TW201944172A - Photosensitive composition, cured film, method for manufacturing color filter, color filter, solid-state imaging element, and image display device - Google Patents

Abstract

The invention provides a photosensitive composition having excellent sensitivity, a cured film, a method for manufacturing a color filter, a color filter, a solid-state imaging element, and an image display device. The photosensitive composition includes a cyclic oxime compound and a polymerizable compound, each of which has a cyclic oxime site having a cyclic structure formed by containing an oxime group, and an electron attracting group having a σ * constant value of 3.5 or more.

Description

Photosensitive composition, cured film, method for manufacturing color filter, color filter, solid-state imaging element, and image display device

The present invention relates to a photosensitive composition. More specifically, it relates to a photosensitive composition containing a cyclic oxime compound and a polymerizable compound. The present invention also relates to a cured film obtained by using the photosensitive composition. The present invention also relates to a method for manufacturing a color filter using the photosensitive composition, a color filter, a solid-state imaging device, and an image display device.

Currently, a photosensitive composition containing a polymerizable compound and a photopolymerization initiator is used to form a cured film for a color filter and the like. As the photopolymerization initiator, for example, oxime compounds described in Japanese Patent Documents 1 to 3 are known.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] International Publication No. WO2008 / 078678
[Patent Document 2] Japanese Patent Laid-Open No. 2010-032985
[Patent Document 3] International Publication WO2002 / 100903

One of the characteristics required for a photosensitive composition includes high sensitivity during exposure. In recent years, it has been desired to further increase the sensitivity of the photosensitive composition.

Therefore, an object of the present invention is to provide a photosensitive composition, a cured film, a method for manufacturing a color filter, a color filter, a solid-state imaging device, and an image display device having excellent sensitivity.

According to the study by the present inventors, it was found that the above-mentioned object can be achieved by using a prescribed cyclic oxime compound as a photopolymerization initiator described later, and the present invention has been completed. The present invention provides the following.
<1> A photosensitive composition comprising a cyclic oxime compound and a polymerizable compound, each of which has a cyclic oxime moiety having a cyclic structure formed by containing an oxime group, and a σ ^* constant value of Taft of 3.5 The above electron attracting group.
<2> The photosensitive composition according to <1>, wherein the cyclic oxime compound has an electron attracting group having a σ ^* constant value of 4 or more of Taft.
<3> The photosensitive composition according to <1> or <2>, wherein the electron attracting group is at least one selected from a nitro group, an alkylsulfonyl group, an arylsulfonyl group, and an onium group.
<4> The photosensitive composition according to any one of <1> to <3>, wherein the cyclic oxime site of the cyclic oxime compound is represented by the following formula (a-1);
[Chemical Formula 1]

In the formula, R ¹ represents a substituent, A represents a ring formed by containing an oxime group, and n represents 0 or 1.
<5> The photosensitive composition according to any one of <1> to <4>, wherein the cyclic oxime compound has at least one selected from an aromatic hydrocarbon ring and a heterocyclic ring bonded to a cyclic oxime site. Ring structure.
<6> The photosensitive composition according to any one of <1> to <5>, wherein the cyclic oxime compound has a fused ring including a carbazole ring or a dibenzothiophene ring bonded to a cyclic oxime site The structure.
<7> The photosensitive composition according to any one of <1> to <6>, wherein the cyclic oxime compound is a compound represented by the following formula (1);
[Chemical Formula 2]

In formula (1), X ¹ represents -O-, -CR ^x1 R ^X2- , -S-, -NR ^x3 -or> C = NOR ^x4 , and R ^x1 to R ^x4 each independently represent a hydrogen atom or a substituent, R ^x1 and R ^x3 may be bonded to R ² , R ³ or a ring represented by B to form a ring. R ¹ to R ³ each independently represent a substituent, and L represents an alkylene group having 1 to 3 carbon atoms or -CR. ^L1 = CR ^L2- , R ^L1 and R ^L2 each independently represent a hydrogen atom or a substituent, B represents a ring containing at least one selected from an aromatic hydrocarbon ring and a heterocyclic ring, and Z ¹ represents a σ ^* constant value of Taft 3.5 or more electron attracting groups, n represents 0 or 1, m represents 0 or 1, q represents an integer of 1 or more, o and p each independently represent an integer of 0 or more, and when p is 2 or more, p R ² may be the same It can also be different. Two R ² can be bonded to each other to form a ring. When o is 2 or more, o R ³ can be the same or different. Two R ³ can be bonded to each other to form a ring. Q is 2 or more. In this case, q Z ¹ may be the same or different.
<8> The photosensitive composition according to any one of <1> to <6>, wherein the cyclic oxime compound is a compound represented by the following formula (2);
[Chemical Formula 3]

In formula (2), X ¹ represents -O-, -CR ^x1 R ^X2- , -S-, -NR ^x3 -or> C = NOR ^x4 , and R ^x1 to R ^x4 each independently represent a hydrogen atom or a substituent, R ^x1 and R ^x3 may be bonded to R ² or R ^3a to form a ring, L represents an alkylene group having 1 to 3 carbon atoms or -CR ^L1 = CR ^L2- , and R ^L1 and R ^L2 each independently represent a hydrogen atom or Substituents, R ¹ , R ² , R ^3a and R ^3b each independently represent a substituent, Z ^1a and Z ^1b each independently represent an electron attracting group whose Taft σ ^* constant value is 3.5 or more, and Y ¹ represents -CR ^Y1 R ^Y2- , -NR ^Y3 -or -S-, R ^Y1 to R ^Y3 each independently represent a hydrogen atom or a substituent, n represents 0 or 1, m represents 0 or 1, o1, o2, p, q1 and q2 respectively Independently represents an integer of 0 or more, at least one of q1 and q2 represents an integer of 1 or more, when p is 2 or more, p R ² may be the same or different, and two R ² may be bonded to each other to form a ring When o1 is 2 or more, o1 R ^3a may be the same or different, and two R ^3a may be bonded to each other to form a ring. When o2 is 2 or more, o2 R ^3b may be the same or different, and two R ^3b may be bonded to each other to form a ring. When q1 is 2 or more, q1 Z ^1a may be formed. It may be the same or different. When q2 is 2 or more, q2 Z ^1b may be the same or different.
<9> The photosensitive composition according to any one of <1> to <6>, wherein the cyclic oxime compound is a compound represented by the following formula (3a) or (3b);
[Chemical Formula 4]

In formula (3a), X ¹ represents -O-, -CR ^x1 R ^X2- , -S-, -NR ^x3 -or> C = NOR ^x4 , and R ^x1 to R ^x4 each independently represent a hydrogen atom or a substituent, R ^x1 and R ^x3 may be bonded to R ² or R ^3c to form a ring, Y ² represents -CR ^Y21 R ^Y22- , -NR ^Y23- , or -S-, and R ^Y21 to R ^Y23 each independently represent a hydrogen atom or a substitution base;
In formula (3b), X ² represents> CR ^X10 -or> N-, and R ^x10 represents a hydrogen atom or a substituent;
In formula (3a) and formula (3b), R ¹ , R ² , R ^3c and R ^3d each independently represent a substituent, and L represents an alkylene group having 1 to 3 carbon atoms or -CR ^L1 = CR ^L2- , R ^L1 and R ^L2 each independently represent a hydrogen atom or a substituent, Z ^1c and Z ^1d each independently represent an electron attracting group having a σ ^* constant value of 3.5 or more, n represents 0 or 1, m represents 0 or 1, and o3 , O4, p, q3, and q4 each independently represent an integer of 0 or more, and at least one of q3 and q4 represents an integer of 1 or more. When p is 2 or more, p R ² may be the same or different, and 2 R ² may be bonded to each other to form a ring. When o 3 is 2 or more, o 3 R ^3c may be the same or different. 2 R 3 ^c may be bonded to each other to form a ring. When o 4 is 2 or more, o 4 R ^3d may be The same or different, two R ^3d may be bonded to each other to form a ring. When q3 is 2 or more, q3 Z ^1c may be the same or different. When q4 is 2 or more, q4 Z ^1d may be the same or different. different.
<10> The photosensitive composition according to any one of <1> to <9>, further comprising a resin.
<11> The photosensitive composition according to any one of <1> to <10>, further comprising a color material.
<12> The photosensitive composition according to <11>, wherein the color material contains a pigment.
<13> The photosensitive composition according to <11> or <12>, wherein the color material contains at least one selected from a color colorant, a white colorant, a black colorant, and a near-infrared absorbing pigment.
<14> The photosensitive composition according to any one of <1> to <13>, which is a composition for forming a pixel of a color filter.
<15> A cured film obtained using the photosensitive composition according to any one of <1> to <14>.
<16> A method for manufacturing a color filter, comprising: a process for forming a photosensitive composition layer by applying the photosensitive composition according to any one of <1> to <14> on a support; A process of exposing the composition layer into a pattern; and a process of developing the exposed photosensitive composition layer to form a pattern.
<17> A color filter having the cured film according to <15>.
<18> A solid-state imaging element having the cured film according to <15>.
<19> An image display device having the cured film according to <15>.
[Inventive effect]

According to the present invention, it is possible to provide a method for producing a photosensitive composition, a cured film, a color filter, a color filter, a solid-state imaging device, and an image display device having excellent sensitivity.

Hereinafter, the content of this invention is demonstrated in detail.
In this specification, "~" is used as the meaning which includes the numerical value before and after that as a lower limit value and an upper limit value.
In the description of the group (atomic group) in this specification, the unsubstituted and unsubstituted tags include a group (atomic group) having no substituent, and also include a group (atomic group) having a substituent. For example, "alkyl" means not only an alkyl group (unsubstituted alkyl group) without a substituent, but also an alkyl group (substituted alkyl group) with a substituent.
In this specification, "(meth) acrylate" means both or any of acrylate and methyl acrylate, "(meth) acrylic" means both or any of acrylic and methacrylic, and "(meth "Acryl" refers to both or both acryl and methacryl.
In this specification, Me in the structural formula represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl.
In this specification, weight average molecular weight and number average molecular weight are polystyrene conversion values measured by GPC (gel permeation chromatography) method.
In this specification, near-infrared light means light having a wavelength of 700 to 2500 nm.
In this specification, the total solid content refers to the total mass of a component from which the solvent is removed from the total component of the composition.
In this specification, the term "process" includes not only independent processes, but even if it cannot be clearly distinguished from other processes, as long as the intended role of the process is achieved, it is also included in this term.

<Photosensitive composition>
The photosensitive composition of the present invention is characterized by containing a cyclic oxime compound and a polymerizable compound, the oxime compound having a cyclic oxime site having a cyclic structure formed by including an oxime group, and a σ ^* constant value of 3.5 or more Electron attraction group.

The photosensitive composition of the present invention is excellent in sensitivity during exposure. The reason for obtaining such an effect is presumably based on the following.
The cyclic oxime compound contained in the photosensitive composition of the present invention has a cyclic oxime moiety having a cyclic structure formed by containing an oxime group. That is, the cyclic oxime compound has a structure in which an oxime group is incorporated into a ring structure. It is presumed that the structure surrounding the oxime group is hardened by incorporating the oxime group into the ring structure, thereby sharpening the absorption spectrum of the cyclic oxime compound and further increasing the absorbance. In addition, it is presumed that the cyclic oxime compound includes such a cyclic oxime site, thereby suppressing the deactivation path of the excited state of the oxime compound, and presumably improving the decomposition efficiency by light irradiation. In addition, it is presumed that the cyclic oxime compound has an electron attracting group having a Ta ^* sigma constant value of 3.5 or more in addition to the cyclic oxime site, thereby shifting the maximum absorption wavelength of the cyclic oxime compound to a longer wavelength side. In order to match the wavelength of the light irradiated from the light source during the exposure. Therefore, it is presumed that this cyclic oxime compound can efficiently generate radicals upon exposure.
In addition, it is presumed that the cyclic oxime compound has the above-mentioned predetermined electron attracting group, so that the cyclic oxime compound and the polymerizable compound and other components easily interact in the membrane, and it is presumed that the cyclic oxime compound exists in the polymerizable compound. In the vicinity of the components, free radicals can be generated in the vicinity of the components.
Therefore, it is presumed that by irradiating the photosensitive composition of the present invention with light and exposing it, the cyclic oxime compound is effectively decomposed and free radicals are generated, and further, it is effective in the vicinity of components such as the polymerizable compound. Radicals are generated, and as a result, it is estimated that excellent sensitivity can be obtained.

In addition, with the photosensitive composition of the present invention, the curability of the cured film obtained can be further improved, and for example, a cured film having excellent properties such as solvent resistance can also be obtained. In addition, since the photosensitive composition is excellent in sensitivity, it can also form a pattern having excellent adhesion, rectangularity, and linearity. In particular, it is possible to form a fine pattern with excellent adhesion.

In addition, the photosensitive composition of the present invention has excellent sensitivity and excellent storage stability. The reason why such an effect is obtained is presumed to be that the oxime structure becomes a hard structure, so that it is possible to suppress the degradation of the oxime compound with time, such as hydrolysis. In addition, when the sensitivity of the photosensitive composition is high, storage stability generally tends to decrease. However, the photosensitive composition of the present invention can use both the cyclic oxime compound specified above to achieve both sensitivity and sensitivity at a higher level than before. Storage stability.

In general, when a coloring material is contained in a photosensitive composition, the sensitivity tends to be lowered. However, by including the cyclic oxime compound of the present invention as defined above in the photosensitive composition, even when the photosensitive composition further contains Even in color materials, excellent sensitivity can be maintained. Among them, when a coloring material such as a coloring agent or a black coloring agent that has absorption in the visible area is used, the sensitivity tends to be easily reduced, but because it can maintain excellent sensitivity even when it contains such a coloring material, The photosensitive composition is particularly effective when such a color material is included. For example, the photosensitive composition of the present invention can be suitably used as a composition for forming a pixel of a color filter and a composition for forming a light-shielding film such as a black matrix.

When the light-transmitting property of the photosensitive composition is low, the sensitivity tends to be lowered for the same reasons as described above, and the photosensitive composition contains the cyclic oxime compound specified in the present invention. A low-sensitivity photosensitive composition can maintain excellent sensitivity.
As one embodiment of such a photosensitive composition having low light transmittance, for example, the following photosensitive composition can be cited. When the photosensitive composition is used to produce a film having a thickness of 2.0 μm after drying, the above-mentioned film has a wavelength relative to the wavelength. The optical density of 365 nm light has a spectral characteristic of 1.5 or more (preferably 1.8 or more, and more preferably 2.1 or more). The upper limit of the optical density is not particularly limited, and can be set to 5.0 or less. In addition, the optical density (OD) is a value that expresses the degree of light absorption in a logarithm, and is a value defined by the following formula.
OD (λ) = Log ₁₀ [T (λ) / I (λ)]
λ represents the wavelength, T (λ) represents the amount of transmitted light at the wavelength λ, and I (λ) represents the amount of incident light at the wavelength λ.

Moreover, as another embodiment of the photosensitive composition with low light transmittance, the photosensitive composition is mentioned. When using the photosensitive composition to manufacture a film having a thickness of 4.0 μm after drying, the wavelength of the film is 360. The maximum value of the transmittance in the range of -700 nm is less than 40% (preferably less than 30%, more preferably less than 20%, even more preferably less than 10%).

The photosensitive composition of the present invention can be used for a color filter, a near-infrared transmission filter, a near-infrared cut filter, a black matrix, a light-shielding film, a refractive index adjustment film, a photosensitive layer of a lithographic printing plate precursor, a protective film, and ultraviolet curing. Ink, various photoresist, various display materials, coating materials, dental materials, varnishes, powder coatings, adhesives, dental compositions, gel coatings, electronic parts, magnetic recording materials, micromechanical parts, waveguides , Optical switches, masks for electroplating, color calibration systems, glass fiber cable coatings, screen printing stencils, three-dimensional objects based on three-dimensional printing, image recording materials for full-term recording, microelectronic circuits, health care materials, etc.

Examples of the color filter include a filter having colored pixels that transmit light of a specific wavelength, and a filter having at least one colored pixel selected from red pixels, blue pixels, green pixels, yellow pixels, cyan pixels, and magenta pixels. Device is better. The color filter can be formed using a photosensitive composition containing a colorant.

Examples of the near-infrared cut filter include a filter having a maximum absorption wavelength in a wavelength range of 700 to 1800 nm. The near-infrared cut-off filter is preferably a filter having a maximum absorption wavelength in a wavelength range of 700 to 1300 nm, and a filter having a maximum absorption wavelength in a wavelength range of 700 to 1000 nm is more preferable. The near-infrared cut filter has a transmittance of 70% or more in all ranges of wavelengths from 400 to 650 nm, more preferably 80% or more, and more preferably 90% or more. The transmittance of at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less.
In addition, the ratio of the absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter to the absorbance A550 at a wavelength of 550 nm, that is, the absorbance Amax / absorbance A550 is preferably 20 to 500, more preferably 50 to 500, and 70 to 450. More preferably, 100 to 400 is particularly preferred. The near-infrared cut filter can be formed using a photosensitive composition containing a near-infrared absorbing pigment.

The near-infrared transmitting filter is a filter that transmits at least a portion of near-infrared rays. The near-infrared transmission filter may be a filter (transparent film) that transmits both visible light and near-infrared light, or may be a filter that shields at least a portion of visible light and transmits at least a portion of near-infrared light. As the near-infrared transmission filter, those having a maximum transmittance that satisfies a range of wavelengths of 400 to 640 nm are 20% or less (preferably 15% or less, and more preferably 10% or less) and 1100 to 1300 nm The minimum value of the transmittance in the range is 70% or more (preferably 75% or more, more preferably 80% or more) of a spectral characteristic filter, and the like. The near-infrared transmission filter is preferably a filter that satisfies the spectral characteristics of any one of the following (1) to (4).
(1): The maximum transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, and more preferably 10% or less) and the minimum transmittance in the wavelength range of 800 to 1300 nm is 70. % Or more (preferably 75% or more, more preferably 80% or more).
(2): The maximum transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, and more preferably 10% or less) and the minimum transmittance in the wavelength range of 900 to 1300 nm is 70. % Or more (preferably 75% or more, more preferably 80% or more).
(3): The maximum transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the minimum transmittance in the wavelength range of 1000 to 1300 nm is 70. % Or more (preferably 75% or more, more preferably 80% or more).
(4): The maximum value of the transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the minimum transmittance in the wavelength range of 1100 to 1300 nm is 70. % Or more (preferably 75% or more, more preferably 80% or more).

When the photosensitive composition of the present invention is used as a composition for a near-infrared filter, the photosensitive composition of the present invention satisfies the minimum value Amin of the absorbance in the wavelength range of 400 to 640 nm and the maximum value of the absorbance in the wavelength range of 1100 to 1300 nm. A ratio of the values Bmax, that is, a spectral characteristic in which Amin / Bmax is 5 or more is preferable. Amin / Bmax is more preferably 7.5 or more, more preferably 15 or more, and particularly preferably 30 or more.

The absorbance Aλ at a certain wavelength λ is defined by the following formula (1).
Aλ = -log （Tλ / 100） …… (1)
Aλ is the absorbance at the wavelength λ, and Tλ is the transmittance (%) at the wavelength λ.
In the present invention, the value of the absorbance may be a value measured in the state of a solution or a value in a film obtained by forming a film using a photosensitive composition. When the absorbance is measured in the state of a film, a photosensitive composition is coated on a glass substrate by a method such as spin coating so that the thickness of the dried film becomes a predetermined thickness, and dried at 100 ° C. using a hot plate 120 It is better to measure the film prepared after seconds.

When the photosensitive composition of the present invention is used as a composition for a near-infrared filter, the photosensitive composition of the present invention preferably satisfies any one of the following spectral characteristics (11) to (14).
(11): The ratio of the minimum value Amin1 of the absorbance in the range of 400 to 640 nm to the maximum value Bmax1 of the absorbance in the range of 800 to 1300 nm, that is, Amin1 / Bmax1 is 5 or more, 7.5 or more is preferable, and 15 or more is more Good, 30 or more is further preferred. According to this aspect, a film capable of transmitting light having a wavelength of 720 nm or more can be formed by blocking light in a wavelength range of 400 to 640 nm.
(12): The ratio of the minimum value Amin2 of the absorbance in the range of 400 to 750nm to the maximum value Bmax2 of the absorbance in the range of 900 to 1300nm, that is, Amin2 / Bmax2 is 5 or more, preferably 7.5 or more, and 15 or more is more Good, 30 or more is further preferred. According to this aspect, a film capable of transmitting light having a wavelength of 850 nm or more can be formed by blocking light in a wavelength range of 400 to 750 nm.
(13): The ratio of the minimum value Amin3 of the absorbance in the range of wavelength 400 to 850nm to the maximum value Bmax3 of the absorbance in the range of wavelength 1000-1300nm, that is, Amin3 / Bmax3 is 5 or more, 7.5 or more is preferable, and 15 or more is more Good, 30 or more is further preferred. According to this aspect, a film capable of transmitting light having a wavelength of 940 nm or more can be formed by blocking light in a wavelength range of 400 to 850 nm.
(14): The ratio of the minimum value Amin4 of the absorbance in the range of wavelength 400 to 950nm to the maximum value Bmax4 of the absorbance in the wavelength 1100 to 1300nm, that is, Amin4 / Bmax4 is 5 or more, preferably 7.5 or more, and 15 or more Good, 30 or more is further preferred. According to this aspect, a film capable of transmitting light having a wavelength of 1040 nm or more can be formed by blocking light in a wavelength range of 400 to 950 nm.

Since the photosensitive composition of the present invention is excellent in sensitivity and can form a fine pattern, it can be suitably used as a photosensitive composition for a color filter. Specifically, it can be preferably used as a photosensitive composition for forming a pixel of a color filter, and more preferably as a photosensitive composition for forming a pixel of a color filter used in a solid-state imaging element.

Hereinafter, each component used in the photosensitive composition of this invention is demonstrated.

<< Cyclic oxime compound A >>
The photosensitive composition of the present invention contains a cyclic oxime compound (hereinafter, this cyclic oxime compound is also referred to as a cyclic oxime compound A), and each of the cyclic oxime compounds has a cyclic structure having a cyclic structure including an oxime group. The σ ^* constant value of the oxime site and Taft is an electron attracting group of 3.5 or more. That is, the cyclic oxime compound A is a compound having a cyclic oxime moiety and the above-mentioned electron attracting group in the same molecule, respectively.

First, an electron-attracting group (hereinafter, also referred to as an electron-attracting group A) having a Taft σ ^* constant value of 3.5 or more of the cyclic oxime compound A will be described.

Considering that the cyclic oxime compound A is more accessible to the polymerizable compound by interacting with the polymerizable compound and the like contained in the photosensitive composition, σ ^* of Taft of the electron attracting group A included in the cyclic oxime compound A The constant value is preferably 4 or more, and more preferably 4.2 or more. From the viewpoint of the stability of the compound, the upper limit is preferably 10 or less. The σ ^* constant of Taft is a parameter indicating the polarity of the substituent. In this specification, Taft's σ ^* constant value is described in "DD Perrin, B. Dempset, EP Serjeant," pka Prediction for organic Acids And Bases ", Table A.1 of Springer (1981) P109-126". The value of σ ^* . When not listed in Table A.1 of the above-mentioned literature, the Journal of the American Chemical Society (Taft, R.W, 1952, 74, 2729), the Journal of the American Chemical Society (Taft, R.W, 1952, 74, 3120) or the method described in the Journal of the American Chemical Society (Taft, R.W, 1953, 75, 4538).

