n=9.

[ chemical formula 44]

P-3: 30 mass% PGMEA solution of the resin of the following structure. The numbers noted in the main chain are molar ratios, and the numbers noted in the side chains are the numbers of repeating units. Mw:21,000.

[ chemical formula 45]

P-4: 30 mass% PGMEA solution of the resin of the following structure. The number noted in the side chain is the number of repeating units. Mw:9,000.

[ chemical formula 46]

P-5: 30 mass% PGMEA solution of the resin of the following structure. The number noted in the side chain is the number of repeating units. Mw:10,000.

[ chemical formula 47]

< solvent >

S-1: propylene Glycol Monomethyl Ether Acetate (PGMEA)

S-2: propylene Glycol Monomethyl Ether (PGME)

S-3: cyclohexanone

< production of curable composition >

Curable compositions of examples and comparative examples were prepared by mixing 1 part by mass of a dispersion liquid shown in tables 2 to 5 below, 1 part by mass of a resin shown in tables 2 to 5 below, 1 part by mass of a surfactant 1 shown below, and 0.1 part by mass of a polymerization inhibitor (p-methoxyphenol) shown below, with a radical polymerization initiator shown in tables 2 to 5 below, 1 part by mass of a solvent shown in tables 2 to 5 below, and an epoxy compound (manufactured by EHPE-3150,Daicel Corporation).

Surfactant 1: 1% by mass PGMEA solution of KF-6001 (Shin-Etsu Chemical Co., ltd.).

TABLE 2

TABLE 3

TABLE 4

TABLE 5

The details of the materials shown by abbreviations in tables 2 to 5 indicating the formulations of the curable compositions other than the above are as follows.

< resin >

Ba-1: the resin of the following structure (the number noted in the main chain is a molar ratio, the weight average molecular weight is 11,000)

[ chemical formula 48]

a-2: the resin of the following structure (the number noted in the main chain is a molar ratio, the weight average molecular weight is 15,000)

[ chemical formula 49]

Ba-3: cardo resin V-259ME (manufactured by nippon steel & sumitomo metal corporation)

[ chemical formula 50]

< polymerizable Compound >

D-1: KAYARAD DPHA (6-functional acrylate compound, manufactured by Nippon Kayaku Co., ltd.)

D-2: NK ESTER A-DPH-12E (ethylene oxide (EO) -modified 6-functional acrylate compound, SHIN-NAKAMURA CHEMICAL Co., ltd.

D-3: NK ESTER A-TMMT (4-functional acrylate compound, SHIN-NAKAMURA CHEMICAL Co., ltd.)

D-4: ARONIX M-510 (3-4 functional acrylate compound, TOAGOSEI CO., LTD.)

D-5: LIGHT ACRYLATE DCP-A (2-functional alicyclic acrylate Compound, KYOEISHA CHEMICAL Co., LTD.)

< photopolymerization initiator >

a-1: IRGACURE OXEO1, BASF corporation, oxime ester photopolymerization initiator

a-2: IRGACURE OXE02, BASF corporation, oxime ester photopolymerization initiator

a-3: IRGACURE OXE03, BASF corporation, oxime ester photopolymerization initiator

CA-1: alpha-aminoalkylbenzophenone photopolymerization initiator, prepared by Omnirad907, IGM Resins B.V.)

CA-2: alpha-aminoalkylbenzophenone photopolymerization initiator, produced by Omnirad379, IGM Resins B.V.)

< evaluation >

Gassing inhibition

Each photosensitive composition was applied to a silicon wafer using a spin coater, and then heated (prebaked) at 100℃for 120 seconds using a heating plate, to obtain a coating film having a film thickness of 1.0. Mu.m.

Next, an i-ray stepper FPA-3000i is usedS+ (manufactured by Canon Inc.), 400mJ/cm with a 0.8 μm checkered pattern of mask interposed therebetween ² Is exposed to light. Next, in a vacuum cleaning oven, the outgassing was collected at 100℃for 1 hour, and the outgassing was calculated from peaks obtained from a gas chromatography mass spectrometer (GC/MS).

Evaluation criterion-

A: the gas release amount is less than 0.01ppm

B: the gas release amount is more than 0.01ppm and less than 0.05ppm

C: the gas release amount is more than 0.05ppm and less than 0.10ppm

D: the gas release amount is more than 0.10ppm and less than 1ppm

E: the gas release amount is more than 1ppm

Sensitivity (sensitivity)

Next, using an i-ray stepping exposure apparatus FPA-3000iS+ (manufactured by Canon Inc.), a 0.8 μm checkered pattern was formed on the mask at a rate of 10mJ/cm ² Is irradiated with 50-1000 mJ/cm ² Exposure process (exposure process). Then, spin-coating immersion development was performed at 23℃for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH), followed by rinsing with pure water by rotary spraying for 20 seconds and further rinsing with pure water. Then, the water droplets adhering to the surface of the pattern were removed by air blowing, and the pattern was naturally dried to obtain a pattern.

In the sensitivity evaluation, the minimum exposure amount (optimum exposure amount) when the film thickness after development in the region irradiated with light in the exposure step is 95% or more with respect to 100% of the film thickness before exposure was measured, and this was evaluated as sensitivity. The smaller the value of the minimum exposure amount (optimum exposure amount) is, the higher the sensitivity is.

Evaluation criterion-

A: less than 50mJ/cm ²

B：50mJ/cm ² Above and less than 100mJ/cm ²

C：100mJ/cm ² Above and less than 200mJ/cm ²

D：200mJ/cm ² Above and below 300mJ/cm ²

E：300mJ/cm ² Above mentioned

Adhesion (adhesive properties)

Next, using an i-ray stepping exposure apparatus FPA-3000iS+ (manufactured by Canon Inc.), the film was subjected to a mask pattern of 0.8 μm with a checkered pattern interposed therebetween, at 400mJ/cm ² Is exposed to light. Then, spin-coating immersion development was performed at 23℃for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH), followed by rinsing with pure water by rotary spraying for 20 seconds and further rinsing with pure water. Then, the water droplets adhering to the surface of the pattern were removed by air blowing, and the pattern was naturally dried to obtain a pattern.

The silicon wafer on which the pattern was formed was observed by SEM (Scanning Flectron Microscope: scanning electron microscope: magnification: 20,000 times), and the ratio of the frames of the pattern defects in 100 frames was observed from SEM photograph, whereby the adhesion was evaluated. The evaluation criteria were as follows.

Evaluation criterion-

A: the pattern defect rate was 0%

B: the ratio of pattern defects exceeds 0% and is less than 10%

C: the pattern defect rate is more than 10% and less than 20%

D: the pattern defect rate is more than 20% and less than 50%

E: the pattern defect rate is more than 50 percent

Undercut(s)

Patterns were formed in the same order as the above evaluation of adhesion. The cross-sectional shape of the obtained pattern was observed by SEM (Scanning Electron Microscope: scanning electron microscope: magnification: 20,000), 5 patterns were extracted from the SEM photograph, the average slope of the cross-section of the 5 patterns was obtained, and pattern cross-sectional shape 1 was evaluated according to the following criteria. The slope of the cross section of the pattern refers to the slope in the thickness direction of the pattern on the silicon wafer in the portion where the pattern is formed. Specifically, the angle of the portion consisting of the surface of the silicon wafer and the side in the thickness direction of the pattern was measured. The slope of the pattern exceeding 90 degrees with respect to the surface of the silicon wafer means that the surface side area of the pattern from the silicon wafer side toward the pattern becomes large, that is, an edge (edge) is generated at the bottom surface of the pattern, which is not preferable.

Evaluation criterion-

A: the angle exceeds 80 degrees and is less than 90 degrees

B: the angle exceeds 90 degrees and is less than 100 degrees

C: the angle exceeds 100 degrees and is less than 110 degrees

D: the angle exceeds 110 degrees and is less than 150 degrees

E: the angle exceeds 150 DEG

Solubility (solubility)

As an index of the storage stability of the radical polymerization initiator represented by formula 1 under low temperature conditions, the solubility was evaluated according to the following method.

100g of each curable composition obtained above was placed in a plastic container and sealed, and after 3 months of storage at 0℃the weight of the precipitate was confirmed after returning to room temperature (25 ℃). The cured composition after storage was filtered through filter paper (manufactured by ADVANTEC No.4a, advantec Toyo Kaisha, ltd.) and the weight of the precipitate remaining on the filter paper after filtration was weighed.

Evaluation criterion-

A: no precipitate was found at all (0 g of precipitate).

B: the precipitate exceeds 0g and is less than 0.1g.

C: the amount of the precipitate is 0.1g or more and less than 0.5g.

D: the amount of the precipitate is 0.5g or more and less than 1.0g.

E: the amount of precipitate is 1.0g or more.

The evaluation results are summarized in tables 6 to 9.

TABLE 6

TABLE 7

TABLE 8

TABLE 9

As shown in tables 6 to 9, the curable compositions of examples were curable compositions with less outgas from the obtained cured product, as compared with the curable compositions of comparative examples.

As shown in tables 6 to 9, the curable compositions of examples were also excellent in sensitivity, adhesion, undercut-suppressing property, and solubility.