As the above-mentioned electron attracting group A, nitro, alkylsulfonyl, arylsulfonyl, and onium are considered because the polymerizable compound and the like contained in the photosensitive composition interact more easily with the cyclic oxime compound A. A nitro group is preferred, a nitro group, an alkylsulfonyl group, and an arylsulfonyl group are more preferred, and a nitro group is particularly preferred.

The alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. Specific examples include methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, hexylsulfonyl, cyclohexylsulfonyl, and octyl Sulfonyl, 2-ethylhexylsulfonyl, decylsulfonyl, dodecylsulfonyl, octadecylsulfonyl, cyanomethylsulfonyl, methoxymethylsulfonyl Fluorenyl, perfluoroalkylsulfonyl and the like.

As the arylsulfonyl group, an arylsulfonyl group having 6 to 30 carbon atoms is preferred. Specific examples include benzenesulfonyl, 1-naphthylsulfonyl, 2-naphthylsulfonyl, 2-chlorobenzenesulfonyl, 2-methylbenzenesulfonyl, and 2-methoxybenzene Sulfonyl, 2-butoxybenzenesulfonyl, 3-chlorobenzenesulfonyl, 3-trifluoromethylbenzenesulfonyl, 3-cyanobenzenesulfonyl, 3-nitrobenzenesulfonyl , 4-fluorobenzenesulfonyl, 4-cyanobenzenesulfonyl, 4-methoxybenzenesulfonyl, 4-methylsulfanylbenzenesulfonyl, 4-phenylsulfanylbenzenesulfonyl Group, 4-dimethylaminobenzenesulfonyl and the like.

Examples of the onium group include an ammonium group, a fluorenyl group, and a fluorenyl group. An ammonium group is preferred. Examples of the ammonium group include a group represented by -N ⁺ (Ro ¹ ) (Ro ² ) (Ro ³ ). Ro ¹ to Ro ³ each independently represent a hydrogen atom, an alkyl group, and an aryl group, an alkyl group and an aryl group are preferred, and an alkyl group is more preferred. The carbon number of the alkyl group is preferably from 1 to 20, more preferably from 1 to 10, and even more preferably from 1 to 5. The alkyl group may be any of a straight chain, a branched chain, and a cyclic ring. A straight or branched chain alkyl group is preferred, and a straight chain alkyl group is further preferred.

When the electron attracting group is an onium group, it is preferable that the cyclic oxime compound has a counter anion. As the counter anion include a halogen ion ^{(Cl -, Br -, I} -), a sulfonate anion, a carboxylate anion, sulfonic acyl acyl imide _{^{anion, PF 6 -, BF 4 -}} , ClO 4 -, tris (haloalkyl sulfo acyl group) methide anion _{(e.g., (CF 3 SO 2) 3} C -), bis (sulfo-haloalkyl acyl) acyl imide anion (e.g. _{(CF 3 SO 2) 2 N} -), tetraarylphosphonium Borate anion, tetracyanoborate anion, etc.

The cyclic oxime compound A may have only one of the above-mentioned electron attracting groups A, or may have two or more (preferably 2 to 5 and more preferably 2 to 3). When there is only one of the above-mentioned electron attracting groups A, it is easy to further improve the solvent solubility. When there are two or more of the above-mentioned electron attraction groups A, it is easy to further improve the radical generation efficiency. When there are two or more of the electron-attracting groups A, the plurality of electron-attracting groups A may be the same or different. From the viewpoint of simplicity of synthesis, it is preferable that the plurality of electron attracting groups A are the same.

Next, the cyclic oxime site which the cyclic oxime compound A has is demonstrated.
The cyclic oxime compound A includes a cyclic oxime moiety having a cyclic structure formed by containing an oxime group. More specifically, the cyclic oxime compound A includes a cyclic oxime site containing a cyclic structure formed by directly bonding to a carbon atom of a nitrogen atom of an oxime group. That is, the cyclic oxime compound A has a structure in which an oxime group is incorporated into a ring structure.

The cyclic oxime moiety is preferably a cyclic structure with a 5 to 8 member ring, and a cyclic structure with a 5 to 7 member ring is more preferred. Considering the stability of the compound, the cyclic structure of the 5 or 6 member ring is Further preferred. The cyclic oxime moiety may include a hetero atom as an atom constituting a ring. Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom.

The cyclic oxime moiety has a carbonyl group directly bonded to a carbon atom of the oxime group, and the oxime group and the carbonyl group may be incorporated into a ring structure. Examples of such a ring structure include a structure in which n is 1 in formula (a-1) described later. With this aspect, it is easy to obtain more excellent photobleaching properties. When the cyclic oxime moiety does not include the carbonyl group (that is, when n is 0 in the formula (a-1) described later), higher sensitivity can be expected.

The cyclic oxime site may contain two or more oxime groups. When the cyclic oxime moiety contains two or more oxime groups, it is easy to further improve the radical generation efficiency. When the cyclic oxime site contains only one oxime group, it is easy to further improve the solubility of the solvent.

The cyclic oxime site is preferably a structure represented by the following formula (a-1).
[Chemical Formula 5]

In the formula (a-1), A represents a ring formed by containing an oxime group. The ring system represented by A is more preferably a 5 to 8-membered ring, and a 5 to 7-membered ring is more preferable. From the viewpoint of stability of the compound, a 5 or 6-membered ring is more preferable. The ring represented by A may include a hetero atom as an atom constituting the ring. Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom. The ring represented by A may contain two or more oxime groups.

In formula (a-1), n represents 0 or 1. From the viewpoint of high sensitivity, n is preferably 0. From the viewpoint of photobleachability, n-based 1 is preferred.

In the formula (a-1), R ¹ represents a substituent. Examples of the substituent represented by R ¹ include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkylsulfinylfluorenyl group, an arylsulfinylfluorenyl group, an alkylsulfonyl group, an arylsulfonyl group, and fluorene. Group, alkoxycarbonyl, aryloxycarbonyl, phosphino, heterocyclic, alkylthiocarbonyl, arylthiocarbonyl, dialkylaminocarbonyl, dialkylaminothiocarbonyl, and the like. These groups may also have a substituent. Examples of the further substituent include a halogen group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a fluorenyloxy group, a fluorenyl group, an alkylsulfinylfluorene group, and an arylsulfinylfluorene group. Group, alkylamino group, dialkylamino group, arylamino group, hydroxyl group, carboxyl group, formamyl group, mercapto group, sulfo group, amine group, cyano group, and the like.

The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and examples thereof include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, and octadecyl Alkyl, isopropyl, isobutyl, second butyl, third butyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, trifluoromethyl, 2-ethylhexyl, benzamidine (Phenacyl), 1-naphthylmethyl, 2-naphthylmethyl, 4-methylmercaptobenzyl methyl, 4-phenylmercaptobenzyl methyl, 4-dimethyl Aminobenzylmethyl, 4-cyanobenzylmethyl, 4-methylbenzylmethyl, 2-methylbenzylmethyl, 3-fluorobenzylmethyl, 3-tribenzylmethyl Fluoromethylbenzylmethyl and 3-nitrobenzylmethyl.

As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferable, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, and a 9-phenanthryl group. , 1-fluorenyl, 5-fused tetraphenyl, 1-indenyl, 2-fluorenyl, 9-fluorenyl, terphenyl, quarterphenyl, o-toluene Methyl, m-tolyl and p-tolyl, xylyl, o-cumenyl, m-cumenyl and p-cumenyl, 2,4,6-trimethylenyl (mesityl), and cyclopentadienyl (pentalenyl ), Binaphthalenyl, teraphthyl, tetranaphthyl, heptalenyl, biphenylenyl, dicyclopentadienyl, indacenyl, propyl [ Two] fluoranthenyl, acenaphthylenyl, aceanthrylenyl, phenalenyl, fluorenyl, anthracenyl, bianthryl, triple anthryl, tetrathryl , Anthraquinolyl, phenanthryl, triphenylenyl, fluorenyl, chrysenyl, fused tetraphenyl, pleiadenyl , Picenyl, perylenyl, pentaphenyl, pentacenyl, tetraphenylenyl, hexaphenyl, hexaphenyl, rubicenyl , Coronenyl, trinaphthylenyl, heptyl, fused heptyl, pyranthrenyl, ovalenyl, tolylmethyl.

The alkenyl group which may have a substituent is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, and a styryl group.

The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

As the alkylsulfinylsulfonyl group which may have a substituent, an alkylsulfinylsulfonyl group having 1 to 20 carbon atoms is preferred, and examples thereof include methylsulfinylsulfonyl, ethylsulfinylsulfinyl, and propylsulfinyl. Fluorenyl, isopropylsulfinyl sulfenyl, butylsulfinyl sulfinyl, hexylsulfinyl sulfinyl, cyclohexylsulfinyl sulfinyl, octylsulfinyl sulfinyl, 2-ethylhexylsulfinyl sulfinyl, decyl Sulfinyl sulfenyl, dodecylsulfinyl sulfinyl, octadecylsulfinyl sulfinyl, cyanomethylsulfinyl sulfinyl, methoxymethylsulfinyl sulfinyl and the like.

As the arylsulfinylsulfonyl group which may have a substituent, an arylsulfinylsulfonyl group having 6 to 30 carbon atoms is preferred, and examples thereof include phenylsulfinylsulfonyl group, 1-naphthylsulfinylsulfinyl group, and 2- Naphthylsulfinyl sulfenyl, 2-chlorophenylsulfinyl sulfinyl, 2-methylphenylsulfinyl sulfinyl, 2-methoxyphenylsulfinyl sulfinyl, 2-butoxyphenylsulfinyl sulfinyl Group, 3-chlorophenylsulfinylsulfenyl group, 3-trifluoromethylphenylsulfinylsulfenyl group, 3-cyanophenylsulfinylsulfenyl group, 3-nitrophenylsulfinylsulfenyl group, 4-fluoro Phenylsulfinyl, 4-cyanophenylsulfinyl, 4-methoxyphenylsulfinyl, 4-methylsulfanylphenylsulfinyl, 4-phenylsulfane Phenylphenylsulfinyl, 4-dimethylaminophenylsulfinyl and the like.

As the alkylsulfonyl group which may have a substituent, an alkylsulfonyl group having 1 to 20 carbon atoms is preferred, and examples thereof include methylsulfonyl, ethylsulfonyl, propylsulfonyl, and isopropyl Sulfosulfanyl, butylsulfonyl, hexylsulfonyl, cyclohexylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, decylsulfonyl, dodecylsulfonyl Octadecylsulfonyl, cyanomethylsulfonyl, methoxymethylsulfonyl, perfluoroalkylsulfonyl and the like.

As the arylsulfonyl group which may have a substituent, an arylsulfonyl group having 6 to 30 carbon atoms is preferred. Examples include benzenesulfonyl, 1-naphthylsulfonyl, and 2-naphthylsulfonyl. , 2-chlorobenzenesulfonyl, 2-methylbenzenesulfonyl, 2-methoxybenzenesulfonyl, 2-butoxybenzenesulfonyl, 3-chlorobenzenesulfonyl, 3-trifluoro Methylbenzenesulfonyl, 3-cyanobenzenesulfonyl, 3-nitrobenzenesulfonyl, 4-fluorobenzenesulfonyl, 4-cyanobenzenesulfonyl, 4-methoxybenzenesulfonyl Group, 4-methylsulfanylbenzenesulfonyl, 4-phenylsulfanylbenzenesulfonyl, 4-dimethylaminobenzenesulfonyl and the like.

The fluorenyl group which may have a substituent is preferably a fluorenyl group having 2 to 20 carbon atoms, and examples thereof include ethyl fluorenyl, propyl fluorenyl, butyl fluorenyl, trifluoromethylcarbonyl, pentamyl, benzyl, 1 -Naphthylmethyl, 2-naphthylmethyl, 4-methylsulfanyl benzyl, 4-phenylsulfanyl benzyl, 4-dimethylamino benzyl, 4 -Diethylaminobenzyl, 2-chlorobenzyl, 2-methylbenzyl, 2-methoxybenzyl, 2-butoxybenzyl, 3- Chlorobenzyl, 3-trifluoromethylbenzyl, 3-cyanobenzyl, 3-nitrobenzyl, 4-fluorobenzyl, 4-cyanobenzyl , 4-methoxybenzyl, propionyl and the like.

The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, and hexyloxy group. Carbonyl, octyloxycarbonyl, decyloxycarbonyl, octadecyloxycarbonyl, trifluoromethyloxycarbonyl and the like.

Examples of the aryloxycarbonyl group which may have a substituent include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylsulfanylphenoxycarbonyl group, and a 4-phenylsulfanyl group. Phenoxycarbonyl, 4-dimethylaminophenoxycarbonyl, 4-diethylaminophenoxycarbonyl, 2-chlorophenoxycarbonyl, 2-methylphenoxycarbonyl, 2-methyl Oxyphenoxycarbonyl, 2-butoxyphenoxycarbonyl, 3-chlorophenoxycarbonyl, 3-trifluoromethylphenoxycarbonyl, 3-cyanophenoxycarbonyl, 3-nitrobenzene Oxycarbonyl, 4-fluorophenoxycarbonyl, 4-cyanophenoxycarbonyl, 4-methoxyphenoxycarbonyl and the like.

As the phosphino group which may have a substituent, a phosphino group having a total carbon number of 2 to 50 is preferred, and examples thereof include dimethylphosphino group, diethylphosphino group, dipropylphosphino group, and diphenyl group. Phosphinofluorenyl, dimethoxyphosphinofluorenyl, diethoxyphosphinofluorenyl, dibenzomethylphosphoninophosphonium, bis (2,4,6-trimethylphenyl) phosphinofluorenyl and the like.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic group containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Examples include thienyl, benzo [b] thienyl, benzo [2,3-b] thienyl, thianthrenyl group, furanyl, pyranyl, isobenzofuranyl, and benzophenone Chromenyl group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl group, Pyrimidinyl, pyridazinyl group, indolizinyl group, isoindolyl, 3H-indolyl, indolyl, 1H-indazolyl, purinyl, 4H-quinazinyl ( quinolizinyl group), isoquinolinyl, quinolinyl, phthalazinyl group, naphthyridinyl group, quinoxolinyl, quinazolinyl, cinnolinyl group, fluorinyl (Pteridinyl group), 4aH-carbazolyl, carbazolyl, β-carolinyl, morphinyl, acridyl, perimidinyl group, morpholinyl, morphazinyl, phenarsazinyl group), isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl group, Phenoxazinyl, isoyl, yl, pyrrolidinyl, pyrrolinyl, imidazolyl, imidazolinyl, pyrazolyl, pyrazolinyl, piperidinyl, piperazinyl group, indole Phenyl, isoindolyl, Ring group (quinuclidinyl group), phosphono group, thioxanthone group and so on.

Examples of the alkylthiocarbonyl group which may have a substituent include methylthiocarbonyl, propylthiocarbonyl, butylthiocarbonyl, hexylthiocarbonyl, octylthiocarbonyl, decylthiocarbonyl, octadecylthiocarbonyl, Trifluoromethylthiocarbonyl and the like.

Examples of the arylthiocarbonyl group which may have a substituent include 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, and 4-phenylsulfanylphenylthiocarbonyl group. , 4-dimethylaminophenylthiocarbonyl, 4-diethylaminophenylthiocarbonyl, 2-chlorophenylthiocarbonyl, 2-methylphenylthiocarbonyl, 2-methoxyphenylthio Carbonyl, 2-butoxyphenylthiocarbonyl, 3-chlorophenylthiocarbonyl, 3-trifluoromethylphenylthiocarbonyl, 3-cyanophenylthiocarbonyl, 3-nitrophenylthiocarbonyl, 4 -Fluorophenylthiocarbonyl, 4-cyanophenylthiocarbonyl, 4-methoxyphenylthiocarbonyl, and the like.

Examples of the dialkylaminocarbonyl group which may have a substituent include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a dipropylaminocarbonyl group, and a dibutylaminocarbonyl group.

Examples of the dialkylaminothiocarbonyl group which may have a substituent include a dimethylaminothiocarbonyl group, a dipropylaminothiocarbonyl group, a dibutylaminothiocarbonyl group, and the like.

From the viewpoint of high sensitivity, the fluorenyl group which may have a substituent in the R ¹ system of the formula (a-1) is more preferred, and the ethenyl, propionyl, benzyl, and tolyl groups are more preferred.

The cyclic oxime compound A preferably has a structure in which at least one ring selected from the group consisting of an aromatic hydrocarbon ring and a heterocyclic ring is bonded to the above-mentioned cyclic oxime site. More specifically, a fused ring containing a cyclic oxime moiety formed by condensing at least one ring selected from an aromatic hydrocarbon ring and a heterocyclic ring at the cyclic oxime site is preferable. By using a cyclic oxime compound A having such a structure, higher sensitivity can be achieved. The electron attracting group A is preferably bonded to the aromatic hydrocarbon ring or heterocyclic ring.

The aromatic hydrocarbon ring may be a monocyclic ring or a fused ring. Specific examples of the aromatic hydrocarbon ring include a benzene ring, a biphenylene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a fluorene ring, and the like.

The heterocyclic ring may be a single ring or a fused ring. A heterocyclic ring is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, or a sulfur atom, more preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom or an oxygen atom, and even more preferably a nitrogen ring. Atomic aromatic or aliphatic heterocyclic ring. Specific examples of the heterocyclic ring include a pyrrole ring, a furan ring, a thiophene ring, a pyridine ring, a pyrimyl ring, a pyrimidine ring, a da ring, a piperidine ring, a piperan ring, a chroman ring, an imidazole ring, a thiazole ring, and a pyrazole ring. Ring A hydroxyphenazine ring and a dibenzothiophene ring are preferred. A thiophene ring, a carbazole ring, a thiathracene ring, a dihydroxyphenazine ring, and a dibenzothiophene ring are more preferred. Further preferred.

From the reason that it is easier to achieve high sensitivity, it is preferable that the cyclic oxime compound A has a structure in which a fused ring including a carbazole ring or a dibenzothiophene ring is bonded to the above-mentioned cyclic oxime site.

The cyclic oxime compound A used in the present invention is preferably a compound represented by the following formula (1).
[Chemical Formula 6]

In formula (1), X ¹ represents -O-, -CR ^x1 R ^X2- , -S-, -NR ^x3 -or> C = NOR ^x4 , and R ^x1 to R ^x4 each independently represent a hydrogen atom or a substituent, R ^x1 and R ^x3 may be bonded to R ² , R ³ or a ring represented by B to form a ring. R ¹ to R ³ each independently represent a substituent, and L represents an alkylene group having 1 to 3 carbon atoms or -CR. ^L1 = CR ^L2- , R ^L1 and R ^L2 each independently represent a hydrogen atom or a substituent, B represents a ring containing at least one selected from an aromatic hydrocarbon ring and a heterocyclic ring, and Z ¹ represents Taft's σ ^* constant value 3.5 or more electron attracting groups, n represents 0 or 1, m represents 0 or 1, q represents an integer of 1 or more, o and p each independently represent an integer of 0 or more, and when p is 2 or more, p R ² may be the same It can also be different. Two R ² can be bonded to each other to form a ring. When o is 2 or more, o R ³ can be the same or different. Two R ³ can be bonded to each other to form a ring. Q is 2 or more. In this case, q Z ¹ may be the same or different.

The meaning of the electron-attracting group of Taft having a σ ^* constant value of 3.5 or more represented by Z ^{1 in} the formula (1) is the same as that of the electron-attracting group A described above, and the preferred range is also the same.

X ^{1 in} formula (1) represents -O-, -CR ^x1 R ^X2- , -S-, -NR ^x3 -or> C = NOR ^x4 , and R ^x1 to R ^x4 each independently represent a hydrogen atom or a substituent.
From the reason that it is easier to improve the photodecomposition efficiency, X ¹ -O-, -CR ^x1 R ^X2- , -S- are preferable.
Examples of the substituent represented by R ^x1 to R ^x3 include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, and a heterocyclic group. The meanings of the details of these groups are the same as those described for R ¹ in formula (a-1).
Examples of the substituent represented by R ^x4 include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkylsulfinylene group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and fluorene. Group, alkoxycarbonyl, aryloxycarbonyl, phosphino, heterocyclyl, alkylthiocarbonyl, arylthiocarbonyl, dialkylaminocarbonyl, dialkylaminothiocarbonyl, etc. From a viewpoint perspective, fluorene is preferred. The meanings of the details of these groups are the same as those described for R ¹ in formula (a-1).
R ^x1 and R ^x3 may be bonded to R ² , R ³ or a ring represented by B to form a ring. The formed ring may be an aliphatic ring or an aromatic ring.

R ¹ to R ^{3 in} formula (1) each independently represent a substituent. Represented by R ¹ in the same range as the ^one described in the substituent group R with the meanings of formula (a-1) a. Examples of the substituents represented by R ² and R ³ include a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a fluorenyl group, and a heterocyclic group. The meanings of the details of these groups are the same as those described for R ¹ in formula (a-1).

L in formula (1) represents an alkylene group having 1 to 3 carbon atoms or -CR ^L1 = CR ^L2- , and R ^L1 and R ^L2 each independently represent a hydrogen atom or a substituent. The alkylene group represented by L is preferably an alkylene group having 1 or 2 carbon atoms, and an alkylene group having 1 carbon atom is more preferred. The alkylene group represented by L may have a substituent.
Examples of the substituent that the alkylene group represented by L may have include a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a fluorenyl group, a heterocyclic group, and an alkylene group. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, and examples thereof include methine, ethylene, propylene, isopropylidene, and butylene. Examples of the alkyl group, the aryl group, the alkenyl group, the alkynyl group, the fluorenyl group, and the heterocyclic group include the groups described for R ¹ in the formula (a-1).
Examples of the substituents represented by R ^L1 and R ^L2 include a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a fluorenyl group, and a heterocyclic group. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group, the aryl group, the alkenyl group, the alkynyl group, the fluorenyl group, and the heterocyclic group include the groups described for R ¹ in the formula (a-1).

B in Formula (1) represents a ring containing at least one selected from an aromatic hydrocarbon ring and a heterocyclic ring. The aromatic hydrocarbon ring may be a monocyclic ring or a fused ring. Specific examples of the aromatic hydrocarbon ring include a benzene ring, a biphenylene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a fluorene ring, and the like. The heterocyclic group may be a single ring or a fused ring. A heterocyclic ring is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, or a sulfur atom, more preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom or an oxygen atom, and even more preferably a nitrogen ring. Atomic aromatic or aliphatic heterocyclic ring. Specific examples of the heterocyclic ring include a pyrrole ring, a furan ring, a thiophene ring, a pyridine ring, a pyrimyl ring, a pyrimidine ring, a da ring, a piperidine ring, a piperan ring, a chroman ring, an imidazole ring, a thiazole ring, and a pyrazole ring. , Phthaloline ring, carbazole ring, thiathracene ring, dihydroxyphenazine ring, dibenzothiophene ring and fused rings containing these rings, pyrrole ring, furan ring, thiophene ring, carbazole ring, thiathracene ring, two A hydroxyphenazine ring and a dibenzothiophene ring are preferred. A thiophene ring, a carbazole ring, a thiathracene ring, a dihydroxyphenazine ring, and a dibenzothiophene ring are more preferred. The carbazole ring and the dibenzothiophene ring are Further preferred.

N in the formula (1) represents 0 or 1. From the viewpoint of high sensitivity, n is preferably 0.
M in the formula (1) represents 0 or 1. Q in Formula (1) represents an integer of 1 or more, and 1 or 2 is preferable. In the formula (1), o and p each independently represent an integer of 0 or more, 0 to 2 is preferable, and 0 to 1 is more preferable. When p is 2 or more, p R ² may be the same or different, and two R ² may be bonded to each other to form a ring. When o is 2 or more, o R ³ may be the same or different, and two R ³ may be bonded to each other to form a ring. The ring formed by bonding these groups to each other may be an aliphatic ring or an aromatic ring.

The cyclic oxime compound A used in the present invention is preferably a compound represented by the following formula (2).
[Chemical Formula 7]

In formula (2), X ¹ represents -O-, -CR ^x1 R ^X2- , -S-, -NR ^x3 -or> C = NOR ^x4 , and R ^x1 to R ^x4 each independently represent a hydrogen atom or a substituent, R ^x1 and R ^x3 may be bonded to R ² or R ^3a to form a ring, L represents an alkylene group having 1 to 3 carbon atoms or -CR ^L1 = CR ^L2- , and R ^L1 and R ^L2 each independently represent a hydrogen atom or Substituents, R ¹ , R ² , R ^3a and R ^3b each independently represent a substituent, Z ^1a and Z ^1b each independently represent an electron attracting group having a σ ^* constant value of 3.5 or more, and Y ¹ represents -CRY ¹ RY ^2- , -NRY ³ -or -S-, RY ¹ to RY ³ each independently represent a hydrogen atom or a substituent, n represents 0 or 1, m represents 0 or 1, o1, o2, p, q1, and q2 respectively independently represents an integer of 0, q1 and q2 is at least one represents an integer of 1, p is 2 or more, P R ² s may be the same or different, two R ² may be bonded to each other to form a ring When o1 is 2 or more, o1 R ^3a may be the same or different, and two R ^3a may be bonded to each other to form a ring. When o2 is 2 or more, o2 R ^3b may be the same or different, and two R ^3b may be bonded to each other to form a ring. When q1 is 2 or more, q1 Z ^1a may be formed. It may be the same or different. When q2 is 2 or more, q2 Z ^1b may be the same or different.

X of formula (2) is ^{1, L, R 1, R} 2, m and n have the meaning as in formula (1), ^{X 1, L, R 1,} R 2, m and n are the same as the preferred ranges are also the same . The meanings of R ^3a and R ^3b in formula (2) are the same as those of R ³ in formula (1), and preferred ranges are also the same. The meanings of o1 and o2 in formula (2) are the same as those of o in formula (1), and the preferred ranges are also the same. In formula (2), when o1 is 2 or more, o1 R ^3a may be the same or different, and two R ^3a may be bonded to each other to form a ring. When o2 is 2 or more, o2 R ^3b may be the same or may be different. Differently, two R ^3b may be bonded to each other to form a ring. The ring formed by bonding these groups to each other may be an aliphatic ring or an aromatic ring.

The meaning of the electron-attracting group of Taft σ ^* constant value of 3.5 or more represented by Z ^1a and Z ^{1b in} the formula (2) is the same as that of the electron-attracting group A described above, and the preferable range is also the same. In Formula (2), q1 and q2 are each independently an integer of 0 or more, and at least one of q1 and q2 represents an integer of 1 or more. q1 and q2 each independently indicate that 0 to 2 is preferable, and 0 or 1 is more preferable. In formula (2), when q1 is 2 or more, q1 Z ^1a may be the same or different, and when q2 is 2 or more, q2 Z ^1b may be the same or different.

Y ^{1 in} formula (2) represents -CR ^Y1 R ^Y2- , -NR ^Y3- , or -S-, and R ^Y1 to R ^Y3 each independently represent a hydrogen atom or a substituent. Examples of the substituents represented by R ^Y1 to R ^Y3 include a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a fluorenyl group, and a heterocyclic group. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group, the aryl group, the alkenyl group, the alkynyl group, the fluorenyl group, and the heterocyclic group include the groups described for R ¹ in the formula (a-1).

The cyclic oxime compound A used in the present invention is preferably a compound represented by the following formula (3a) or (3b). These compounds have more excellent sensitivity and are particularly preferably used.
[Chemical Formula 8]

In formula (3a), X ¹ represents -O-, -CR ^x1 R ^X2- , -S-, -NR ^x3 -or> C = NOR ^x4 , and R ^x1 to R ^x4 each independently represent a hydrogen atom or a substituent, R ^x1 and R ^x3 may be bonded to R ² or R ^3c to form a ring, Y ² represents -CR ^Y21 R ^Y22- , -NR ^Y23- , or -S-, and R ^Y21 to R ^Y23 each independently represent a hydrogen atom or a substitution In formula (3b), X ² represents> CR ^X10 -or> N-, and R ^x10 represents a hydrogen atom or a substituent;
In formula (3a) and formula (3b), R ¹ , R ² , R ^3c and R ^3d each independently represent a substituent, and L represents an alkylene group having 1 to 3 carbon atoms or -CR ^L1 = CR ^L2- , R ^L1 and R ^L2 each independently represent a hydrogen atom or a substituent, Z ^1c and Z ^1d each independently represent an electron attracting group having a σ ^* constant value of 3.5 or more, n represents 0 or 1, m represents 0 or 1, and o3 , O4, p, q3, and q4 each independently represent an integer of 0 or more, and at least one of q3 and q4 represents an integer of 1 or more. When p is 2 or more, p R ² may be the same or different, and 2 R ² may be bonded to each other to form a ring. When o3 is 2 or more, o3 R ^3c may be the same or different. 2 R ^3c may be bonded to each other to form a ring. When o4 is 2 or more, o4 R ^3d may be the same. It can also be different. Two R ^3ds can be bonded to each other to form a ring. When q3 is 2 or more, q3 Z ^1c can be the same or different. When q4 is 2 or more, q4 Z ^1d can be the same or different. .

X of formula (3a) is ^{1, L, R 1, R} 2, X m and n are as defined in the formula (1) is ^{1, L, R 1, R} 2, m and n are the same as the preferred ranges are also the same .

Y ^{2 in} formula (3a) represents -CR ^Y21 R ^Y22- , -NR ^Y23- , or -S-, and R ^Y21 to R ^Y23 each independently represent a hydrogen atom or a substituent. Examples of the substituents represented by R ^Y21 to R ^Y23 include a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a fluorenyl group, and a heterocyclic group. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group, the aryl group, the alkenyl group, the alkynyl group, the fluorenyl group, and the heterocyclic group include the groups described for R ¹ in the formula (a-1).

Of formula (3b) of the ^{L, R 1, L R 2} , m and n have the meaning as in formula (1), R ^1, R ^2, m and n are the same as the preferred ranges are also the same.

X ^{2 in} formula (3b) represents> CR ^X10 -or> N-, and R ^x10 represents a hydrogen atom or a substituent. Examples of the substituent represented by R ^x10 include a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a fluorenyl group, and a heterocyclic group. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group, the aryl group, the alkenyl group, the alkynyl group, the fluorenyl group, and the heterocyclic group include the groups described for R ¹ in the formula (a-1).

The meanings of R ^3c and R ^3d in formula (3a) and formula (3b) are the same as those of R ³ in formula (1), and preferred ranges are also the same. The meanings of o3 and o4 in formula (3a) and formula (3b) are the same as those of o in formula (1), and the preferred ranges are also the same. In formulas (3a) and (3b), when o3 is 2 or more, o3 R ^3c may be the same or different, and two R ^3c may be bonded to each other to form a ring. When o4 is 2 or more, o4 R ^3d They may be the same or different, and two R ^3ds may be bonded to each other to form a ring.
The ring formed by bonding these groups to each other may be an aliphatic ring or an aromatic ring.

The electron-attracting group of Taft having a σ ^* constant value of 3.5 or more represented by Z ^1c and Z ^{1d in} the formulae (3a) and (3b) has the same meaning as the electron-attracting group A described above, and the preferable range is also the same. In formulas (3a) and (3b), q3 and q4 are each independently an integer of 0 or more, and at least one of q3 and q4 represents an integer of 1 or more. Each of q3 and q4 independently indicates that 0 to 2 is preferable, and 0 or 1 is more preferable. In formula (3a) and formula (3b), when q3 is 2 or more, q3 Z ^1c may be the same or different, and when q4 is 2 or more, q4 Z ^1d may be the same or different.

The cyclic oxime compound A used in the present invention is preferably a compound represented by the following formula (4a) or (4b). When these compounds are used, it is easier to improve the stability of the photosensitive composition over time.
[Chemical Formula 9]

In formula (4a), X ¹ represents -O-, -CR ^x1 R ^X2- , -S-, -NR ^x3 -or> C = NOR ^x4 , and R ^x1 to R ^x4 each independently represent a hydrogen atom or a substituent, R ^x1 and R ^x3 may be bonded to R ² or R ^3a to form a ring;
In the formulae (4a) and (4b), R ¹ , R ^3e and R ^3f each independently represent a substituent, Z ^1e and Z ^1f each independently represent an electron attracting group having a σ ^* constant value of 3.5 or more, and o5 , O6, q5, and q6 each independently represent an integer of 0 or more, at least one of q5 and q6 represents an integer of 1 or more, and when o5 is 2 or more, o5 R ^3e may be the same or different, and two R ^3e are each other It can be bonded to form a ring. When o6 is 2 or more, o6 R ^3f can be the same or different. Two R ^3f can be bonded to each other to form a ring. When q5 is 2 or more, q5 Z ^1e can be the same. It may be different. When q6 is 2 or more, q6 Z ^1f may be the same or different.

The meanings of X ¹ and R ¹ in formula (4a) are the same as those of X ¹ and R ¹ in formula (1), and preferred ranges are also the same.

The meaning of R ¹ in formula (4b) is the same as that of R ¹ in formula (1), and the preferred range is also the same.

The meanings of R ^3e and R ^3f in formula (4a) and formula (4b) are the same as those of R ³ in formula (1), and preferred ranges are also the same. The meanings of o5 and o6 in formula (4a) and formula (4b) are the same as those of o in formula (1), and the preferred ranges are also the same. In formulas (4a) and (4b), when o5 is 2 or more, o5 R ^3e may be the same or different, and two R ^3e may be bonded to each other to form a ring. When o6 is 2 or more, o6 R ^3f It may be the same or different, and two R ^3f may be bonded to each other to form a ring.
The ring formed by bonding these groups to each other may be an aliphatic ring or an aromatic ring.

The electron-attracting group of Taft having a σ ^* constant value of 3.5 or more represented by Z ^1e and Z ^{1f in} the formulae (4a) and (4b) has the same meaning as the electron-attracting group A described above, and the preferred range is also the same. In Formula (4a) and Formula (4b), q5 and q6 each independently represent an integer of 0 or more, and at least one of q5 and q6 represents an integer of 1 or more. It is preferable that q5 and q6 are independently 0 to 2, and 0 or 1 is more preferable. In formula (4a) and formula (4b), when q5 is 2 or more, q5 Z ^1e may be the same or different, and when q6 is 2 or more, q6 Z ^1f may be the same or different.

Specific examples of the cyclic oxime compound A include compounds having the following structures.
[Chemical Formula 10]

[Chemical Formula 11]

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

The cyclic oxime compound A preferably has a maximum absorption wavelength in a range of 350 to 500 nm, and more preferably has a maximum absorption wavelength in a range of 360 to 480 nm. In addition, the molar absorption coefficient of the cyclic oxime compound A at a wavelength of 365 nm or a wavelength of 405 nm is preferably 10,000 to 300,000, more preferably 15,000 to 300,000, and more preferably 20,000 to 200,000. The Molar absorption coefficient of the cyclic oxime compound A can be measured using a known method. For example, a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) is preferably used to measure the concentration of 0.01 g / L using an ethyl acetate solvent.

The content of the cyclic oxime compound A is preferably 0.1 to 30% by mass in the total solid content of the photosensitive coloring composition. The lower limit is more preferably 0.5% by mass or more, more preferably 1% by mass or more, and 2% by mass or more is particularly preferable. The upper limit is more preferably 25% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less. The cyclic oxime compound A may be used individually by 1 type, and may use 2 or more types together. When two or more cyclic oxime compounds A are used in combination, the total amount of these is preferably in the above range.

<<< Polymerizable Compound >>
The photosensitive composition of the present invention contains a polymerizable compound. Examples of the polymerizable compound include compounds having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, a (meth) allyl group, and a (meth) acrylfluorenyl group. The polymerizable compound is preferably a compound (radically polymerizable compound) that can be polymerized by a radical.

The polymerizable compound may be any of chemical forms such as a monomer, a prepolymer, and an oligomer, but a monomer is preferred. The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, and more preferably 250 or more.

The polymerizable compound is preferably a compound containing three or more ethylenically unsaturated groups, more preferably a compound containing 3 to 15 ethylenically unsaturated groups, and a compound containing 3 to 6 ethylenically unsaturated groups. Better. The polymerizable compound is preferably a 3 to 15-functional (meth) acrylate compound, and more preferably a 3 to 6-functional (meth) acrylate compound.

Regarding the polymerizable monomer, reference can be made to paragraphs 0095 to 0108 of JP 2009-288705, paragraph 0227 of JP 2013-29760, and paragraphs 0254 to 0257 of JP 2008-292970. These contents are incorporated into this manual. The polymerizable compound is dinepentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by NIPPON KAYAKU CO., Ltd.), and dinepentaerythritol tetraacrylate (KAYARAD D- as a commercial product) 320; manufactured by NIPPON KAYAKU CO., Ltd.), dipentaerythritol penta (meth) acrylate (available commercially as KAYARAD D-310; manufactured by NIPPON KAYAKU CO., Ltd.), dinepentaerythritol Hexa (meth) acrylate (available commercially as KAYARAD DPHA; manufactured by NIPPON KAYAKU CO., Ltd., NK ESTER A-DPH-12E; manufactured by SHIN-NAKAMURA CHEMICAL CO., Ltd.), and the like ( Compounds having a structure in which a meth) acrylfluorenyl group is bonded via ethylene glycol and / or propylene glycol residues (for example, SR454 and SR499 marketed by SARTOMER Company, Inc.) are preferred. These oligomer types can also be used. As the polymerizable compound, NK ESTER A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040, and DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.) can also be used. As polymerizable compounds, trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, and trimethylolpropane ethylene oxide modified Trifunctional (meth) acrylate compounds such as tri (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate are also preferred. Examples of commercially available trifunctional (meth) acrylate compounds include ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, and M-306. , M-305, M-303, M-452, M-450 (manufactured by TOAGOSEI CO., Ltd.), NK ESTER A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A- TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (Nippon Kayaku Co., Ltd.) and so on.

The polymerizable compound may have an acid group. Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphate group. A carboxyl group is preferred. Examples of commercially available products of the radically polymerizable compound having an acid group include ARONIX M-510, M-520, and ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.).

The polymerizable compound having an acid group preferably has an acid value of 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the solubility in the developer is good, and if it is 40 mgKOH / g or less, it is advantageous in terms of manufacturing or handling.

The polymerizable compound is also a compound having a caprolactone structure. The polymerizable compound having a caprolactone structure is marketed by, for example, NIPPON KAYAKU CO., Ltd. as the KAYARAD DPCA series, and examples include DPCA-20, DPCA-30, DPCA-60, and DPCA-120.

The polymerizable compound is also a compound having an alkoxy group. A polymerizable compound having an alkoxy group is preferably a compound having an ethoxy group and / or a propyloxy group, and a compound having an ethoxy group is more preferred, having 4 to 20 ethoxy groups. The 3 to 6-functional (meth) acrylate compound having an oxygen group is more preferable. As a commercially available product of a polymerizable compound having an alkoxy group, for example, SR-494, which is a tetrafunctional (meth) acrylate having four ethoxy groups, and three having ethoxy groups, are available from Sartomer Company, Inc. Trifunctional (meth) acrylic acid isobutylene such as KAYARAD TPA-330.

Examples of the polymerizable compound include urethanes described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 2-032293, and Japanese Patent Publication No. 2-016765. Acrylates or those having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Urethane compounds are also preferred. Also, a polymerizable compound having an amine structure or a thioether structure in a molecule described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 1-105238 is also used Better. Examples of commercially available products include UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH -600, T-600, AI-600 (manufactured by Kyoeisha chemical Co., Ltd.), etc.
In addition, as the polymerizable compound, 8UH-1006, 8UH-1012 (the above are manufactured by TAISEI FINE CHEMICAL Co., Ltd.), LIGHT ACRYLATEPOB-A0 (manufactured by Kyoeisha chemical Co., Ltd.), and the like are also preferable.
In addition, as the polymerizable compound, compounds described in Japanese Patent Application Laid-Open No. 2017-048367, Japanese Patent No. 6058791, and Japanese Patent No. 6031807 can be used.

The content of the polymerizable compound is preferably 0.1 to 50% by mass in the total solid content of the photosensitive coloring composition. The lower limit is more preferably 0.5% by mass or more, more preferably 1% by mass or more, and particularly preferably 5% by mass or more. The upper limit is more preferably 45% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less. The polymerizable compound may be used singly or in combination of two or more kinds. When two or more polymerizable compounds are used in combination, the total amount of these is preferably in the above range.

＜＜ Color Material ＞＞
The photosensitive composition of the present invention preferably contains a color material. Examples of the color material include a colorant, a white colorant, a black colorant, and a near-infrared absorbing pigment. The type of the color material can be appropriately selected according to the use of the photosensitive composition. The color material may be a pigment or a dye. From the reason that a film having more excellent light resistance is easily obtained, a pigment is preferred.

(Color colorant)
Examples of the colorant include a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant, and an orange colorant. The coloring agent may be a pigment or a dye. A pigment is preferred. The average particle diameter (r) of the pigment is more preferably 20nm≤r≤300nm, more preferably 25nm≤r≤250nm, and 30nm≤r≤200nm is more preferable. The "average particle diameter" as used herein refers to the average particle diameter of secondary particles obtained by assembling primary particles of a pigment. Regarding the particle size distribution of the secondary particles of the pigment that can be used (hereinafter, also simply referred to as "particle size distribution"), 70% by mass or more of the secondary particles included in the range of the average particle size ± 100 nm are More preferably, 80 mass% or more is more preferable.

Pigment-based organic pigments are preferred. Examples of the organic pigment include the following.
Color Index (CI) 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, 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 , 138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176 , 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc. (the above are yellow pigments),
CI 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 Etc. (the above are orange pigments),
CI 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, 254, 255, 264, 270, 272, 279, etc. (the above are Red pigment),
CI Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, etc. (the above are green pigments),
CI Pigment Violet 1, 19, 23, 27, 32, 37, 42 etc. (above, purple pigment),
CI Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc. (the above are blue pigments) .
These organic pigments can be used alone or in combination.

In addition, as the yellow pigment, a metal azo pigment containing at least one anion selected from an azo compound represented by the following formula (I) and an azo compound having a tautomeric structure, Two or more metal ions and melamine compounds.
[Chemical Formula 19]

In the formula, R ¹ and R ² are each independently -OH or -NR ⁵ R ⁶ , R ³ and R ⁴ are each independently = O or = NR ⁷ , and R ⁵ to R ⁷ are each independently a hydrogen atom or an alkane base. The carbon number of the alkyl group represented by R ⁵ to R ⁷ is preferably 1 to 10, more preferably 1 to 6 and even more preferably 1 to 4. The alkyl group may be any of a straight chain, a branch, and a cyclic ring. A straight chain or a branch is preferable, and a straight chain is more preferable. The alkyl group may have a substituent. The substituent is preferably a halogen atom, a hydroxyl group, an alkoxy group, a cyano group, and an amine group.

In formula (I), R ¹ and R ² are preferably -OH. R ³ and R ⁴ == 0 are more preferred.

The melamine compound in the metal azo pigment is preferably a compound represented by the following formula (II).
[Chemical Formula 20]

In the formula, R ¹¹ to R ¹³ are each independently a hydrogen atom or an alkyl group. The carbon number of the alkyl group is preferably from 1 to 10, more preferably from 1 to 6, and even more preferably from 1 to 4. The alkyl group may be any of a straight chain, a branch, and a cyclic ring. A straight chain or a branch is preferable, and a straight chain is more preferable. The alkyl group may have a substituent. The substituent is preferably a hydroxyl group. R ¹¹ ~ R ¹³ at least one hydrogen atom is preferred based, R ¹¹ ~ R ¹³ is more preferably a hydrogen atom entire system.

The metal azo pigment system includes at least one anion selected from the azo compound represented by the formula (I) and an azo compound having a tautomeric structure, a metal ion including at least Zn ²⁺ and Cu ²⁺ , and A metal azo pigment in the form of a melamine compound is preferred. In this aspect, based on 1 mole of the total metal ions of the metal azo pigment, it is more preferable to contain 95 to 100 mole% of Zn ²⁺ and Cu ²⁺ in total, and 98 to 100 mole%. More preferably, it is more preferable to contain 99.9 to 100 mole%, and it is particularly preferable to contain 100 mole%. In addition, the molar ratio of Zn ²⁺ and Cu ²⁺ in the metal azo pigment is Zn ²⁺ : Cu ²⁺ = 199: 1 to 1:15 is more preferable, and 19: 1 to 1: 1 is more preferable. 9: 1 to 2: 1 are further preferred. In this aspect, the metal azo pigment may further include divalent or trivalent metal ions (hereinafter, also referred to as metal ions Me1) other than Zn ²⁺ and Cu ²⁺ . Examples of the metal ion Me1 include Ni ²⁺ , Al ³⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ²⁺ , Nd ³⁺ , Sm ²⁺ , Sm ³⁺ , Eu ²⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Yb ²⁺ , Yb ³⁺ , Er ³⁺ , Tm ³⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Mn ²⁺ , Y ³⁺ , Sc ³⁺ , Ti ²⁺ , Ti ³⁺ , Nb ³⁺ , Mo ²⁺ , Mo ³⁺ , V ²⁺ , V ³⁺ , Zr ²⁺ , Zr ³⁺ , Cd ²⁺ , Cr ³⁺ , Pb ²⁺ , Ba ²⁺ , selected from Al ³⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Yb ³⁺ , Er ³⁺ , Tm ³⁺ , Mg At least one of ²⁺ , Ca ²⁺ , Sr ²⁺ , Mn ^2+, and Y ³⁺ is preferred, and is selected from the group consisting of Al ³⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , La ^{At least one of 3+} , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Tb ³⁺ , Ho ^3+, and Sr ²⁺ is further preferred, and is selected from Al ³⁺ , Fe ²⁺ , At least one of Fe ³⁺ , Co ²⁺ and Co ³⁺ is particularly preferred. The content of the metal ion Me1 is based on 1 mol of the total metal ions of the metal azo pigment, preferably 5 mol% or less, more preferably 2 mol% or less, and more preferably 0.1 mol% or less.