The same effect can be obtained by the curable compositions of the examples even when KrF rays are irradiated instead of i rays. As the conditions for KrF radiation, for example, exposure light can be set: krF radiation (wavelength 248 nm), exposure: 10mJ/cm ² ～500mJ/cm ² Maximum instantaneous illuminance: 250,000,000W/m ² (average illuminance: 30,000W/m) ² ) Pulse width: 30 nanoseconds, frequency: 4kHz.

Claims

1. A curable composition comprising:

a radical polymerization initiator represented by the following formula 1; and

A radical-polymerizable compound having a radical-polymerizable group,

2. The curable composition according to claim 1, wherein,

the radical polymerization initiator represented by the above formula 1 is a radical polymerization initiator represented by the following formula 2,

ar in formula 2 ² Represents an aromatic or heteroaromatic ring, X ² representing-OR ²⁴ or-NR ²⁵ R ²⁶ ，Y ² Represents a single bond or a 2-valent linking group, R ²¹ ～R ²⁶ Each independently represents a hydrogen atom or a substituent, R ²⁵ And R is R ²⁶ Optionally linked to form a ring, n represents an integer of 1 to 3.

3. The curable composition according to claim 1 or 2, wherein,

The radical polymerization initiator represented by the formula 1 is a radical polymerization initiator represented by the following formula 3A or formula 3B,

in formula 3A or formula 3B, X ³ representing-OR ³⁴ or-NR ³⁵ R ³⁶ ，Y ³ Represents a single bond, -O-or-S-, R ³¹ Represents alkyl or aryl, R ³² ～R ³⁶ Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ³⁵ And R is R ³⁶ Optionally linked to form a ring, n represents an integer from 1 to 3, R ³⁹ Each independently represents a substituent, and m represents an integer of 0 to 2.

4. The curable composition according to any one of claim 1 to 3, wherein,

the radical polymerization initiator represented by the above formula 1 is a radical polymerization initiator represented by the following formula 4,

in formula 4, X ⁴ representing-OR ⁴⁴ or-NR ⁴⁵ R ⁴⁶ ，Y ⁴ Represents a single bond, -O-or-S-, R ⁴¹ Represents alkyl or aryl, R ⁴² ～R ⁴⁶ Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ⁴⁵ And R is R ⁴⁶ Optionally linked to form a ring, n represents an integer from 1 to 3, L ¹ L and L ² Respectively and independently represent a single bond, -CR ⁴⁷ R ⁴⁸ -, -O-, -S-or-NR ⁴⁹ -，R ⁴⁷ ～R ⁴⁹ Each independently represents a hydrogen atom, an alkyl group or an aryl group, p represents 0 or 1, q represents an integer of 0 to 2, Z ¹ Represents alkyl, aryl, halogen, nitro, cyano, carboxyl, sulfo or-C (=O) Z ² ，Z ² Represents aryl or heteroaryl.

5. The curable composition according to any one of claims 1 to 4, further comprising a colorant.

6. The curable composition according to any one of claims 1 to 5, further comprising an oxime compound.

7. The curable composition according to any one of claims 1 to 6, wherein,

from the table of the table 1The radical polymerization initiator has a molar absorption coefficient of 1000 L.mol with respect to light having a wavelength of 248nm in acetonitrile at 25 DEG C ^-1 ·cm ^-1 The above.

8. A method for producing a cured product, comprising the step of irradiating the curable composition according to any one of claims 1 to 7 with light having a wavelength of 150nm to 300 nm.

9. A film obtained by curing the curable composition according to any one of claims 1 to 7.

10. An optical element having the film of claim 9.

11. An image sensor having the film of claim 9.

12. A solid-state imaging element having the film according to claim 9.

13. An image display device having the film of claim 9.

14. A radical polymerization initiator represented by the following formula 1,

15. The radical polymerization initiator according to claim 14, wherein,

16. The radical polymerization initiator according to claim 14 or 15, wherein,

17. The radical polymerization initiator according to any one of claim 14 to 16, wherein,

in formula 4, X ⁴ representing-OR ⁴⁴ or-NR ⁴⁵ R ⁴⁶ ，Y ⁴ Represents a single bond, -0-or-S-, R ⁴¹ Represents alkyl or aryl, R ⁴² ～R ⁴⁶ Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ⁴⁵ And R is R ⁴⁶ Optionally linked to form a ring, n represents an integer of 1 to 3, L1 and L2 each independently represent a single bond, -CR ⁴⁷ R ⁴⁸ -, -0-, -S-or-NR ⁴⁹ -，R ⁴⁷ ～R ⁴⁹ Each independently represents a hydrogen atom, an alkyl group or an aryl group, p represents 0 or 1, q represents an integer of 0 to 2, Z ¹ Represents alkyl, aryl, halogen, nitro, cyano, carboxyl, sulfo or-C (=0) Z ² ，Z ² Represents aryl or heteroaryl.