Regarding the metal azo pigments, refer to paragraphs 0011 to 0061, paragraphs 0137 to 0276 of Japanese Patent Laid-Open No. 2017-171912, paragraphs 0010 to 0061, paragraphs 0138 to 0295 of Japanese Patent Laid-Open No. 2017-171913, and Japanese Patent Laid-Open Paragraphs 0011 to 0061, paragraphs 0139 to 0190 of 2017-171914, paragraphs 0010 to 0065, and paragraphs 0142 to 0222 of JP 2017-171915 are incorporated in this specification.

In addition, as the red pigment, a compound having a structure in which an aromatic ring group is bonded to a diketopyrrolopyrrole skeleton can also be used: the aromatic ring group is introduced with an aromatic ring bond and an oxygen atom, a sulfur atom, or nitrogen Atomic groups. As such a compound, a compound represented by the formula (DPP1) is preferable, and a compound represented by the formula (DPP2) is more preferable.
[Chemical Formula 21]

In the above formula, R ¹¹ and R ¹³ each independently represent a substituent, R ¹² and R ¹⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and n11 and n13 each independently represent an integer of 0 to 4. , X ¹² and X ¹⁴ each independently represent an oxygen atom, a sulfur atom, or a nitrogen atom, when X ¹² is an oxygen atom or a sulfur atom, m12 represents 1, when X ¹² is a nitrogen atom, m12 represents 2, and X ¹⁴ is an oxygen atom or sulfur atom, M14 represents 1 when X ¹⁴ is a nitrogen atom, M14 represents 2. Examples of the substituents represented by R ¹¹ and R ¹³ include an alkyl group, an aryl group, a halogen atom, a fluorenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, a fluorenylamino group, a cyano group, and a nitrate. As a preferable specific example, a methyl group, a trifluoromethyl group, a fluorenylene group, a sulfo group, and the like are used.

In addition, as the green pigment, a zinc halide phthalocyanine pigment having an average of 10 to 14 halogen atoms, 8 to 12 bromine atoms, and 2 to 5 chlorine atoms per molecule can be used. Specific examples include compounds described in International Publication No. WO2015 / 118720.

As the blue pigment, an aluminum phthalocyanin compound having a phosphorus atom can also be used. Specific examples include compounds described in paragraphs 0022 to 0030 of JP 2012-247591, and paragraphs 0047 of JP 2011-157478.

The dye is not particularly limited, and a known dye can be used. For example, a pyrazole azo system, an aniline azo system, a triarylmethane system, an anthraquinone system, an anthrapyridone system, a benzimine system, an oxacyanine system, and a pyrazolotriazole couple are mentioned. Nitrogen, pyridone azo, cyanine, phenanthrene, pyrrolopyrazoleimine, Based, phthalocyanine based, benzopyran based, indigo based, and pyrrole methylene based dyes. A multimer of these dyes may also be used. The dyes described in Japanese Patent Application Laid-Open No. 2015-028144 and Japanese Patent Application Laid-Open No. 2015-034966 can also be used.

(White colorant)
In the present invention, the white colorant includes not only pure white, but also a bright gray (for example, off-white, light gray, etc.) coloring agent that is close to white. The white colorant may be a pigment or a dye. Examples of the white pigment include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconia, alumina, barium sulfate, silicon dioxide, talc, mica, aluminum hydroxide, calcium silicate, and silicate Aluminum, hollow resin particles, zinc sulfide, etc. The white colorant is preferably a particle having titanium atoms, and more preferably titanium oxide.

The content (purity) of titanium dioxide (TiO ₂ ) in the titanium oxide is preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 85% by mass or more. The content of low-order titanium oxide, titanium oxynitride, and the like represented by Ti _n O _2n-1 (n represents a number of 2 to 4) in titanium oxide is preferably 30% by mass or less, and more preferably 20% by mass or less. 15 mass% or less is more preferable.

The shape of titanium oxide is not particularly limited. Examples include shapes such as isotropic shapes (eg, spherical, polyhedral, etc.), anisotropic shapes (eg, needle-like, rod-like, plate-like, etc.), and irregular shapes. The hardness (Mohs hardness) of titanium oxide is preferably 5 to 8, and more preferably 7 to 7.5. The true specific gravity (density) of titanium oxide is preferably 1.0 to 6.0 g / cm ^{3, and more} preferably 3.9 to 4.5 g / cm ³ . The bulk specific gravity of titanium oxide is preferably 0.1 g / cm ³ to 1.0 g / cm ^{3, and more} preferably 0.2 g / cm ³ to 0.4 g / cm ³ .

As the white colorant, a commercially available product can be used. Commercially available products can be used directly or used after being classified. Examples of commercially available products of titanium oxide include the trade names Tipaque R-550, R-580, R-630, R-670, R-680, R-780, and R-780- manufactured by Ishihara Sangyo Kaisha, Ltd. 2.R-820, R-830, R-850, R-855, R-930, R-980, CR-50, CR-50-2, CR-57, CR-58, CR-58-2, CR-60, CR-60-2, CR-63, CR-67, CR-Super70, CR-80, CR-85, CR-90, CR-90-2, CR-93, CR-95, CR- 953, CR-97, PF-736, PF-737, PF-742, PF-690, PF-691, PF-711, PF-739, PF-740, PC-3, S-305, CR-EL, PT-301, PT-401M, PT-401L, PT-501A, PT-501R, UT771, TTO-51C, TTO-80A, TTO-S-2, A-220, MPT-136, MPT-140, MPT- 141; trade names R-3L, R-5N, R-7E, R-11P, R-21, R-25, R-32, R-42, R-44, manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD. R-45M, R-62N, R-310, R-650, SR-1, D-918, GTR-100, FTR-700, TCR-52, A-110, A-190, SA-1, SA- 1L, STR-100A-LP, STR-100C-LP, TCA-123E; trade names JR, JRNC, JR-301, JR-403, JR-405, JR-600A, JR-600E, JR- 603, JR-605, JR-701, JR-800, JR-805, JR-806, JR-1000, MT-01, M T-05, MT-10EX, MT-100S, MT-100TV, MT-100Z, MT-100AQ, MT-100WP, MT-100SA, MT-100HD, MT-150EX, MT-150W, MT-300HD, MT- 500B, MT-500SA, MT-500HD, MT-600B, MT-600SA, MT-700B, MT-700BS, MT-700HD, MT-700Z; Titan Kogyo, Ltd. trade names KR-310, KR-380 , KR-380N, ST-485SA15; trade names TR-600, TR-700, TR-750, TR-840, TR-900 made by FUJI TITANIUM INDUSTRY CO., LTD .; products made by SHIRAISHI CALCIUM KAISHA, Ltd. Name Brilliant1500 and so on. In addition, titanium oxide described in paragraphs 0025 to 0027 of JP-A-2015-67794 can also be used. As a commercial item of a strontium titanate, SW-100 (made by Titan Kogyo, Ltd.) etc. are mentioned. Examples of commercially available products of barium sulfate include BF-1L (manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD.). Examples of commercially available products of zinc oxide include Zincox Super F-1 (manufactured by Hakusuitech Co., Ltd.). Examples of commercially available products of zirconia include Z-NX (manufactured by TAIYO KOKO CO., LTD.). It is also possible to use the titanium oxide described in "Titanium Oxide Physical Properties and Applied Technology, Kiyoshi Scholarship, pages 13-45, June 25, 1991, published by Kyododo".

As the white colorant, not only a single inorganic substance can be used, but also particles obtained by compounding with other materials can be used. For example, using particles with voids or other materials inside, particles with a large number of inorganic particles attached to the core particles, and core-shell composite particles composed of core particles including polymer particles and a shell layer including inorganic nano particles are Better. As the core-shell composite particles composed of the core particles including the polymer particles and the shell layer including the inorganic nano-particles, for example, the descriptions in paragraphs 0012 to 0042 of Japanese Patent Application Laid-Open No. 2015-047520 can be referred to, and the contents are incorporated herein. In this manual.

The white colorant can also use hollow inorganic particles. A hollow inorganic particle is an inorganic particle having a hollow structure inside, and refers to an inorganic particle having a cavity surrounded by a shell. Examples of the hollow inorganic particles include hollow inorganic particles described in Japanese Patent Application Laid-Open No. 2011-075786, International Publication No. WO2013-061621, Japanese Patent Application Laid-Open No. 2015-164881, and the like, which are incorporated into this specification .

(Black colorant)
Examples of the black colorant include inorganic black colorants (inorganic black pigments) such as carbon black, titanium black, zirconium oxynitride, vanadium oxynitride, and niobium oxynitride, or bisbenzofuranone compounds and methylimine compounds. Organic black colorants such as, fluorene compounds, azo compounds.

As the inorganic black colorant, titanium black is preferred. Titanium black is black particles containing titanium atoms, and low-order titanium oxide or titanium oxynitride is preferred. Titanium black can modify the surface as needed for the purpose of improving dispersibility and suppressing cohesion. For example, the surface of titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconia. Further, a treatment using a water-repellent substance as shown in Japanese Patent Application Laid-Open No. 2007-302836 can also be performed. It is preferable that either the primary particle diameter or the average primary particle diameter of each particle of titanium black is small. Specifically, the average primary particle diameter is preferably 10 to 45 nm.

Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and silicon dioxide particles, and the content ratio of the Si atoms to the Ti atoms in the dispersion is adjusted to be in the range of 0.20 to 0.50, and the like. Regarding the above-mentioned dispersion, the descriptions in paragraphs 0020 to 0105 of Japanese Patent Application Laid-Open No. 2012-169556 can be referred to, and the contents are incorporated into this specification. As commercially available products of titanium black, titanium black 10S, 12S, 13R, 13M, 13M-C, 13R-N, 13M-T (trade name: Mitsubishi Materials Corporation), Tilack D (trade name: Ako Kasei Co) ., Ltd.) Etc. The carbon black described in paragraph 0149 of Japanese Patent Application Laid-Open No. 2013-249471 can also be used.

As for the organic black colorant, a bisbenzofuranone compound and a fluorene compound are preferable. Examples of the bisbenzofuranone compounds include those described in Japanese Patent Application Publication No. 2010-534726, Japanese Patent Application Publication No. 2012-515233, Japanese Patent Application Publication No. 2012-515234, and the like, and can be produced, for example, by BASF Corporation. "Irgaphor Black". Examples of the fluorene compound include CI Pigment Black 31 and 32.
Examples of the methylimine compound include those described in Japanese Patent Application Laid-Open No. 1-170601 and Japanese Patent Application Laid-Open No. 2-034664. For example, "CHROMO" manufactured by Daichiniseka Color & Chemicals Mfg. Co., Ltd. can be used. FINE BLACK A1103 ". The bisbenzofuranone compound is preferably a compound represented by any one of the following formulas or a mixture of these.
[Chemical Formula 22]

In the formula, R ¹ and R ² each independently represent a hydrogen atom or a substituent, R ³ and R ⁴ each independently represent a substituent, a and b each independently represent an integer of 0 to 4, and when a is 2 or more, plural R ³ may be the same or different, and a plurality of R ³ may be bonded to form a ring. When b is 2 or more, a plurality of R ⁴ may be the same or different, and a plurality of R ⁴ may be bonded to form a ring.

The substituents represented by R ¹ to R ⁴ represent a halogen atom, cyano, nitro, alkyl, alkenyl, alkynyl, aralkyl, aryl, heteroaryl, -OR ³⁰¹ , -COR ³⁰² , -COOR ³⁰³ , -OCOR ³⁰⁴ , -NR ³⁰⁵ R ³⁰⁶ , -NHCOR ³⁰⁷ , -CONR ³⁰⁸ R ³⁰⁹ , -NHCONR ³¹⁰ R ³¹¹ , -NHCOOR ³¹² , -SR ³¹³ , -SO ₂ R ³¹⁴ , -SO ₂ OR ³¹⁵ , -NHSO ₂ R ³¹⁶ or -SO ₂ NR ³¹⁷ R ³¹⁸ , and R ³⁰¹ to R ³¹⁸ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group.

For details of the bisbenzofuranone compound, refer to the descriptions in paragraphs 0014 to 0037 of Japanese Patent Application Publication No. 2010-534726, which is incorporated into this specification.

(Near-infrared absorbing pigment)
As the near-infrared absorbing pigment, a compound having a maximum absorption wavelength in a wavelength range of 700 to 1800 nm is more preferable, and a compound having a maximum absorption wavelength in a wavelength range of 700 to 1300 nm is more preferable. Compounds with a wavelength are further preferred. The ratio A ¹ / A ² of the absorbance A ¹ at a wavelength of 500 nm of the near-infrared absorber to the absorbance A ² at the maximum absorption wavelength is preferably 0.08 or less, and more preferably 0.04 or less.

Examples of near-infrared absorbing pigments include pyrrolopyrrole compounds, cyanine compounds, squaraine compounds, phthalocyanine compounds, naphthalene [phthalocyanine] compounds, tetralin compounds, merocyanin compounds, and ketonium ( croconium compound, oxacyanine compound, immonium compound, dithiol compound, triarylmethane compound, pyrrole methylene compound, methylimine compound, anthraquinone compound, and dibenzofuranone compound, etc., selected from pyrrole At least one of a pyrrole compound, a cyanine compound, a squarylium compound, a ketonium compound, a phthalocyanine compound, a naphthalene [phthalocyanine] compound, and an ammonium compound is preferably selected from the group consisting of pyrrolopyrrole compounds, cyanine compounds, At least one of a squaraine compound, a ketonium compound, and an immonium compound is more preferable, and a pyrrolopyrrole compound is particularly preferable. Examples of the phthalocyanine compound include compounds described in paragraph 0093 of Japanese Patent Application Laid-Open No. 2012-077153, titanium phthalocyanine described in Japanese Patent Laid-Open No. 2006-343631, and Japanese Patent Laid-Open No. 2013-195480. The compounds described in paragraphs 0013 to 0029 and the vanadium phthalocyanine described in Japanese Patent No. 6081771 are incorporated in this specification. Examples of naphthalene [phthalocyanine] compounds include compounds described in paragraph 093 of Japanese Patent Application Laid-Open No. 2012-077153, and the contents are incorporated into the present specification. In addition, as the near-infrared absorbing dye, a compound described in Japanese Patent Application Laid-Open No. 2016-146619 can be used.

Examples of the pyrrolopyrrole compounds include compounds represented by the formula (PP).
[Chemical Formula 23]

In the formula, R ^1a and R ^1b each independently represent an alkyl group, an aryl group or a heteroaryl group, R ² and R ³ each independently represent a hydrogen atom or a substituent, and R ² and R ³ may be bonded to each other to form a ring. R ⁴ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^4A R ^4B or a metal atom, and R ⁴ may be covalently bonded to at least one selected from R ^1a , R ^1b and R ³ Or coordination bonding, and R ^4A and R ^4B each independently represent a substituent. R ^4A and R ^4B may be bonded to each other to form a ring. For details of the formula (PP), refer to paragraphs 0017 to 0047 of Japanese Patent Application Laid-Open No. 2009-263614, paragraphs 0011 to 0036 of Japanese Patent Laid-Open No. 2011-068731, and 0010 to 0024 of International Publication WO2015 / 166873. These paragraphs are incorporated into this specification.

In the formula (PP), it is preferable that R ^1a and R ^1b are each independently an aryl group or a heteroaryl group, and an aryl group is more preferable. The alkyl group, aryl group, and heteroaryl group represented by R ^1a and R ^1b may have a substituent, or may be unsubstituted. Examples of the substituent include the substituents described in paragraphs 0020 to 0022 of Japanese Patent Application Laid-Open No. 2009-263614 or the following substituents T.

(Substituent T)
Alkyl (preferably alkyl having 1 to 30 carbons), alkenyl (preferably alkenyl having 2 to 30 carbons), alkynyl (preferably alkynyl having 2 to 30 carbons), aryl (Preferably aryl having 6 to 30 carbons), amine (preferably amine having 0 to 30 carbons), alkoxy (preferably alkoxy having 1 to 30 carbons), aryloxy Group (preferably aryloxy group having 6 to 30 carbon atoms), heteroaryloxy group, fluorenyl group (preferably fluorenyl group having 1 to 30 carbon atoms), alkoxycarbonyl group (preferably 2 to 30 carbon atoms) Alkoxycarbonyl group), aryloxycarbonyl group (preferably aryloxycarbonyl group having 7 to 30 carbon atoms), fluorenyl group (preferably fluorenyloxy group having 2 to 30 carbon atoms), fluorenylamino group (more Preferred is fluorenylamino having 2 to 30 carbon atoms), alkoxycarbonylamino (preferably alkoxycarbonylamino group having 2 to 30 carbons), aryloxycarbonylamino group (preferably 7 carbon atoms) Aryloxycarbonylamino group of 30), sulfamoyl group (preferably aminesulfonyl group having 0 to 30 carbon atoms), carbamoyl group (preferably carbamoylmethyl group having 1 to 30 carbon atoms) , Alkylthio (preferably alkylthio having 1 to 30 carbons), arylthio (preferably arylthio having 6 to 30 carbons), heteroarylthio (more Is 1-30 carbons), alkylsulfonyl (preferably 1-30 carbons), arylsulfonyl (preferably 6-30 carbons), heteroarylsulfonyl (preferably Carbon number 1-30), alkylsulfinylsulfonyl group (preferably carbon number 1-30), arylsulfinylsulfonyl group (preferably 6-30 carbon number), heteroarylsulfinylsulfonyl group (more It is preferably a carbon number of 1 to 30), a urea group (preferably a carbon number of 1 to 30), a hydroxyl group, a carboxyl group, a sulfo group, a phosphate group, a carboxylic acid amine group, a sulfonic acid amine group, a fluorenyl acid group, Mercapto group, halogen atom, cyano group, alkylsulfinyl group, arylsulfinyl group, hydrazine group, imino group, and heteroaryl group (preferably having 1 to 30 carbon atoms). When these groups are groups which can be further substituted, they may further have a substituent. Examples of the substituent include those described in the above-mentioned substituent T.

Specific examples of the group represented by R ^1a and R ^1b include an aryl group having an alkoxy group as a substituent, an aryl group having a hydroxy group as a substituent, and an aryl group having a fluorenyloxy group as a substituent.

In the formula (PP), R ² and R ³ each independently represent a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned substituent T. It is preferable that at least one of R ² and R ³ is an electron attracting group. Examples of the electron attracting group include a cyano group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, and an arylsulfonyl group. Is better.

In the formula (PP), R ² represents an electron attracting group (preferably a cyano group), and R ³ represents a heteroaryl group. Heteroaryl is more preferably a 5-membered ring or a 6-membered ring. In addition, a heteroaryl monocyclic or fused ring is more preferred, a monocyclic or fused ring having a fused number of 2 to 8 is more preferred, and a monocyclic or fused ring of a fused number of 2 to 4 is further preferred. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, and more preferably 1 to 2. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. The heteroaryl group preferably has one or more nitrogen atoms. The two R ² in the formula (PP) may be the same as or different from each other. The two R ³ in the formula (PP) may be the same as or different from each other.

In the formula (PP), R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or a group represented by -BR ^4A R ^4B , and a hydrogen atom, an alkyl group, an aryl group or -BR ^4A R ^4B shows the group is more preferred, a group represented by the sum -BR ^4A R ^4B is further preferred. As the substituents represented by R ^4A and R ^4B , a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group is preferable, an alkyl group, an aryl group, or a heteroaryl group is more preferable, and an aryl group is particularly preferable. . These groups may further have a substituent. The two R ⁴ in formula (PP) may be the same as or different from each other. R ^4A and R ^4B may be bonded to each other to form a ring.

Specific examples of the pyrrolopyrrole compound include compounds described in Examples described later. Examples of the pyrrolopyrrole compounds include compounds described in paragraphs 0016 to 0058 of JP 2009-263614, compounds described in paragraphs 0037 to 0052 of JP 2011-068731, and international publications. The compounds and the like described in paragraphs 0010 to 0033 of WO2015 / 166873 are incorporated herein.

The squaraine compound is preferably a compound represented by the following formula (SQ1).
[Chemical Formula 24]

In the formula, As ¹ and As ² each independently represent an aryl group, a heterocyclic group, or a group represented by the formula (As-1);
[Chemical Formula 25]

In the formula, * represents a bonding bond, Rs ¹ to Rs ³ each independently represent a hydrogen atom or an alkyl group, As ³ represents a heterocyclic group, n _s1 represents an integer of 0 or more, and Rs ¹ and Rs ² may be bonded to each other to form A ring, Rs ¹ and As ³ may be bonded to each other to form a ring, and Rs ² and Rs ³ may be bonded to each other to form a ring. When n _s1 is 2 or more, the plurality of Rs ² and Rs ³ may be the same or different.

The carbon number of the aryl group represented by As ¹ and As ² is preferably from 6 to 48, more preferably from 6 to 22, and particularly preferably from 6 to 12.

The heterocyclic group represented by As ¹ , As ² and As ³ is preferably a 5- or 6-membered heterocyclic ring. A heterocyclic group is preferably a monocyclic heterocyclic group or a fused ring heterocyclic group having a fused number of 2 to 8. A monocyclic heterocyclic group or a fused ring heterocyclic group of fused numbers of 2 to 4 is preferred. A cyclic group is more preferred, a monocyclic heterocyclic group or a fused ring heterocyclic group having a fused number of 2 or 3 is more preferred, a monocyclic heterocyclic group or a fused ring heterocyclic group having a fused number of 2 Especially good. Examples of the hetero atom of the ring constituting the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. A nitrogen atom and a sulfur atom are preferred. The number of heteroatoms constituting the ring of the heterocyclic group is 1 to 3, and 1 to 2 is more preferable.

Rs ¹ to Rs ³ in the formula (As-1) each independently represent a hydrogen atom or an alkyl group. The carbon number of the alkyl group represented by Rs ¹ to Rs ³ is preferably 1 to 20, more preferably 1 to 15 and even more preferably 1 to 8. The alkyl group may be any of a straight chain, a branched chain, and a cyclic group, and a straight chain or a branched chain is preferred. Rs ¹ to Rs ³ are preferably hydrogen atoms.

N _s1 in the formula (As-1) represents an integer of 0 or more. n _s1 is an integer of 0 to 2 is preferred, 0 or 1 is more preferred, and 0 is further preferred.

In formula (As-1), Rs ¹ and Rs ² may be bonded to each other to form a ring, Rs ¹ and As ³ may be bonded to each other to form a ring, and Rs ² and Rs ³ may be bonded to each other to form a ring. As the linking group when forming the ring, a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, an alkylene group having 1 to 10 carbon atoms, and a combination thereof is preferred. good. The alkylene group as the linking group may be unsubstituted or may have a substituent. Examples of the substituent include the above-mentioned substituent T.

In the formula (SQ1), it is preferred that the groups represented by As ¹ and As ² have a substituent. Examples of the substituent include the above-mentioned substituent T.

In the formula (SQ1), As ¹ and As ² are each independently an aryl group or a heterocyclic group, or As ¹ and As ² are each independently a group represented by the formula (As-1).

In addition, in the formula (SQ1), a cation exists in a delocalized manner as follows.
[Chemical Formula 26]

Specific examples of the squaraine compound include compounds described in paragraphs 0044 to 0049 of Japanese Patent Laid-Open No. 2011-208101, compounds described in paragraphs 0060 to 0061 of Japanese Patent No. 6065169, and International Publication WO2016. The compound described in paragraph 0040 of / 181987, the compound described in International Publication No. WO2013 / 133099, the compound described in International Publication No. WO2014 / 088063, and Japanese Patent Application Laid-Open No. 2014-126642. Compounds, compounds described in JP 2016-146619, compounds described in JP 2015-176046, compounds described in JP 2017-25311, international publication WO2016 / 154782 Compounds described in Japanese Patent Publication, Japanese Patent No. 5854953, Japanese Patent No. 6036689, Japanese Patent No. 5810604, Japanese Patent Laid-Open No. 2017-068120 Compounds and the like described are incorporated into this specification.

The cyanine compound is preferably a compound represented by the formula (Cy1).
[Chemical Formula 27]

Rcy ¹ to Rcy ⁵ each independently represent a hydrogen atom or a substituent, and two of Rcy ¹ to Rcy ⁵ may be bonded to form a ring. n _cy1 represents an integer from 0 to 2. When n _cy1 is 2, a plurality of Rcy ⁴ and Rcy ⁵ may be the same or different. Acy ¹ and Acy ² each independently represent an aryl group or a heterocyclic group. When the part represented by Cy in the formula is a cationic part, Y represents a counter anion, c represents the number required to balance the charge, and when the part represented by Cy in the formula is an anion part, Y represents a counter cation, c Represents the number required to balance the charge. When the charge of the site represented by Cy in the formula is neutralized in the molecule, c is 0.

Rcy ¹ to Rcy ⁵ each independently represent a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned substituent T. In the formula (Cy1), two of Rcy ¹ to Rcy ⁵ may be bonded to form a ring. As the linking group when forming the ring, a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, an alkylene group having 1 to 10 carbon atoms, and a combination thereof is preferred. good. The alkylene group as the linking group may be unsubstituted or may have a substituent. Examples of the substituent include the above-mentioned substituent T.

n _cy1 represents an integer of 0 to 2, and 0 or 1 is preferred. When n _cy1 is 2, the plurality of Rcy ⁴ and Rcy ⁵ may be the same or different.

The carbon number of the aryl group represented by Acy ¹ and Acy ² is preferably 6 to 48, more preferably 6 to 22, and particularly preferably 6 to 12. The heterocyclic group represented by Acy ¹ and Acy ² is preferably a 5- or 6-membered heterocyclic ring. A heterocyclic group is preferably a monocyclic heterocyclic group or a fused ring heterocyclic group having a fused number of 2 to 8. A monocyclic heterocyclic group or a fused ring heterocyclic group of fused numbers of 2 to 4 is preferred. A cyclic group is more preferred, a monocyclic heterocyclic group or a fused ring heterocyclic group having a fused number of 2 or 3 is more preferred, a monocyclic heterocyclic group or a fused ring heterocyclic group having a fused number of 2 Especially good. Examples of the hetero atom constituting the ring of the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. An oxygen atom and a sulfur atom are preferred. The number of heteroatoms constituting the ring of the heterocyclic group is 1 to 3, and 1 to 2 is more preferable. The groups represented by Acy ¹ and Acy ² may have a substituent. Examples of the substituent include the above-mentioned substituent T.

In the formula (Cy1), when the part represented by Cy in the formula is a cationic part, Y represents a counter anion, and c represents a number required for balancing the charge. As the counter anion include a halogen ion ^{(Cl -, Br -, I} -), a sulfonate anion, a carboxylate anion, sulfonic acyl acyl imide _{^{anion, PF 6 -, BF 4 -}} , ClO 4 -, tris (haloalkyl sulfo acyl group) methide anion _{(e.g., (CF 3 SO 2) 3} C -), bis (sulfo-haloalkyl acyl) acyl imide anion (e.g. _{(CF 3 SO 2) 2 N} -), tetraarylphosphonium Borate anion, tetracyanoborate anion, etc.
In the formula (Cy1), when the part represented by Cy in the formula is an anion part, Y represents a counter cation, and c represents a number required for the balance of electric charges. Examples of counter cations include alkali metal ions (Li ⁺ , Na ⁺ , K ^+, etc.), alkaline earth metal ions (Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Sr ^2+, etc.), and transition metal ions (Ag ⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ^2+, etc.), other metal ions (Al ^3+, etc.), ammonium ion, triethylammonium ion, tributylammonium ion, pyridine ion , Tetrabutylammonium ion, guanidinium ion, tetramethylguanidinium ion, diazinebicycloundecene ion, and the like.
In formula (Cy1), when the charge of the site represented by Cy in the formula is neutralized in the molecule, Y does not exist. That is, c is 0.

Specific examples of the cyanine compound include compounds described in paragraphs 0044 to 0045 of JP 2009-108267, compounds described in paragraphs 0026 to 0030 of JP 2002-194040, and Compounds described in JP 2015-172004, compounds described in JP 2015-172102, compounds described in JP 2008-088426, and JP 2017-031394 The recorded compounds and the like are incorporated into this specification.

(Gram ketonium compound)
The ketonium compound is preferably a compound represented by the following formula (Cr1).
[Chemical Formula 28]

In the formula, Ac ¹ and Ac ² each independently represent an aryl group, a heterocyclic group, or a group represented by the formula (Ac-1);
[Chemical Formula 29]

In the formula, * represents a bonding bond, Rc ¹ to Rc ³ each independently represent a hydrogen atom or an alkyl group, Ac ³ represents a heterocyclic group, n _c1 represents an integer of 0 or more, and Rc ¹ and Rc ² can be formed by bonding each other. A ring, Rc ¹ and Ac ³ may be bonded to each other to form a ring, Rc ² and Rc ³ may be bonded to each other to form a ring, and when n _c1 is 2 or more, a plurality of Rc ² and Rc ³ may be the same or different.

The carbon number of the aryl group represented by Ac ¹ and Ac ² is preferably 6 to 48, more preferably 6 to 22, and particularly preferably 6 to 12.

The heterocyclic group represented by Ac ¹ , Ac ² and Ac ³ is preferably a 5-membered ring or 6-membered ring heterocyclic group. A heterocyclic group is preferably a monocyclic heterocyclic group or a fused ring heterocyclic group having a fused number of 2 to 8. A monocyclic heterocyclic group or a fused ring heterocyclic group of fused numbers of 2 to 4 is preferred. A cyclic group is more preferred, a monocyclic heterocyclic group or a fused ring heterocyclic group having a fused number of 2 or 3 is more preferred, a monocyclic heterocyclic group or a fused ring heterocyclic group having a fused number of 2 Especially good. Examples of the hetero atom of the ring constituting the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. A nitrogen atom and a sulfur atom are preferred. The number of heteroatoms constituting the ring of the heterocyclic group is 1 to 3, and 1 to 2 is more preferable.

Rc ¹ to Rc ³ in the formula (Ac-1) each independently represent a hydrogen atom or an alkyl group. The carbon number of the alkyl group represented by R ^c1 to R ^c3 is preferably 1 to 20, more preferably 1 to 15 and even more preferably 1 to 8. The alkyl group may be any of a straight chain, a branched chain, and a cyclic ring, and a straight chain or a branched chain is preferred. Rc ¹ to Rc ³ are preferably hydrogen atoms.

N _c1 in the formula (Ac-1) represents an integer of 0 or more. n _c1 is an integer of 0 to 2 is preferred, 0 or 1 is more preferred, and 1 is further preferred.

In formula (Ac-1), Rc ¹ and Rc ² may be bonded to each other to form a ring, Rc ¹ and Ac ³ may be bonded to each other to form a ring, and Rc ² and Rc ³ may be bonded to each other to form a ring. As the linking group when forming the ring, a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, an alkylene group having 1 to 10 carbon atoms, and a combination thereof is preferred . The alkylene group as the linking group may be unsubstituted or may have a substituent. Examples of the substituent include the above-mentioned substituent T.

In the formula (Cr1), it is preferred that the groups represented by Ac ¹ and Ac ² have a substituent. Examples of the substituent include the above-mentioned substituent T.

In the formula (Cr1), it is preferable that Ac ¹ and Ac ² are each independently an aryl group or a heterocyclic group, or Ac ¹ and Ac ² are each independently a group represented by the formula (Ac-1).

In addition, in the formula (Cr1), cations are delocalized and exist as follows.
[Chemical Formula 30]

Specific examples of the ketonium compound include compounds described in Japanese Patent Application Laid-Open No. 5-155145 and compounds described in Japanese Patent Application Laid-Open No. 2007-031644, which are incorporated into this specification.

The ammonium compound is preferably a compound represented by the following formula (Im).

Formula (Im)
[Chemical Formula 31]

In the formula, R ¹¹ to R ¹⁸ each independently represent an alkyl group or an aryl group, V ¹¹ to V ¹⁵ each independently represent an alkyl group, an aryl group, a halogen atom, an alkoxy group, or a cyano group, X represents a counter anion, and c represents The numbers required for the balance of the electric charges, n1 to n5 are each independently 0 to 4.

R ¹¹ to R ¹⁸ each independently represent an alkyl group or an aryl group. The carbon number of the alkyl group is preferably from 1 to 20, more preferably from 1 to 12, and particularly preferably from 1 to 8. The alkyl group may be any of a straight chain, a branched chain, and a cyclic ring, and a straight chain or a branched chain is preferred. The carbon number of the aryl group is preferably 6 to 25, 6 to 15 is more preferable, and 6 to 12 is more preferable.
The alkyl group and the aryl group may have a substituent or may be unsubstituted. Examples of the substituent include those described in the above-mentioned substituent T.

V ¹¹ to V ¹⁵ each independently represent an alkyl group, an aryl group, a halogen atom, an alkoxy group, or a cyano group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The carbon number of the alkyl group is preferably from 1 to 20, more preferably from 1 to 12, and particularly preferably from 1 to 8. The alkyl group may be any of a straight chain, a branched chain, and a cyclic ring. A straight chain or a branched chain is preferred, and a straight chain is particularly preferred. The carbon number of the aryl group is preferably 6 to 25, 6 to 15 is more preferable, and 6 to 12 is more preferable. The carbon number of the alkoxy group is preferably from 1 to 20, more preferably from 1 to 12, and particularly preferably from 1 to 8. The alkoxy group may be any of a linear chain, a branched chain, and a cyclic ring. A linear or branched chain is preferred, and a linear chain is particularly preferred.

n1 to n5 are each independently 0 to 4. n1 to n4 are preferably 0 to 2 and more preferably 0 or 1. n5 is more preferably 0 to 3, and more preferably 0 to 2.

X represents a counter anion. As the counter anion include a halogen ion ^{(Cl -, Br -, I} -), a sulfonate anion, a carboxylate anion, sulfonic acyl acyl imide _{^{anion, PF 6 -, BF 4 -}} , ClO 4 -, tris (haloalkyl sulfo acyl group) methide anion _{(e.g., (CF 3 SO 2) 3} C -), bis (sulfo-haloalkyl acyl) acyl imide anion (e.g. _{(CF 3 SO 2) 2 N} -), tetraarylphosphonium Borate anion, tetracyanoborate anion, etc.

c represents a number required for balancing the electric charges, and for example, 2 is preferable.

Specific examples of the ammonium compound include the compounds described in Japanese Patent Application Publication No. 2008-528706, the compounds described in Japanese Patent Application Publication No. 2012-012399, and the compounds described in Japanese Patent Application Publication No. 2007-092060. Compounds, which are incorporated into this specification.

As the near-infrared absorbing pigment, a commercially available product can also be used. Examples of commercially available products of near-infrared absorbing pigments include SDO-C33 (manufactured by Arimoto Chemical Co., Ltd.), EX Color IR-14, EX Color IR-10A, EX Color TX-EX-801B, and EX Color TX- EX-805K (manufactured by NIPPON SHOKUBAI CO., Ltd.), ShigenoxNIA-8041, ShigenoxNIA-8042, ShigenoxNIA-814, ShigenoxNIA-820, ShigenoxNIA-839 (manufactured by Hakko Chemical Co., Ltd.), EpoliteV-63, Epolight3801, Epolight3036 (manufactured by EPOLIN INC.), PRO-JET825LDI (manufactured by FUJIFILM Corporation), NK-3027, NK-5060 (manufactured by HAYASHIBARA CO., LTD.), YKR-3070 (manufactured by Mitsui Chemicals, Inc.), and the like.

The content of the color material in the total solid content of the photosensitive composition is preferably 5 mass% or more, more preferably 10 mass% or more, more preferably 20 mass% or more, 30 mass% or more is further preferable, and 40 mass % Or more is more preferable, and 50% by mass or more is further preferable. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and more preferably 70% by mass or less. In particular, as the content of the color material in the photosensitive composition increases, the sensitivity tends to decrease, but with the photosensitive composition of the present invention, even if the content of the color material in the photosensitive composition is high, it can maintain excellent The sensitivity. Therefore, when the content of the color material in the total solid content of the photosensitive composition is high, the effect of the present invention is more pronounced.

The color material used in the photosensitive composition of the present invention preferably contains at least one selected from the group consisting of a coloring agent, a black coloring agent, and a white coloring agent, and more preferably contains at least one selected from the group consisting of a coloring agent and a black coloring agent. It is more preferable to include a coloring agent. The content of the coloring agent and the black coloring agent in the total mass of the coloring material is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 70% by mass or more. The upper limit can be set to 100% by mass or 90% by mass or less.

When the photosensitive composition of the present invention is used as a composition for a color filter (more specifically, a composition for forming a colored pixel of a color filter), the content of the colorant in the total solid content of the photosensitive composition The content is preferably 30% by mass or more, more preferably 40% by mass or more, and more preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and more preferably 70% by mass or less. The content of the colorant in the total mass of the color material is preferably 25% by mass or more, more preferably 45% by mass or more, and more preferably 65% by mass or more. The upper limit can be set to 100% by mass or 75% by mass or less.

When the photosensitive composition of the present invention is used as a composition for forming a light-scattering layer or a composition for forming white pixels of a color filter, etc., the amount of white colorant in the total solid content of the photosensitive composition The content is preferably 30% by mass or more, more preferably 40% by mass or more, and more preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and more preferably 70% by mass or less. The content of the white colorant in the total mass of the color material is preferably 25% by mass or more, more preferably 45% by mass or more, and more preferably 65% by mass or more. The upper limit can be set to 100% by mass or 75% by mass or less.

When the photosensitive composition of the present invention is used as a composition for forming a light-shielding film or a composition for forming a black matrix, a black colorant (preferably an inorganic black colorant) in the total solid content of the photosensitive composition The content is preferably 30% by mass or more, more preferably 40% by mass or more, and more preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and more preferably 70% by mass or less. The content of the black colorant in the total mass of the color material is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 70% by mass or more. The upper limit can be set to 100% by mass or 90% by mass or less.

When the photosensitive composition of the present invention is used as a composition for a near-infrared transmission filter, it is preferable that the color material used in the present invention satisfies at least one of the following requirements (1) to (3) .

(1): Two or more kinds of coloring agents are included, and black is formed by a combination of two or more kinds of coloring agents. It is preferable that black is formed from a combination of two or more colorants selected from the group consisting of a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant.
(2): Contains organic black colorant.
(3): The above (1) or (2) further includes a near-infrared absorbing pigment.

As a preferable combination of the aspect of said (1), the following are mentioned, for example.
(1-1) A state containing a red colorant and a blue colorant.
(1-2) A state containing a red colorant, a blue colorant, and a yellow colorant.
(1-3) A state containing a red colorant, a blue colorant, a yellow colorant, and a purple colorant.
(1-4) A state containing a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant.
(1-5) A state containing a red colorant, a blue colorant, a yellow colorant, and a green colorant.
(1-6) A state containing a red colorant, a blue colorant, and a green colorant.
(1-7) A state containing a yellow colorant and a purple colorant.

In the aspect (2), it is also preferable to further contain a coloring agent. By using an organic black colorant and a color colorant together, it is easy to obtain excellent spectral characteristics. Examples of the colorant used in combination with the organic black colorant include red colorants, blue colorants, and purple colorants. Red colorants and blue colorants are preferred. These can be used alone or in combination of two or more. In addition, the mixing ratio of the coloring agent and the organic black coloring agent is preferably from 100 to 200 parts by mass of the organic black coloring agent, and more preferably from 15 to 150 parts by mass.

In the aspect (3), the content of the near-infrared absorbing pigment in the total mass of the color material is preferably 5 to 40% by mass. The upper limit is preferably 30% by mass or less, and more preferably 25% by mass or less. The lower limit is more preferably 10% by mass or more, and more preferably 15% by mass or more.

＜＜ Resin ＞＞
The photosensitive composition of the present invention can contain a resin. In addition, in the present invention, a resin-based organic compound other than a color material means an organic compound having a molecular weight of 3,000 or more.
The resin is blended, for example, for the purpose of dispersing particles such as pigments in a composition or the use of a binder. A resin mainly used for dispersing particles such as pigments is also referred to as a dispersant. However, these uses of the resin are examples, and they can be used for purposes other than these uses.

The weight average molecular weight (Mw) of the resin is preferably 3000 to 2,000,000. The upper limit is preferably 1000000 or less, and more preferably 500,000 or less. The lower limit is preferably 4,000 or more, and more preferably 5,000 or more.

Examples of the resin include a (meth) acrylic resin, an olefin-thiol resin, a polycarbonate resin, a polyether resin, a polyarylate resin, a polyfluorene resin, a polyether resin, a polyphenylene resin, and a polyarylene ether. Phosphine oxide resin, polyimide resin, polyimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, etc. These resins may be used alone or in combination of two or more.

In the present invention, a resin having an acid group is preferably used as the resin. According to this aspect, the developability of the photosensitive composition can be improved, and a pixel having excellent rectangularity can be easily formed. Examples of the acid group include a carboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxyl group. A carboxyl group is preferred. The resin having an acid group can be used as an alkali-soluble resin, for example.

It is preferable that the resin having an acid group includes a repeating unit having an acid group on a side chain, and it is more preferable that all repeating units of the resin include a repeating unit having an acid group on a side chain of 5 to 70 mole%. The upper limit of the content of the repeating unit having an acid group on the side chain is preferably 50 mol% or less, and more preferably 30 mol% or less. The lower limit of the content of the repeating unit having an acid group on the side chain is preferably 10 mol% or more, and more preferably 20 mol% or more.

The resin having an acid group includes a compound derived from a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds are also sometimes referred to as "ether dimers" The repeating unit of the monomer component is also preferred.

[Chemical Formula 32]

In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
[Chemical Formula 33]

In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For details of the formula (ED2), refer to the description of Japanese Patent Application Laid-Open No. 2010-168539, which is incorporated into this specification.

As a specific example of the ether dimer, refer to, for example, paragraph 0317 of Japanese Patent Application Laid-Open No. 2013-029760, which is incorporated into the present specification.

It is also preferable that the resin used in the present invention contains a repeating unit derived from a compound represented by the following formula (X).
[Chemical Formula 34]

In the formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. n represents an integer from 1 to 15.

Regarding the resin having an acid group, refer to the description of paragraphs 0558 to 0571 of Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to paragraphs 0685 to 0700 of US Patent Application Publication No. 2012/0235099), Japanese Patent Laid-Open No. 2012-198408 The contents of paragraphs 0076 to 0099 of the Gazette are incorporated into this specification. In addition, as the resin having an acid group, a commercially available product can also be used.

The acid value of the resin having an acid group is preferably 30 to 500 mgKOH / g. The lower limit is preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more. The upper limit is preferably 400 mgKOH / g or less, more preferably 300 mgKOH / g or less, and even more preferably 200 mgKOH / g or less. The weight average molecular weight (Mw) of the resin having an acid group is preferably 5,000 to 100,000. The number average molecular weight (Mn) of the resin having an acid group is preferably 1,000 to 20,000.

Examples of the resin having an acid group include resins having the following structures.
[Chemical Formula 35]

The photosensitive composition of the present invention can further contain a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acid resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acid resin) means a resin having more acid groups than basic groups. For acidic dispersants (acid resins), when the total amount of acid groups and basic groups is 100 mol%, resins with an acid group content of 70 mol% or more are preferred, and essentially only contain Acid-based resins are more preferred.
It is preferred that the acidic group of the acidic dispersant (acid resin) is a carboxyl group. The acid value of the acidic dispersant (acid resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and still more preferably 60 to 105 mgKOH / g. The basic dispersant (basic resin) means a resin having a larger number of basic groups than an acid group. For the basic dispersant (basic resin), when the total amount of the acid group and the amount of the basic group is 100 mol%, a resin having an amount of the basic group greater than 50 mol% is preferred. It is preferred that the basic group of the basic dispersant is an amine group.

It is preferable that the resin used as a dispersant contains a repeating unit having an acid group. The resin used as a dispersant contains a repeating unit having an acid group, and thereby, when a pattern is formed by a photolithography method, the development residue can be further suppressed.

It is also preferred that the resin used as the dispersant is a graft resin. The details of the graft resin can be found in paragraphs 0025 to 0094 of Japanese Patent Application Laid-Open No. 2012-255128, and the contents are incorporated into this specification. Specific examples of the graft resin include resins having the following structures.
[Chemical Formula 36]

The resin used as a dispersant is also a polyimide-based dispersant containing a nitrogen atom in at least one of a main chain and a side chain. As the polyimide-based dispersant, a resin having a main chain and a side chain and having a basic nitrogen atom on at least one of the main chain and the side chain is preferable. The main chain contains a resin having a functional group of pKa14 or less. In a partial structure, the side chain includes a side chain having 40 to 10,000 atoms. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. Regarding the polyimide-based dispersant, the description in paragraphs 0102 to 0166 of Japanese Patent Application Laid-Open No. 2012-255128 can be referred to, and this content is incorporated into this specification. Specific examples of the polyimide-based dispersant include resins having the following structures.
[Chemical Formula 37]

The resin used as a dispersant is also a resin having a structure in which a plurality of polymer chains are bonded to a core. Examples of such resins include dendrimers (including star polymers). Further, as specific examples of the dendrimer, the polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of Japanese Patent Application Laid-Open No. 2013-043962 and compounds having the following structures may be mentioned.
[Chemical Formula 38]

Moreover, the resin (alkali soluble resin) which has the said acid group can also be used as a dispersing agent.

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

Dispersants can also be obtained as commercially available products. Examples of such dispersants include DISPERBYK series (for example, DISPERBYK-111, 161, etc.) manufactured by BYKChemie GmbH, and SOLSPERSE series (for example, SOLSPERSE76500, etc.) manufactured by Lubrizol Japan Limited. . In addition, the pigment dispersant described in paragraphs 0041 to 0130 of Japanese Patent Application Laid-Open No. 2014-130338 can also be used, and the content is incorporated into this specification. The resin described as the dispersant can also be used for applications other than dispersants. For example, it can also be used as a binder.

When the photosensitive composition of the present invention contains a resin, the content of the resin in the total solid content of the photosensitive composition is preferably 5 to 50% by mass. The lower limit is more preferably 10% by mass or more, and more preferably 15% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less. The content of the resin having an acid group in the total solid content of the photosensitive composition is preferably 5 to 50% by mass. The lower limit is more preferably 10% by mass or more, and more preferably 15% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less. In addition, from the reason that it is easy to obtain excellent developability, the content of the resin having an acid group in the total resin is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 70% by mass or more. , 80% by mass or more is particularly preferred. The upper limit can be 100% by mass, 95% by mass, or 90% by mass or less.

From the viewpoints of curability, developability, and film-forming property, the total content of the polymerizable compound and the resin in the total solid content of the photosensitive composition is preferably 15 to 65% by mass. The lower limit is more preferably 20% by mass or more, more preferably 25% by mass or more, and more preferably 30% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less. The resin is preferably contained in an amount of 30 to 300 parts by mass based on 100 parts by mass of the polymerizable compound. The lower limit is preferably 50 parts by mass or more, and more preferably 80 parts by mass or more. The upper limit is preferably 250 parts by mass or less, and more preferably 200 parts by mass or less.

<<< Compound with a cyclic ether group >>
The photosensitive composition of the present invention can contain a compound having a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. The compound having a cyclic ether group is preferably a compound having an epoxy group. Examples of the compound having an epoxy group include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferred. It is preferable to have 1 to 100 epoxy groups in one molecule. The upper limit of the epoxy group can be, for example, 10 or less, or 5 or less. The lower limit of the epoxy group is preferably two or more. As the compound having an epoxy group, paragraphs 0034 to 0036 of Japanese Patent Application Publication No. 2013-011869, paragraphs 0147 to 0156 of Japanese Patent Application Publication No. 2014-043556, and 0085 to Japanese Patent Publication No. 2014-089408 can also be used. The compound described in paragraph 0092 and the compound described in Japanese Patent Application Laid-Open No. 2017-179172. Such content is incorporated into this specification.

The compound having an epoxy group may be a low-molecular compound (for example, a molecular weight of less than 2000 and further a molecular weight of less than 1000) or a macromolecule (for example, in the case of a polymer having a molecular weight of 1,000 or more, the weight average molecular weight is 1000 or more). The weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, and more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

As the compound having an epoxy group, an epoxy resin can be preferably used. Examples of the epoxy resin include epoxy resins of glycidyl etherification of phenol compounds, epoxy resins of glycidyl etherification of various novolak resins, alicyclic epoxy resins, aliphatic epoxy resins, Heterocyclic epoxy resin, glycidyl ester-based epoxy resin, glycidylamine-based epoxy resin, epoxy resin obtained by glycidizing halogenated phenols, silicon compounds having epoxy groups, and other silicon Condensates of compounds, copolymers of polymerizable unsaturated compounds having epoxy groups and other polymerizable unsaturated compounds other than them, and the like. The epoxy equivalent of the epoxy resin is preferably 310 to 3300 g / eq, more preferably 310 to 1700 g / eq, and still more preferably 310 to 1000 g / eq.

Examples of commercially available compounds having a cyclic ether group include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (above, manufactured by NOF Corporation, epoxy-containing polymer), etc.

When the photosensitive composition of the present invention contains a compound having a cyclic ether group, the content of the compound having a cyclic ether group in the total solid content of the photosensitive composition is preferably 0.1 to 20% by mass. The lower limit is, for example, preferably 0.5% by mass or more, and more preferably 1% by mass or more.
The upper limit is, for example, preferably 15% by mass or less, and more preferably 10% by mass or less. The compound having a cyclic ether group may be only one kind, or two or more kinds. When there are two or more kinds, the total amount is preferably in the above range.

<< Other photopolymerization initiators >>
The photosensitive composition of the present invention may contain other photopolymerization initiators (hereinafter, also referred to as other photopolymerization initiators) other than the cyclic oxime compound. Examples of other photopolymerization initiators include trihalo methyl triazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, fluorenylphosphine compounds, Phosphine oxide compound, metallocene compound, oxime compound, triarylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene-iron complex, halogen Methyloxadiazole compounds, coumarin compounds, and the like, oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds, and fluorenylphosphine compounds are more preferable, and oxime compounds and α-hydroxyketone compounds are more preferable. Examples of the oxime compound as another photopolymerization initiator include an oxime compound having no cyclic oxime moiety described above, or an oxime compound having no electron attracting group described above. For details of other photopolymerization initiators, refer to paragraphs 0013 to 0031 of Japanese Patent Application Laid-Open No. 2017-126044, which are incorporated into this specification.

As a commercially available product of an α-hydroxy ketone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (the above are manufactured by BASF) can be used. Examples of commercially available products of the α-amino ketone compound include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (the above are manufactured by BASF). Examples of commercially available fluorenylphosphine compounds include IRGACURE-819, DAROCUR-TPO (the above is made by BASF), and the like.

As the oxime compound, a compound described in JP 2001-233842, a compound described in JP 2000-080068, a compound described in JP 2006-342166, and Japanese Patent Compounds described in Japanese Patent Publication No. 2016-021012. Examples of the oxime compound that can be preferably used in the present invention include 3-benzyloxyiminobutane-2-one, 3-ethoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-ethoxymethyliminopentane-3-one, 2-ethoxymethylimino-1-phenylpropane-1- Ketone, 2-benzyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxy Carbooxyimino-1-phenylpropane-1-one and the like. Another example is J. C. S. Perkin II (1979, pp. 1653-1660), JCS Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), Japanese Patent Laid-Open No. 2000-066385 The compounds described in Japanese Patent Application Publication No. 2000-080068, Japanese Patent Application Publication No. 2004-534797, and Japanese Patent Application Publication No. 2006-342166. Examples of commercially available oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF), and TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.) ), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photopolymerization initiator 2 described in JP 2012-014052), ADEKA ARKLS NCI-730, NCI-831, NCI-930 (the above is ADEKA Corporation制) and so on.

As another photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include compounds described in Japanese Patent Application Laid-Open No. 2014-137466. This content is incorporated into this specification.

As another photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom include compounds described in Japanese Patent Application Laid-Open No. 2010-262028, compounds 24, 36-40 of Japanese Patent Application No. 2014-500852, and Japanese Patent Laid-Open No. 2013 Compound (C-3) and the like described in JP-164471. This content is incorporated into this specification.

As another photopolymerization initiator, an oxime compound having a nitro group can be used.
An oxime compound having a nitro group is also preferred as a dimer. Specific examples of the nitro-containing oxime compound include the compounds described in paragraphs 0031 to 0047 of Japanese Patent Application Laid-Open No. 2013-114249, paragraphs 0008 to 0012 and 0070-0079 of Japanese Patent Laid-Open No. 2014-137466 Compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4222071, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

In the present invention, a bifunctional or trifunctional or more photopolymerization initiator can be used as the photopolymerization initiator. By using such a photopolymerization initiator, two or more active species such as radicals are generated from one molecule of the photopolymerization initiator, and therefore, good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, crystallinity is reduced, solubility in a solvent and the like is improved, precipitation is difficult to occur over time, and the stability of the composition over time can be improved. Specific examples of such a photopolymerization initiator include Japanese Patent Application Publication No. 2010-527339, Japanese Patent Application Publication No. 2011-524436, International Publication No. WO2015 / 004565, and Japanese Patent Application Publication No. 2016-532675. Paragraphs ~ 0412, dimers of oxime compounds described in paragraphs 0039 to 0055 of International Publication WO2017 / 033680, compounds (E) and compounds (G) described in Japanese Patent Publication No. 2013-522445, International Cmpd1 to 7 described in WO2016 / 034963, oxime ester photoinitiators described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, and paragraphs 0020 to 0033 of Japanese Patent Publication No. 2017-167399 are disclosed. The photoinitiator described in Japanese Patent Application Laid-Open No. 2017-151342, and the photopolymerization initiator (A) described in paragraphs 0017 to 0026.

When the photosensitive composition of the present invention contains other photopolymerization initiators, the content of the other photopolymerization initiators is preferably 10 to 90 parts by mass based on 100 parts by mass of the cyclic oxime compound A. The lower limit is preferably 15 parts by mass or more, and more preferably 20 parts by mass or more. The upper limit is preferably 80 parts by mass or less, and more preferably 70 parts by mass or less. When the ratio of the cyclic oxime compound A to the other photopolymerization initiator is in the above range, it is easy to obtain a film sufficiently hardened to a deep portion.

It is also preferable that the photosensitive composition of the present invention does not substantially contain other photopolymerization initiators. With this aspect, it is easy to further suppress variations in the degree of hardening of the obtained film. When the photosensitive composition of the present invention does not substantially contain other photopolymerization initiators, it means that the content of other photopolymerization initiators in the total solid content of the photosensitive composition is 0.1 or less, and preferably 0.05% by mass or less. 0.01 mass% or less is more preferable, and it is particularly preferable not to contain other photopolymerization initiators.

＜〈 Sensitizer 〉＞
The photosensitive composition of the present invention may further contain a sensitizer for the purpose of improving the radical generation efficiency of the cyclic oxime compound A or increasing the wavelength of the photosensitive wavelength. Examples of the sensitizer include polynuclear aromatic compounds (for example, phenanthrene, anthracene, fluorene, pyrene, triphenylene, 9,10-dialkoxyanthracene), (Xanthene) compounds (e.g. luciferin, eosin, erythrosine, rose red B, bengal rose red), xanthene compounds (e.g. isopropylthioanthone, diethylthioanthone, chlorine Thia anthrone), cyanine compounds (e.g., thiocarbocyanine, oxocyanine), merocyanine compounds (e.g., merocyanine, oxocyanine), phthalocyanine compounds, thiazine compounds (e.g. Fluorene, methylene blue, toluidine blue), acridine compounds (e.g. acridine orange, chloroflavin, acridine xanthophyll), anthraquinone compounds (e.g. anthraquinone), squaraine compounds (e.g. squaraine), Coumarin compounds (eg, 7-diethylamino-4-methylcoumarin), coumarin compounds, phenothiazine compounds, phenazine compounds, styrylbenzene compounds, azo compounds, Phenylmethane compound, triphenylmethane compound, distyrylbenzene compound, carbazole compound, porphyrin compound, spiro compound, quinacridone compound, indigo compound, pyranium compound, pyrrole methylene compound, pyrazole Benzotriazole compounds, benzothiazole compounds, Acid derivative than properly derivatives, thiobarbituric acid derivatives, acetophenone compounds, benzophenone compounds, thioxanthone compounds, which meters Le ketone compounds. The sensitizer is preferably a compound having a maximum absorption wavelength in a wavelength range of 300 to 450 nm. Specific examples of the sensitizer include compounds described in Examples described later, and compounds described in paragraphs 0172 to 0222 of Japanese Patent Application Laid-Open No. 2013-249471.

When the photosensitive composition of the present invention contains a sensitizer, the content of the sensitizer in the total solid content of the photosensitive composition is preferably 0.1 to 20% by mass. The lower limit is, for example, preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. The sensitizer may be only one kind, or two or more kinds. When there are two or more kinds, the total amount is preferably in the above range.

＜ Silane Coupling Agent ＞＞
The photosensitive composition of the present invention can contain a silane coupling agent. According to this aspect, the adhesiveness with the support body of the obtained cured film can be further improved. In the present invention, the silane coupling agent refers to a silane compound having a hydrolyzable group and a functional group other than the silane compound. The hydrolyzable group refers to a substituent directly bonded to a silicon atom and capable of generating a siloxane bond by any of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and a fluorenyl group. An alkoxy group is preferred. 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) acrylfluorenyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, and a urea. Groups, thioether groups, isocyanate groups, phenyl groups, etc., amino groups, (meth) acrylfluorenyl groups, and epoxy groups are preferred. Specific examples of the silane coupling agent include compounds described in paragraphs 0018 to 0036 of JP 2009-288703, and compounds described in paragraphs 0056 to 0066 of JP 2009-242604. The content is incorporated into this manual.

The content of the silane coupling agent in the total solid content of the photosensitive composition is preferably 0.1 to 5% by mass. The upper limit is preferably 3% by mass or less, and more preferably 2% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The silane coupling agent may be only one kind, or two or more kinds. When there are two or more kinds, it is preferable that the total amount falls within the above range.

<< Pigment Derivatives >>
When the photosensitive composition of the present invention contains a pigment, it is preferable to further contain a pigment derivative.
Examples of the pigment derivative include compounds having a structure in which a part of a chromophore is substituted with an acid group, a basic group, or a phthalimide methyl group.

Examples of the chromophore constituting the pigment derivative include a quinoline-based skeleton, a benzimidazolone-based skeleton, a diketopyrrolopyrrole-based skeleton, an azo-based skeleton, a phthalocyanin-based skeleton, an anthraquinone-based skeleton, and quinacridine. Ketone skeleton, difluorene skeleton, purple ring ketone skeleton, fluorene skeleton, Thioindigo skeleton, isoindolline skeleton, isoindolinone skeleton, quinoline yellow skeleton, Shihlin (Threne) -based skeleton, metal complex-based skeleton, etc., quinoline-based skeleton, benzimidazolone-based skeleton, diketopyrrolopyrrole-based skeleton, azo-based skeleton, quinoline yellow-based skeleton, isoindoline-based skeleton A skeleton and a phthalocyanin-based skeleton are preferable, and an azo-based skeleton and a benzimidazolone-based skeleton are more preferable. As the acid group having a pigment derivative, a sulfo group and a carboxyl group are preferred, and a sulfo group is more preferred. As the basic group possessed by the pigment derivative, an amine group is preferable, and a tertiary amine group is more preferable. As a specific example of a pigment derivative, the description of paragraph 0162 to 0183 of Unexamined-Japanese-Patent No. 2011-252065 can be referred, for example, and this content is integrated into this specification.

When the photosensitive composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass relative to 100 parts by mass of the pigment. One type of pigment derivative may be used, or two or more types may be used in combination. The photosensitive composition of the present invention may contain only one kind of pigment derivative, or may contain two or more kinds. When two or more types of pigment derivatives are contained, the total amount of these is preferably in the above range.

＜ solvent ＞
The photosensitive composition of the present invention preferably contains a solvent. Examples of the solvent include organic solvents. The solvent is not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition. Examples of the organic solvent include esters, ethers, ketones, and aromatic hydrocarbons. Regarding such details, refer to paragraph 0223 of International Publication No. WO2015 / 166779, which is incorporated into this specification. In addition, an ester-based solvent substituted with a cyclic alkyl group and a ketone-based solvent substituted with a cyclic alkyl group can also be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, methylene chloride, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl cellosolve acetate. , Ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol ethyl Acid esters, butylcarbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. In the present invention, one type of organic solvent may be used alone, or two or more types may be used in combination. From the viewpoint of improving solubility, 3-methoxy-N, N-dimethylpropanamide and 3-butoxy-N, N-dimethylpropanamide are also preferable. However, the aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as the solvent may be reduced for environmental reasons (for example, it may be 50 mass ppm relative to the total amount of the organic solvent ( Parts per million) can be set to 10 mass ppm or less, or 1 mass ppm or less).

In the present invention, it is preferable to use a solvent with a small metal content. For example, the metal content of the solvent is preferably 10 mass ppb (parts per billion) or less. If required, solvents with quality ppt (parts per trillion) grade can also be used. Such high-purity solvents are provided by, for example, TOYO Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015 ).

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

The solvent may contain isomers (compounds having the same number of atoms but different structures). The isomers may include only one kind or plural kinds.

In the present invention, the content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and it is more preferable not to contain peroxide.

The content of the solvent in the photosensitive composition is preferably 10 to 95% by mass. The lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, 40% by mass or more is further preferable, 50% by mass or more is further preferable, 55% by mass or more is further preferable, and 60% by mass The above is particularly good. The upper limit is preferably 90% by mass.

From the viewpoint of environmental regulations, it is preferable that the photosensitive composition of the present invention does not substantially contain environmental regulations. In addition, in the present invention, substantially no environmental regulatory substance means that the content of the environmental regulatory substance in the photosensitive composition is 50 mass ppm or less, 30 mass ppm or less is preferred, and 10 mass ppm or less is further preferred, 1 Mass ppm is particularly preferred. Examples of environmental regulations include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These substances are registered as environmentally regulated substances under the REACH (Registration Evaluation Authorization and Restriction of CHemicals) regulations, the PRTR (Pollutant Release and Transfer Register) law, and the VOC (Volatile Organic Compounds) regulations, and their usage and disposal methods are strictly controlled. These compounds may be used as a solvent in the production of each component or the like of the photosensitive composition used in the present invention, and may be mixed into the photosensitive composition as a residual solvent. From the viewpoint of human safety and environmental considerations, it is better to reduce these substances as much as possible. Examples of the method for reducing environmental regulatory substances include heating and depressurizing the inside of the system to have a boiling point of the environmental regulatory substances, and distilling and reducing environmental regulatory substances from the system. Moreover, when a small amount of environmental regulations are removed by distillation, azeotropy with a solvent having the same boiling point as the solvent in order to improve efficiency is also useful. In addition, when a compound having a radical polymerizable property is contained, after adding a polymerization inhibitor, it can be distilled off under reduced pressure in order to suppress the progress of the radical polymerization reaction during the reduced pressure distillation to cause cross-linking between molecules. These distillation removal methods can be at any of the raw material stage, the stage of reacting the raw materials (such as a polymerized resin solution and a polyfunctional monomer solution), or a stage of a composition produced by mixing these compounds. In progress.

<< polymerization inhibitors >>
The photosensitive composition of this invention can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tertiary-butyl-p-cresol, gallophenol, tertiary-butylcatechol, benzoquinone, 4,4'-sulfur Substituted bis (3-methyl-6-tertiary-butylphenol), 2,2'-methylenebis (4-methyl-6-tertiary-butylphenolaldehyde), N-nitrosophenylhydroxylamine Salt (ammonium salt, first cerium salt, etc.). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the photosensitive composition is preferably 0.001 to 5% by mass.

＜ Interfacial Active Agents ＞＞
The photosensitive composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. Regarding the surfactant, paragraphs 0238 to 0245 of International Publication No. WO2015 / 166779 can be referred to, and this content is incorporated into the present specification.

In the present invention, the surfactant is preferably a fluorine-based surfactant. By containing a fluorine-based surfactant in the photosensitive composition, the liquid characteristics (especially, fluidity) can be further improved, and the liquid saving property can be further improved. Moreover, a film with small thickness unevenness can also be formed.

The fluorine content in 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. A fluorine-based surfactant having a fluorine content ratio within this range is effective from the viewpoint of the uniformity of the thickness of the coating film and the liquid saving property, and the solubility in the composition is also good.

Examples of the fluorine-based surfactant include the surfactants described in Japanese Patent Application Laid-Open No. 2014-041318, paragraphs 0060 to 0064 (corresponding to International Publication No. 2014/017669, paragraphs 0060 to 0064), and the like. The surfactants described in paragraphs 0117 to 0132 of the 2011-132503 publication are incorporated into this specification. Examples of commercially available fluorine-based surfactants include Magaface F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, and MFS. -330 (above, manufactured by DIC Corporation), Fluorad FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by ASAHI GLASS CO., LTD.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA SOLUTIONS INC.), Etc.

Further, as the fluorine-based surfactant, an acrylic compound containing a molecular structure having a functional group containing a fluorine atom, and a part of the functional group containing a fluorine atom being cleaved upon heating, and a fluorine atom volatilizing can be preferably used. Examples of such fluorine-based surfactants include Magaface DS series (Chemical Industry Daily, February 22, 2016) (Nikkei Industry News, February 23, 2016) manufactured by DIC Corporation, such as Magaface DS-21.

It is also preferable that the fluorine-based surfactant is 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. Such a fluorine-based surfactant can be referred to the description in Japanese Patent Application Laid-Open No. 2016-216602, and the content is incorporated into this specification.

As the fluorine-based surfactant, a block polymer may be used. Examples thereof include compounds described in Japanese Patent Application Laid-Open No. 2011-089090. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound containing: a repeating unit derived from a (meth) acrylate compound having a fluorine atom; and derived from a compound having two or more ( It is preferably 5 or more) repeating units of a (meth) acrylate compound of an alkoxy group (preferably an ethoxy group and a propyleneoxy group). The following compounds are exemplified as the fluorine-based surfactant used in the present invention.
[Chemical Formula 39]

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

In addition, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond group in a side chain can also be used. Specific examples include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Laid-Open No. 2010-164965, such as MEGAFACE RS-101, RS-102, RS-718K, RS- 72-K and so on. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate and glycerol ethoxylate). Etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilauric acid Ester, polyethylene glycol distearate, sorbitan fatty acid ester, PLURONIC L10, L31, L61, L62, 10R5, 17R2, 25R2 (made by BASF), TETRONIC 304, 701, 704, 901, 904 , 150R1 (manufactured by BASF), SOLSPERSE 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D -6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.) and the like.

Examples of the silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above, Dow Corning Toray Co. , Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive performance Materials Inc.), KP-341, KF-6001, KF-6002 (above, Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie GmbH), and the like.

The content of the surfactant in the total solid content of the photosensitive composition is preferably 0.001% to 5.0% by mass, and more preferably 0.005 to 3.0% by mass. The surfactant may be only one kind, or two or more kinds. When there are two or more kinds, it is preferable that the total amount falls within the above range.

＜＜ Ultraviolet absorbent ＞＞
The photosensitive composition of this invention can contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an amino diene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyl tri compound, an indole compound, or a trivalent compound can be used. Compounds etc. For details, please refer to paragraphs 0052 to 0072 of Japanese Patent Application Laid-Open No. 2012-208374, paragraphs 0317 to 0334 of Japanese Patent Laid-Open No. 2013-068814, and paragraphs 0061 to 0080 of Japanese Patent Laid-Open No. 2016-162946. In the description, these contents are incorporated into this specification. Specific examples of the ultraviolet absorber include compounds having the following structures. As a commercial item of an ultraviolet absorber, UV-503 (made by DAITO CHEMICAL CO., LTD.) Etc. are mentioned, for example. Examples of the benzotriazole compound include the MYUA series manufactured by MIYOSHI OIL & FAT CO., LTD. (Chemical Industry Daily, February 1, 2016).
[Chemical Formula 40]

The content of the ultraviolet absorber in the total solid content of the photosensitive composition is preferably 0.01 to 10% by mass, and more preferably 0.01 to 5% by mass. In the present invention, only one kind of ultraviolet absorbent may be used, or two or more kinds may be used. When two or more kinds are used, the total amount is preferably in the above range.

＜〈 Antioxidant 〉＞
The photosensitive composition of the present invention can contain an antioxidant. Examples of the antioxidant include a phenol compound, a phosphite compound, and a thioether compound. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. As a preferable phenol compound, a hindered phenol compound is mentioned. A compound having a substituent at a position adjacent to a phenolic hydroxyl group (ortho position) is preferred. The aforementioned substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. In addition, an antioxidant is preferably a compound having a phenol group and a phosphite group in the same molecule. As the antioxidant, a phosphorus-based antioxidant can be preferably used. Examples of the phosphorus-based antioxidant include tris [2-[[2,4,8,10-tetra (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] di Oxaphosphaheptin-6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1, 3,2] dioxaphosphaheptin-2-yl) oxy] ethyl] amine, and ethylbis (2,4-di-third-butyl-6-methylphenyl) phosphite. Examples of commercially available antioxidants include ADKSTAB AO-20, ADKSTAB AO-30, ADKSTAB AO-40, ADKSTAB AO-50, ADKSTAB AO-50F, ADKSTAB AO-60, ADKSTAB AO-60G, and ADKSTAB AO-80. , ADKSTAB AO-330 (the above is made by ADEKA CORPORATION) and so on.

The content of the antioxidant in the total solid content of the photosensitive composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. The antioxidant may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably in the above range.

＜ Other Other Ingredients ＞＞
The photosensitive composition of the present invention may further contain a hardening accelerator, a filler, a thermal hardening accelerator, a plasticizer, and other auxiliary agents (for example, conductive particles, fillers, defoamers, flame retardants, conditioning agents, etc.) as needed. Leveling agent, peeling accelerator, perfume, surface tension adjuster, chain transfer agent, etc.). By appropriately containing these components, properties such as film physical properties can be adjusted. These components can be referred to, for example, Japanese Patent Application Laid-Open No. 2012-003225 and subsequent paragraphs 0183 (paragraph 0237 of the corresponding US Patent Application Publication No. 2013/0034812), and Japanese Patent Application No. 2008-250074 0101 to The descriptions of paragraphs 0104, 0107 to 0109, etc. are incorporated into this specification. Moreover, the photosensitive composition of this invention may contain a latent antioxidant as needed. Examples of the latent antioxidant include compounds protected by a protective group at a site where the antioxidant functions, and the protective group is heated at 100 to 250 ° C or at 80 to 200 ° C in the presence of an acid / base catalyst. A compound that is detached by heating and functions as an antioxidant. Examples of the latent antioxidant include compounds described in International Publication No. WO2014 / 021023, International Publication No. WO2017 / 030005, and Japanese Patent Application Laid-Open No. 2017-008219. Examples of commercially available products include ADEKARAKLS GPA-5001 (manufactured by ADEKA CORPORATION).

For example, when the film is formed by coating, the viscosity (23 ° C) of the photosensitive composition of the present invention is preferably 1 to 100 mPa ･ s. The lower limit is more preferably 2 mPa ･ s or more, and more preferably 3 mPa 以上 s or more. The upper limit is more preferably 50 mPa · s or less, 30 mPa ･ s or less is more preferable, and 15 mPa · s or less is particularly preferable.

<Container>
The storage container for the photosensitive composition of the present invention is not particularly limited, and a known storage container can be used. In addition, as a storage container, in order to suppress the incorporation of impurities into the raw materials or the composition, it is also preferable to use a multi-layer bottle composed of six kinds of six-layer resins or a bottle having six resins in a seven-layer structure. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

When the photosensitive composition of the present invention is used as a composition for forming a color filter for a liquid crystal display device, the voltage holding ratio of a liquid crystal display element including a color filter formed of the photosensitive composition of the present invention is used. More than 70% is better, more than 90% is better. A known method for obtaining a high voltage holding ratio can be appropriately combined. Typical methods include the use of high-purity raw materials (for example, reduction of ionic impurities) and control of the amount of acidic functional groups in the composition. The voltage holding ratio can be measured, for example, by a method described in paragraph 0243 of Japanese Patent Application Laid-Open No. 2011-008004 and paragraphs 0123 to 0129 of Japanese Patent Laid-Open No. 2012-224847.

<Preparation method of photosensitive composition>
The photosensitive composition of this invention can be prepared by mixing the said component. When preparing a photosensitive composition, all components may be dissolved or dispersed in a solvent at the same time to prepare a photosensitive composition, or two or more kinds of solutions or dispersions obtained by appropriately blending the components may be prepared in advance, These are mixed during use (at the time of coating) to prepare a photosensitive composition.

When the photosensitive composition of the present invention contains particles such as a pigment, a process including dispersing the particles is preferred. In the process of dispersing particles, examples of the mechanical force used in dispersing the particles include compression, pressing, impact, shear, and cavitation. Specific examples of such processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high-speed impeller, a sand mill, Flowjet mixer, high-pressure wet-type micronization, ultrasonic dispersion, etc. In addition, in the pulverization of particles in a sand mixer (bead mill), it is preferable to perform the treatment under conditions that increase the pulverization efficiency by using beads having a small diameter and increasing the filling rate of the beads. After the pulverization treatment, it is preferable to remove coarse particles by filtration, centrifugation, or the like. In addition, the process of dispersing particles and the dispersing machine can better use the "Encyclopedia of Dispersion Technology, issued by JOHOKIKO CO., LTD., July 15, 2005" or "centered on suspension (solid / liquid dispersion system) The actual comprehensive data collection of dispersion technology and industrial applications, issued by the Publishing Department of the Business Development Center, October 10, 1978, and the process and dispersion machine described in paragraph 0022 of Japanese Patent Application Laid-Open No. 2015-157893. In the process of dispersing the particles, the particles can be miniaturized by a salt milling step. The raw materials, equipment, and processing conditions used in the salt milling step can be found in, for example, Japanese Patent Application Laid-Open No. 2015-194521 and Japanese Patent Application Laid-Open No. 2012-046629.

When preparing the photosensitive composition of the present invention, it is preferable to filter the photosensitive composition with a filter for the purpose of removing foreign matter, reducing defects, and the like. The filter can be used without particular limitation as long as it is a filter that has been used for filtration applications and the like so far. Examples include fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefins such as polyethylene and polypropylene (PP). Filters for raw materials such as resins (including high-density, ultra-high molecular weight polyolefin resins). Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred. The pore diameter of the filter is suitably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. As long as the pore diameter of the filter is within the above range, fine foreign matter can be reliably removed. It is also preferable to use a fibrous filter material. Examples of the fibrous filter material include polypropylene fibers, nylon fibers, and glass fibers. Specifically, filter elements of SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.) and SHPX type series (SHPX003, etc.) manufactured by ROKI GROUP CO., Ltd. are mentioned. When using filters, you can also combine different filters (for example, the first filter and the second filter, etc.). At this time, the filtration in each filter may be only once, or may be more than two. Filters with different pore sizes can be combined in the above range. In addition, the filtration in the first filter is performed only on the dispersion liquid, and after mixing the other components, it may be filtered by the second filter.

<Hardened film>
The cured film of the present invention is a cured film obtained from the photosensitive composition of the present invention. The cured film of the present invention can be used for a color filter, a near-infrared transmission filter, a near-infrared cut-off filter, a black matrix, a light-shielding film, a refractive index adjustment film, a photosensitive layer of a lithographic printing plate precursor, a protective film, and a UV-curable ink. , Various photoresist, various display materials, coating materials, dental materials, varnishes, powder coatings, adhesives, dental compositions, gel coatings, electronic parts, magnetic recording materials, micromechanical parts, waveguides, optics Switches, plating masks, color calibration systems, glass fiber cable coatings, screen printing stencils, three-dimensional objects based on three-dimensional printing, image recording materials for full-scale recording, microelectronic circuits, health care materials, etc. The film thickness can be appropriately adjusted according to the purpose.
For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and more preferably 0.3 μm or more.

＜ Manufacturing method of color filter ＞
The manufacturing method of the color filter of the present invention includes: a process of forming the photosensitive composition layer by applying the photosensitive composition of the present invention on a support; a process of exposing the photosensitive composition layer into a pattern; and exposing A process for developing the subsequent photosensitive composition layer to form a pattern. Each step will be described below.

First, the photosensitive composition of the present invention is applied to a support to form a photosensitive composition layer. The support is not particularly limited, and can be appropriately selected depending on the application. For example, a glass substrate, a silicon substrate, etc. are mentioned, A silicon substrate is preferable. In addition, a charge coupled device (CCD), a complementary metal oxide film semiconductor (CMOS), a transparent conductive film, and the like can be formed on a silicon substrate. In addition, a black matrix that isolates each pixel is sometimes formed on a silicon substrate. Further, an undercoat layer is provided on the silicon substrate in order to improve the adhesion with the upper layer, prevent the diffusion of substances, or flatten the surface of the substrate.

As a method of applying the photosensitive composition, a known method can be used. For example, a dropwise addition method (drop casting); a slit coating method; a spray coating method; a roll coating method; a spin coating method (spin coating); a cast coating method; a slit and spin coating method; , The method described in Japanese Patent Application Laid-Open No. 2009-145395); inkjet method (such as on-demand spray method, piezoelectric method, thermal method), nozzle spraying and other ejection printing, flexographic printing, screen printing, gravure Various printing methods such as printing, reverse offset printing, and metal mask printing methods; transfer methods using molds, etc .; nano-imprint methods. The application method based on inkjet is not particularly limited, and examples thereof include "diffuse and usable inkjet-infinite possibilities seen in patents", issued in February 2005, SB Techno-Research Co., Ltd. "(Especially, pages 115 to 133) or Japanese Patent Application Publication No. 2003-262716, Japanese Patent Application Publication No. 2003-185831, Japanese Patent Application Publication No. 2003-261827, Japanese Patent Application Publication No. 2012-126830 The method described in Japanese Patent Publication No. 2006-169325 and the like. Regarding the coating method of the composition, reference may be made to the descriptions of International Publication No. WO2017 / 030174 and International Publication No. WO2017 / 018419, and the contents are incorporated into this specification.

The photosensitive composition layer formed on the support can be dried (pre-baked). When a color filter is manufactured by a low temperature process, pre-baking may not be performed. When performing pre-baking, the pre-baking temperature is preferably below 150 ° C, more preferably below 120 ° C, and even more preferably below 110 ° C. The lower limit can be set to, for example, 50 ° C or higher, and can also be set to 80 ° C or higher. The pre-baking time is preferably 10 to 3000 seconds, more preferably 40 to 2500 seconds, and even more preferably 80 to 2200 seconds. The pre-baking can be performed by a hot plate, an oven, or the like.

Next, the photosensitive composition layer is exposed to a pattern (exposure step). For example, a pattern exposure can be performed by exposing the photosensitive composition layer formed on a support body using an exposure device such as a stepper through a mask having a predetermined mask pattern. Thereby, the photosensitive composition layer of an exposure part can be hardened.

Examples of radiation (light) that can be used during exposure include g-rays and i-rays.
It is also possible to use light having a wavelength of 300 nm or less (preferably light having a wavelength of 180 to 300 nm). Examples of the light having a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and the like, and KrF rays (wavelength 248 nm) are preferred. In addition, a long-wavelength light source of 300 nm or more can be used. Can also use a variety of LED or LD light sources. In addition, a light source in a radiation region such as EB or EUV can be used.

In addition, during exposure, exposure may be performed by continuously irradiating light, or exposure may be performed by pulse irradiation (pulse exposure). In addition, the pulse exposure refers to an exposure method in which light is repeatedly irradiated and paused for a short period of time (for example, less than milliseconds) to perform exposure. In pulse exposure, the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and even more preferably 30 nanoseconds or less. The lower limit of the pulse width is not particularly limited, and can be set to 1 femtosecond (fs) or more, and can also be set to 10 femtosecond or more. The frequency is preferably 1 kHz or more, more preferably 2 kHz or more, and more preferably 4 kHz or more. The upper limit of the frequency is preferably below 50 kHz, more preferably below 20 kHz, and even more preferably below 10 kHz. The maximum instantaneous illuminance is more preferably 50000000W / m ² or more, more preferably 100000000W / m ² or more, and more preferably 200000000W / m ² or more. The upper limit of the maximum instantaneous illuminance is preferably 1000000000 W / m ² or less, more preferably 800000000 W / m ² or less, and more preferably 500000000 W / m ² or less. The pulse width refers to the time during which the light is irradiated during the pulse period. The frequency is the number of pulse cycles per second. In addition, the maximum instantaneous illuminance refers to the average illuminance in the time during which light is irradiated in the pulse period. The pulse period refers to a period in which the irradiation and pause of light during pulse exposure are taken as one cycle.

The irradiation amount (exposure amount) is, for example, preferably 0.03 to 2.5 J / cm ^{2, and more} preferably 0.05 to 1.0 J / cm ² . The oxygen concentration at the time of exposure can be appropriately selected, and in addition to being performed in the atmosphere, it can also be performed in a low-oxygen environment with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially free of oxygen). ) For exposure, or in a high-oxygen environment with an oxygen concentration greater than 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume). In addition, the exposure illuminance can be appropriately set, and can usually be selected from a range of 1000 W / m ² to 100,000 W / m ² (for example, 5000 W / m ² , 15000 W / m ² , or 35000 W / m ² ). Oxygen concentration also may be appropriately combined exposure illuminance condition, for example illuminance 10000W / m ² at an oxygen concentration of 10 vol% under an oxygen concentration of 35% by volume under an illuminance 20000W / m ² and the like.

Next, the exposed photosensitive composition layer is developed to form a pattern (development process). More specifically, a pattern is formed after removing the photosensitive composition layer of an unexposed part by development. The development and removal of the photosensitive composition layer in the unexposed portion can be performed using a developing solution. Thereby, the photosensitive composition layer of an unexposed part melt | dissolved in the developing solution, and only the photohardened part remained on the support body. The temperature of the developer is preferably 20 to 30 ° C. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removal performance, the following steps may be repeated several times: the developer is shaken off every 60 seconds, and the developer is supplied again.

The developing solution is preferably an alkaline aqueous solution (alkaline developing solution) obtained by diluting the alkaline agent with pure water. Examples of the alkaline agent include amine, ethylamine, diethylamine, dimethylethanolamine, diethylene glycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, Tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, Organic basic compounds such as pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene or sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, Inorganic basic compounds such as sodium metasilicate. Regarding the alkali agent, a compound having a large molecular weight is preferable in terms 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, and more preferably 0.01 to 1% by mass. The developing solution may further include a surfactant. Examples of the surfactant include the aforementioned surfactants, and nonionic surfactants are preferred. From the standpoint of convenient transportation and storage, the developing solution can be temporarily prepared as a concentrated solution and diluted to a desired concentration when in use. The dilution ratio is not particularly limited, and can be set in a range of 1.5 to 100 times, for example. It is also preferable to wash (rinse) with pure water after development. The rinsing is preferably performed by supplying a rinsing liquid to the developed photosensitive colored composition layer while rotating the support on which the developed colored photosensitive composition layer is formed. Moreover, it is also preferable to carry out by moving the nozzle which discharges a rinse liquid from the center part of a support body to the peripheral part of a support body. At this time, when moving from the center portion of the support to the peripheral portion of the nozzle, the nozzle can be moved while gradually reducing the moving speed of the nozzle. By performing the rinsing in this manner, it is possible to suppress the in-plane variation of the rinsing. The same effect can also be obtained by gradually reducing the rotation speed of the support while moving from the center of the support to the peripheral portion of the nozzle.

After development, it is preferable to perform heat treatment (post-baking) after drying. Post-baking is a heat treatment for developing after hardening is completed, and the heating temperature is, for example, preferably 100 to 240 ° C, and more preferably 200 to 240 ° C. As for the post-baking, the film after development can be performed in a continuous or discontinuous manner using heating means such as a hot plate or a convection oven (hot air circulation dryer), a high-frequency heater, and the like, so as to satisfy the above conditions.

Patterns (pixels) can be formed through the above process. When manufacturing a color filter having pixels of two or more colors, each of the processes described above is repeated for the desired number of hue phases, whereby a color filter of pixels having a plurality of colors can be manufactured.

Here, as a method for manufacturing the color filter of the present invention, the description will be given focusing on the aspect of using the photosensitive composition of the present invention when forming the pixels of the color filter, but the present invention is not limited to this aspect. For example, the photosensitive composition of the present invention can also be applied to the formation of a black matrix that isolates pixels of each color constituting a color filter. That is, by performing each of the above processes, a black matrix (black pattern) can be formed on the support.

＜ Color filter ＞
Next, a color filter of the present invention will be described. The color filter of the present invention includes the cured film of the present invention described above. When the cured film of the present invention is used for a color filter, the cured film of the present invention preferably contains a coloring agent. That is, it is preferable that the cured film of this invention is formed using the photosensitive composition containing a coloring agent. In the color filter of the present invention, the film thickness of the cured film of 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 even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and more preferably 0.3 μm or more. The color filter of the present invention can be used for a solid-state imaging element such as a CCD (Charge Coupled Element) or a CMOS (Complementary Metal Oxide Film Semiconductor) or an image display device.

<Solid-state image sensor>
The solid-state imaging element of the present invention includes the cured film of the present invention. The structure of the solid-state imaging element of the present invention includes the cured film of the present invention and is not particularly limited as long as it functions as a solid-state imaging element, and examples thereof include the following structures.

The structure is as follows: there are a plurality of diodes and polycrystalline silicon on a substrate, which are composed of a light-receiving area of a solid-state imaging element (a CCD (Charge Coupled Device) image sensor, a CMOS (Complementary Metal Oxide Film Semiconductor) image sensor, and the like). The transmission electrode having the same structure has a light-shielding film having only the light-receiving portion of the diode on the diode and the transmission electrode. The light-shielding film has nitrogen formed so as to cover the entire surface of the light-shielding film and the light-receiving portion of the diode. An element protection film made of silicon and the like has a color filter on the element protection film. Furthermore, it is also possible to have a structure having a light-concentrating mechanism (for example, a micro lens, etc. below) on the element protective film and below the color filter (close to one side of the substrate) or a light-concentrating mechanism on the color filter. The structure, etc.
The color filter may have a structure in which each colored pixel is embedded in a space separated by a partition, for example, in a grid pattern. It is preferable that the partition wall system has a low refractive index with respect to each colored pixel. Examples of the imaging device having such a structure include the devices described in Japanese Patent Application Laid-Open No. 2012-227478 and Japanese Patent Application Laid-Open No. 2014-179577. The imaging device provided with the solid-state imaging element of the present invention can be used as a vehicle-mounted camera or a surveillance camera in addition to a digital camera or an electronic device (mobile phone, etc.) having a camera function.

<Image display device>
An image display device of the present invention includes the cured film of the present invention described above. Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device. Definitions of image display devices and details of each image display device are described in, for example, "Electronic display equipment (by Sasaki Akio, Kogyo Chosakai Publishing Co., Ltd. 1990)", "Display equipment (Ibuki Junaki Author, Sanyo Tosho Publishing Co., Ltd. (issued in 1989) "and so on. The liquid crystal display device is described in, for example, "Next-generation liquid crystal display technology (edited by Uchida Ryuo, Industrial Survey Association, 1994). The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the liquid crystal display device can be applied to various types of liquid crystal display devices described in the "next-generation liquid crystal display technology" described above.
[Example]

Hereinafter, the present invention will be described in more detail through examples. The present invention is not limited to the following examples as long as they do not depart from the gist of the present invention. In the structural formula, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

The photopolymerization initiator used in each of the following test examples is a compound having the following structure. Among the following compounds, OX-1 to OX-21 are cyclic oxime compounds (cyclic oxime compound A) of the present invention. OX-R1 to OX-R4 are comparative compounds.

(Cyclic oxime compound of the present invention)
[Chemical Formula 41]

(Comparative compound)
[Chemical Formula 42]

[Test Example 1]
(Example 1-1)
0.08 mmol of compound OX-1 as a photopolymerization initiator, 1 g of neopentaerythritol tetraacrylate as a polymerizable compound, and 1 g of polymethylmethacrylate (manufactured by Aldrich, weight average molecular weight = 996000) and 16 g of cyclohexanone as a solvent, thereby preparing the photosensitive composition of Example 1-1. The obtained photosensitive composition was applied to a glass substrate by a spin coating method, and dried at 40 ° C. for 10 minutes to form a coating film having a film thickness of 1.5 μm. A gray film of 21 steps (manufactured by Kodak Japan Ltd.) was placed on the coating film, and an exposure machine (manufactured by USHIO INC., "UVC-2534 / 1MNLC3-AA08", 120W / cm ² metal halide lamp) was used. 1 lamp) After irradiating ultraviolet rays with an integrated light amount of 300 mJ / cm ² , it was immersed in toluene for 60 seconds, and developed. As the sensitivity, the number of segments that completely hardened but did not dissolve corresponding to the number of cells was evaluated. As a result, the sensitivity was 6 segments. As for the sensitivity, the larger the number, the higher the sensitivity.

(Examples 1-2 to 1-21, Comparative Examples 1-1 to 1-4)
In Example 1-1, 0.08 mmol of the compound OX-1, which is a photopolymerization initiator, was replaced with 0.08 mmol of the compound described in the following table, and the preparation was performed in exactly the same manner as in Example 1-1. The photosensitive compositions of Examples 1-2 to 1-21 and Comparative Examples 1-1 to 1-4 were evaluated, and the number of sensitivity steps was evaluated in the same manner as in Example 1-1. The evaluation results of Examples 1-2 to 1-21 and Comparative Examples 1-1 to 1-4 and the evaluation results of Example 1-1 are shown in the following table.


[Table 1]

As shown in the above table, the sensitivity of the photosensitive composition of the example is higher than that of the photosensitive composition of the comparative example.

[Test Example 2]
(Preparation of dispersion)
Each of the raw materials described in the following table was mixed with the mass parts described in the following table, and 230 parts by mass of zirconia microspheres with a diameter of 0.3 mm were added, and a bead mill (high-pressure disperser NANO-3000-10 with a pressure reducing mechanism ( (Manufactured by Nippon BEE Co., Ltd.)) were mixed and dispersed for 3 hours to prepare each dispersion.

[Table 2]

The raw materials used to make each dispersion are shown below.

(Color material)
PR254: CI Pigment Red 254 (red pigment)
PR264: CI Pigment Red 264 (red pigment)
PY139: CI Pigment Yellow 139 (yellow pigment)
PY150: CI Pigment Yellow 150 (yellow pigment)
PY185: CI Pigment Yellow 185 (yellow pigment)
PG36: CI Pigment Green 36 (green pigment)
PG58: CI Pigment Green 58 (green pigment)
PB15: 6: CI Pigment Blue 15: 6 (blue pigment)
PV23: CI Pigment Violet 23 (Purple Pigment)

Pc1: Zinc halide phthalocyanine pigment (green pigment) manufactured by the following method
Thiochlorine (45.5 parts by mass), anhydrous aluminum chloride (54.5 parts by mass), and sodium chloride (7 parts by mass) were mixed at 40 ° C, and a zinc phthalocyanine pigment (15 parts by mass) was added. Bromine (35 parts by mass) was added dropwise thereto, and the temperature was raised to 130 ° C over 19.5 hours and maintained for 1 hour. Then, the reaction mixture was dissolved in water, and a zinc halide phthalocyanine crude pigment was precipitated. This aqueous slurry was filtered, washed in hot water at 60 ° C, washed in 1% sodium hydrosulfate water, washed in hot water at 60 ° C, and dried at 90 ° C to obtain 2.7 parts by mass Purified Zinc Halide Phthalocyanine Crude Pigment A. Prepare a purified zinc halide phthalocyanine crude pigment A (1 part by mass), pulverized sodium chloride (10 parts by mass), and diethylene glycol (1 part by mass) in a two-arm kneader at 100 ° C. Mix for 8 hours. After kneading, it was dissolved in water (100 parts by mass) at 80 ° C, and after stirring for 1 hour, it was filtered, washed with hot water, dried, and pulverized to obtain a zinc halide phthalocyanine pigment. From the mass analysis and the halogen content analysis based on the flask combustion ion chromatograph, the obtained zinc halide phthalocyanine pigment has an average composition of ZnPcBr _9.8 Cl _3.1 H _3.1 . In addition, Pc is an abbreviation for phthalocyanine.

PP1, PP2: Compounds of the following structure (near-infrared absorbing pigment)
[Chemical Formula 43]

IBk: Irgaphor Black (black colorant manufactured by BASF)
PBk32: CI Pigment Black 32 (black colorant)
TTO-80A: Titanium oxide (TTO-80A, manufactured by Ishihara Sangyo Kaisha, Ltd., white pigment)

N-Ti: titanium oxynitride-containing particles (black pigment) produced by the method shown below.
In the production of titanium oxynitride-containing particles, the apparatus described in paragraph 042 of Japanese Patent Application Laid-Open No. 2005-343784 and the apparatus shown in FIG. 1 were used. Specifically, an apparatus (hereinafter, referred to as a “nanoparticle manufacturing apparatus”) using the discharge vessel 1 as a stainless steel vacuum chamber (manufactured by FUKUSHIN KOGYO Co., Ltd.) in FIG. 1 of the above publication was used. Particles containing titanium oxynitride. First, the air in the vacuum chamber was exhausted by an exhaust pump. Next, a mixed gas of helium (He) gas (purity 99.99%) and argon gas (mixing ratio 50/50% by volume in the standard state) was supplied to the vacuum chamber until the pressure became 600 Torr (79.99kPa). As the discharge electrode of the nanoparticle manufacturing apparatus, a rod-shaped one having a hollow structure of 500 mm in length, 12 mm in diameter, and 6 mm in hollow diameter was used for forming tungsten. The arrangement of the discharge electrodes is the same as that shown in FIG. 1 of Japanese Patent Application Laid-Open No. 2005-343784. Specifically, twelve discharge electrodes are arranged in two sections every six. The distance between the upper and lower stages is set to approximately 160 mm. The discharge electrode of the hollow structure is connected to the raw material supply device, so that the raw material gas can be supplied into the vacuum chamber from the hollow portion of the discharge electrode. While applying an alternating current (voltage 20 to 40 V, current 70 to 100 A) with a phase difference to each discharge electrode, discharge was started with the tip of each discharge electrode in contact. After the arc discharge is generated, the front ends of the respective discharge electrodes are moved apart, and the distance between the front ends of the adjacent discharge electrodes is set to be 5 to 10 mm, and the arc discharge is continued. After the arc discharge was performed for 15 minutes, the supply tank of the raw material supply device was heated, and the raw material gas was introduced into the vacuum chamber. First, NH ₃ gas (liquefied ammonium ECOAN, manufactured by Showa Denko Co., Ltd.) was introduced at 0.5 atmosphere, H ₂ gas (hydrogen, SHOWA DENKO GASPRODUCTS CO.LTD.) Was introduced at 0.1 atmosphere, and 0.4 atmosphere was introduced. Ar gas (Argon, TAIYO NIPPON SANSO CORPORATION). Next, the supply tank was heated to 210 ° C., and TiCl ₄ gas (TLT-1, manufactured by TOHOTITANIUM CO., LTD.) Was introduced from the discharge electrode at 600 atmospheres. While introducing TiCl ₄ gas, a powder supply device TP-99010FDR (manufactured by JEOL Ltd.) was used to supply sulfur fine powder (fine powder sulfur 325 mesh, manufactured by Tsurumi Chemical Industry Co., Ltd.) using nitrogen. The supply amount was adjusted as follows: The content of the mass basis of the sulfur atom in the obtained titanium oxynitride-containing particles detected by X-ray photoelectron spectroscopy was set to T _E (mass%), and The mass basis content of the sulfur atom detected by the fluorescent X-ray analysis is set to a ratio (T _E / T _X ) of both of T _X (% by mass). After introducing TiCl ₄ gas and nitrogen mixed with fine sulfur powder into the vacuum chamber for 1 hour, the application of voltage from the AC power supply was stopped, and the supply of the gas was stopped. Then, particles attached to the inner wall of the vacuum chamber were recovered. Next, the obtained particles were placed in a closed container in which nitrogen (N ₂ ) gas was introduced to control the O ₂ content and the moisture content to 100 ppm or less, and left to stand for 24 hours. The particles obtained in the above were heated at 200 ° C using a vacuum oven VAC-101P (manufactured by ESPEC Corp.) to obtain particles containing titanium oxynitride. The internal pressure of the reduced-pressure oven during heating was 1.0 × 10 ³ Pa.

N-Zr: oxygen-containing zirconium-containing particles (black pigment) produced by the method shown below
In the production of the titanium oxynitride-containing particles, a powder supply device TP-99010FDR (manufactured by JEOL Ltd.) was used to introduce zirconium powder (zirconium powder manufactured by Wako Pure Chemical Industries, Ltd.) instead of introducing TiCl ₄ gas. Other than that, the particles containing oxygen-assisted zirconium were produced in the same manner as the particles containing titanium oxynitride.

NV: Vanadium oxynitride-containing particles (black pigment) produced by the method shown below
In the production of the above titanium oxynitride-containing particles, a powder supply device TP-99010FDR (manufactured by JEOL Ltd.) was used to introduce vanadium powder (metal vanadium powder VHO manufactured by TAIYO KOKO CO., Ltd.) instead of introducing TiCl ₄ gas. Other than that, particles containing vanadium oxynitride were produced in the same manner as the particles containing titanium oxynitride.

N-Nb: Niobium oxynitride-containing particles (black pigment) produced by the method shown below.
In the production of the above-mentioned titanium oxynitride-containing particles, a powder supply device TP-99010FDR (manufactured by JEOL Ltd.) was used to introduce niobium powder (nitsu powder manufactured by Mitsuwa Chemicals Co., Ltd) instead of introducing TiCl ₄ gas. Other than that, particles of niobium oxynitride were produced in the same manner as the particles of titanium oxynitride.

(Pigment Derivatives)
Syn1 to 4: Compounds of the following structures
[Chemical Formula 44]

(Organic solvents)
PGMEA: propylene glycol monomethyl ether acetate

(Dispersant)
P-1: 30 mass% PGMEA (propylene glycol monomethyl ether acetate) solution of resin p1 synthesized by the following method to 9.05 parts by mass of a polyfunctional thiol compound (compound S-1 of the following structure) and 90.95 parts by mass Propylene glycol monomethyl ether acetate (PGMEA) was added to a mixed solution of a macromonomer (compound MM-1, Mw = 3000 with the following structure), and the solid content concentration was adjusted to 63% by mass, and then heated to 75 ° C. Next, 0.4 part by mass of 2,2'-azobis (isobutyric acid) dimethyl ester (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was added to the mixed solution, and after heating for 2 hours, 0.4 was added again. Mass parts of 2,2'-azobis (isobutyric acid) dimethyl ester were reacted at 90 ° C for 2 hours under a nitrogen gas flow. After that, it was cooled to room temperature (25 ° C, the same applies below). Next, a mixed solution of 76.93 parts by mass of the obtained reactant and 23.06 parts by mass of a monomer having an ethylenically unsaturated bond group (compound m-1 of the following structure) was heated to 75 ° C. under a nitrogen gas stream. Next, 0.4 part by mass of 2,2'-azobis (isobutyric acid) dimethyl was added to the mixed solution, and after heating for 2 hours, 0.4 part by mass of 2,2'-azobis (isobutyl) was added again. The dimethyl acid) was reacted at 90 ° C for 2 hours under a stream of nitrogen. Then, after cooling to room temperature, PGMEA was added to the mixed solution, and the solid content concentration was adjusted to 30% by mass, thereby obtaining a 30% by mass PGMEA solution of the resin p1. The weight average molecular weight (Mw) of the resin p1 was 11,000, the dispersion (Mw / Mn) was 1.8, the acid value was 75 mgKOH / g, and the reduction viscosity was 11 ml / gs.
[Chemical Formula 45]

P-2: 30% by mass PGMEA solution of the resin of the following structure (the value attached to the main chain is the mole ratio, and the value attached to the side chain is the number of repeating units. Mw = 17000, dispersion (Mw / Mn ) = 4.2, acid value = 75mgKOH / g, viscosity reduction = 12.5ml / g).
[Chemical Formula 46]

P-3: 30% by mass PGMEA solution of the resin of the following structure (the value attached to the main chain is the mole ratio, and the value attached to the side chain is the number of repeating units. Mw = 7950)
[Chemical Formula 47]

P-4: 30% by mass PGMEA solution of the resin of the following structure (the value attached to the main chain is the molar ratio. Mw = 12000)
[Chemical Formula 48]

P-5: PGMEA 30% by mass solution of the resin with the following structure (the value attached to the main chain is the mole ratio, and the value attached to the side chain is the number of repeating units. Mw = 30000)
[Chemical Formula 49]

<Manufacture of photosensitive composition>
The raw materials shown in the following table were mixed, and the photosensitive compositions of Examples and Comparative Examples were produced.


[table 3]


[Table 4]

The raw materials used in the production of the composition are as follows.

(Resin)
E1: Resin of the following structure. (The value attached to the main chain is the mole ratio. Mw = 10,000, acid value = 70mgKOH / g)
E2: Resin of the following structure. (The value attached to the main chain is the mole ratio. Mw = 10,000, acid value = 70mgKOH / g)
E3: Resin of the following structure. (The value attached to the main chain is the mole ratio. Mw = 40,000, acid value = 100mgKOH / g)
[Chemical Formula 50]

(Polymerizable compound)
D1: KAYARAD RP-1040 (Nippon Kayaku Co., Ltd., a radical polymerizable compound)
D2: ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD., A radical polymerizable compound)
D3: ARONIX M-305 (manufactured by TOAGOSEI CO., LTD., A radical polymerizable compound)
D4: NK ESTER A-TMMT (free radical polymerizable compound manufactured by Shin-Nakamura Chemical Co., Ltd.)
D5: KAYARAD DPHA (Nippon Kayaku Co., Ltd., a radical polymerizable compound)

(Photopolymerization initiator)
OX-1 to OX-21, OX-R1 to OX-R4: compounds of the above structure
I-1: IRGACURE-369 (manufactured by BASF, α-amino alkyl phenone compound)

(Organic solvents)
J1: Propylene glycol monomethyl ether acetate (PGMEA)
J2: Cyclohexanone
J3: Propylene glycol monomethyl ether (PGME)
J4: Butyl acetate
J5: ethyl lactate

(Other additives)
[Ultraviolet absorbent]
UV1: UV-503 (manufactured by DAITO Chemical Co., Ltd.)
UV2: Compound of the following structure
[Chemical Formula 51]

[Interactive agent]
F1: The following mixture (Mw = 14000, fluorine-based surfactant). In the following formula,% representing the proportion of the repeating unit is mass%.
[Chemical Formula 52]

[Polymerization inhibitor]
G1: p-methoxyphenol
[Antioxidants]
AO1: ADK STAB AO-80 (manufactured by ADEKA Corporation)

[Sensitizer]
Z1 to Z3: Compounds of the following structures
[Chemical Formula 53]

[Near-infrared absorbing pigment]
A5, A8, A12: Compounds of the following structure
[Chemical Formula 54]

＜ Evaluation ＞
The following evaluations were performed using each photosensitive composition obtained as described above.

(Evaluation of storage stability (stability over time))
Each photosensitive composition obtained in the above was placed in a glass container and sealed, and after being stored at 50 ° C for one month, the temperature was returned to room temperature, and the degree of time-dependent change in the sensitivity evaluation described below was evaluated. The benchmark evaluated storage stability.
-Judgment criteria-
A: Changes in sensitivity less than 10 mJ / cm ² .
B: Sensitivity change of 10 mJ / cm ² or more and less than 50 mJ / cm ² .
C: Sensitivity change of 50 mJ / cm ² or more.

(Evaluation of sensitivity)
Each photosensitive composition was coated on a silicon wafer using a spin coater, and then heated (pre-baked) at 100 ° C. for 120 seconds using a hot plate to obtain a coating film having a film thickness of 1.0 μm.
Next, an i-ray stepper exposure device FPA-3000iS + (manufactured by Canon Inc.) was used to change the range of 50 to 1000 mJ / cm ² at a scale of 10 mJ / cm ^{2 through a} mask engraved with a 10 nm line and space pattern. The exposure amount was irradiated (exposure process). Next, a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) was used for spin-immersion development at 23 ° C for 60 seconds, and then rinsed with pure water for 20 seconds using a spin shower, and further purified water was used Washed. After that, the water droplets adhering to the surface of the pattern were removed by air, and the pattern was naturally dried to obtain a pattern.
Regarding the evaluation of sensitivity, the minimum exposure amount (optimal exposure amount) when the film thickness after development with respect to 100% of the film thickness before exposure in the above-mentioned exposure process is measured and measured as the sensitivity is measured as the sensitivity. Commented. The smaller the value of the minimum exposure amount (the optimal exposure amount) is, the higher the sensitivity is.

(Evaluation of developability)
Each photosensitive composition was coated on a silicon wafer using a spin coater, and then heated (pre-baked) at 100 ° C. for 120 seconds using a hot plate to obtain a coating film having a film thickness of 1.0 μm.
Next, exposure was performed using an i-ray stepper exposure device FPA-3000iS + (manufactured by Canon Inc.) through a mask engraved with a pattern of lines and spaces of 10 nm at an exposure amount of 400 mJ / cm ² . Next, a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) was used for spin-immersion development at 23 ° C for 60 seconds, and then rinsed with pure water for 20 seconds using a spin shower, and further purified water was used. Washed. Then, the water droplets adhering to the surface of the pattern were removed by air, and the pattern was naturally dried to obtain a pattern.
The patterned silicon wafer was observed using a SEM (Scanning Electron Microscope, magnification: 20000 times), and the presence or absence of residues in the unirradiated area (unexposed area) was observed from the SEM photograph, and development was evaluated. Sex. The evaluation criteria are as follows.
-Evaluation criteria-
A: No residue was recognized at all in the unexposed portion.
B: Residue was slightly confirmed in the unexposed portion, but there was no problem in practical use.
C: Residue was clearly recognized in the unexposed portion.

(Evaluation of tightness)
A pattern was formed in the same procedure as the evaluation of developability. The obtained pattern was observed using a SEM (Scanning Electron Microscope, magnification: 20000 times), the presence or absence of pattern defects was observed from the SEM photograph, and adhesion was evaluated. The evaluation criteria are as follows.
-Evaluation criteria-
A: No pattern defect was observed at all.
B: Pattern defects are scarcely observed, but only part of the defects are observed. There is no problem in practical terms.
C: Significantly more pattern defects were observed.

＜ Evaluation of color after post-baking ＞
A pattern was formed in the same procedure as the evaluation of developability. The obtained pattern was heated at 200 ° C. for 1 hour using a hot plate, and the color difference ΔEab * before and after post-baking was evaluated using MCPD-3000 manufactured by Otsuka Electronics Co., Ltd. according to the following criteria.
-Evaluation criteria-
A: ΔEab * ≤5
B: 5 <ΔEab * <8
C: ΔEab * ≥8

<Pattern section shape 1 (pattern shape before post-baking)>
A pattern was formed in the same procedure as the evaluation of developability. The cross-sectional shape of the obtained pattern was observed using a SEM (Scanning Electron Microscope, magnification: 20000 times). Five patterns were extracted from the SEM photograph, and the average slope of the cross-sections of the five patterns was determined. The pattern cross-sectional shape 1 was evaluated based on the following criteria. The slope of the cross section of the pattern is 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 a portion composed of the surface of the silicon wafer and the edge in the thickness direction of the pattern was measured. When the slope of the pattern is less than 90 degrees with respect to the surface of the silicon wafer, it means that the pattern is tapered from the silicon wafer side toward the surface side of the pattern (forward cone shape).
-Evaluation criteria-
A: The average slope of the five patterns is 80 degrees or more and less than 100 degrees with respect to the silicon wafer.
B: The average slope of the five patterns is greater than 100 degrees with respect to the silicon wafer.
C: The average slope of the five patterns is less than 80 degrees with respect to the silicon wafer.

<Pattern section shape 2 (pattern shape after post-baking)>
A pattern was formed in the same procedure as the evaluation of developability. The obtained pattern was heated (post-baking) at 200 ° C for 5 minutes using a hot plate. Regarding the pattern after the post-baking, the pattern cross-sectional shape 2 was evaluated in the same order as the pattern cross-sectional shape 1 described above.
-Evaluation criteria-
A: The average slope of the five patterns is 80 degrees or more and less than 100 degrees with respect to the silicon wafer.
B: The average slope of the five patterns is greater than 100 degrees with respect to the silicon wafer.
C: The average slope of the five patterns is less than 80 degrees with respect to the silicon wafer.

[table 5]

As shown in the above table, the sensitivity of the photosensitive composition of the example is higher than that of the photosensitive composition of the comparative example. Furthermore, it is possible to form a pattern with little coloring after post-baking and good rectangularity.

[Test Example 3]
<Preparation of composition for color filters>
(Red Composition 1)
The raw materials shown below were mixed and stirred, and then filtered through a nylon filter (manufactured by NIHON PALL LTD.) Having a pore diameter of 0.45 μm to prepare Red Composition 1.
Red pigment dispersion liquid ... 51.7 parts by mass of 40% by mass PGMEA solution of resin 1 ... 0.6 parts by mass of polymerizable compound 1 ... 0.6 parts by mass of photopolymerization initiator (compound OX-1) ... 0.3 parts by mass of surfactant 0.2 mass% PGMEA solution of 1 ... 4.2 mass parts
PGMEA ... 42.6 parts by mass

(Green composition 1)
The raw materials shown below were mixed and stirred, and then filtered through a nylon filter (manufactured by NIHON PALL LTD.) Having a pore diameter of 0.45 μm to prepare Green Composition 1.
Green pigment dispersion liquid ... 73.7 parts by mass of 40% by mass PGMEA solution of resin 1 ... 0.3 parts by mass of polymerizable compound 2 ... 1.2 parts by mass of photopolymerization initiator (compound OX-1) ... 0.6 parts by mass of surfactant 0.2 mass% PGMEA solution of 1 ... 4.2 mass parts of ultraviolet absorber 1 ... 0.5 mass parts
PGMEA ... 19.5 parts by mass

(Blue composition 1)
The raw materials shown below were mixed and stirred, and then filtered through a nylon filter (manufactured by NIHON PALL LTD.) Having a pore diameter of 0.45 μm to prepare Blue Composition 1.
Blue pigment dispersion ... 44.9 parts by mass of 40% by mass PGMEA solution of resin 1 ... 2.1 parts by mass of polymerizable compound 1 ... 1.5 parts by mass of polymerizable compound 3 ... 0.7 parts by mass of photopolymerization initiator (compound OX-1 ) ... 0.8 parts by mass of 0.2% by mass of PGMEA solution of the surfactant 1 ... 4.2 parts by mass
PGMEA ... 45.8 parts by mass

The raw materials used for the color filter composition are as follows.
The Red pigment dispersion uses a bead mill (0.3mm diameter of zirconia beads) and will include 9.6 parts by mass of CI Pigment Red 254, 4.3 parts by mass of CI Pigment Yellow 139, and 6.8 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie GmbH). And 79.3 parts by mass of the PGMEA mixed solution were mixed and dispersed for 3 hours.
Then, using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism, the dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ . This dispersion treatment was repeated 10 times to obtain a Red pigment dispersion.

The green pigment dispersion liquid uses a bead mill (0.3 mm diameter of zirconia microbeads), and contains 6.4 parts by mass of CI Pigment Green 36, 5.3 parts by mass of CI Pigment Yellow 150, and 5.2 parts by mass of a dispersant (manufactured by Disperbyk-161, BYK Chemie GmbH). And 83.1 parts by mass of the PGMEA mixed solution were mixed and dispersed for 3 hours. Then, using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism, the dispersion treatment was performed at a flow rate of 500 g / min at a pressure of 2000 kg / cm ³ . This dispersion treatment was repeated 10 times to obtain a Green pigment dispersion.

The Blue pigment dispersion uses a bead mill (0.3mm diameter of zirconia microbeads) and will contain 9.7 parts by mass of CI Pigment Blue 15: 6, 2.4 parts by mass of CI Pigment Violet 23, and 5.5 parts by mass of dispersant (Disperbyk-161, BYK Chemie GmbH Made) and 82.4 parts by mass of the PGMEA mixed solution were mixed and dispersed for 3 hours. Then, using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism, the dispersion treatment was performed at a flow rate of 500 g / min at a pressure of 2000 kg / cm ³ . This dispersion treatment was repeated 10 times to obtain a Blue pigment dispersion.

Polymerizable compound 1: Compound of the following structure
[Chemical Formula 55]

Polymerizable compound 2: The aforementioned polymerizable compound D5
Polymerizable compound 3: The aforementioned polymerizable compound D3

Resin 1: Resin E1 above
Surfactant 1: The aforementioned surfactant F1
Ultraviolet absorbent 1: The above-mentioned ultraviolet absorbent UV1

(Production of color filters)
The green composition 1 was applied on a silicon wafer by a spin coating method so that the film thickness after post-baking became 1.0 μm. Next, it was heated (pre-baked) at 100 ° C for 2 minutes using a hot plate. Next, exposure was performed using an i-ray stepper exposure device FPA-3000i5 + (manufactured by Canon Inc.) at a exposure amount of 400 mJ / cm ² via a mask having a 1.0 μm square Bayer pattern. Next, spin-on immersion development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). After that, it was rinsed with a rotary shower, and then washed with pure water. Next, a green plate (green pattern) with a square Bayer pattern of 1.0 μm was formed by heating (post-baking) at 200 ° C. for 5 minutes using a hot plate. The Red composition 1 and the Blue composition 1 were sequentially patterned in the same order as in the case of the Green composition 1, and the missing portions of the green pixels on the silicon wafer were formed into 1.0 μm square island-shaped red patterns. The pixel (red pattern) and the blue pixel (cyan pattern) of a 1.0 μm square island pattern produced a color filter. When this color filter was assembled in a solid-state imaging device, it was confirmed that the solid-state imaging device has high resolution and excellent color separation properties.

Claims (19)

A photosensitive composition comprising: A cyclic oxime compound having a cyclic oxime moiety having a cyclic structure formed by including an oxime group, and an electron attracting group having a σ * constant value of 3.5 or more; and Polymerizable compound. The photosensitive composition according to claim 1, wherein the cyclic oxime compound has an electron attracting group having a σ * constant value of 4 or more. The photosensitive composition according to claim 1, wherein the electron attracting group is at least one selected from the group consisting of a nitro group, an alkylsulfonyl group, an arylsulfonyl group, and an onium group. The photosensitive composition according to any one of claims 1 to 3, wherein the cyclic oxime site of the cyclic oxime compound is represented by the following formula (a-1); [Chemical Formula 1] In the formula, R ¹ represents a substituent, A represents a ring formed by containing an oxime group, and n represents 0 or 1. The photosensitive composition according to any one of claims 1 to 3, wherein the cyclic oxime compound has a structure in which at least one ring selected from an aromatic hydrocarbon ring and a heterocyclic ring is bonded to the cyclic oxime site. . The photosensitive composition according to any one of claims 1 to 3, wherein the cyclic oxime compound has a structure in which a fused ring including a carbazole ring or a dibenzothiophene ring is bonded to the cyclic oxime site. The photosensitive composition according to any one of claims 1 to 3, wherein the cyclic oxime compound is a compound represented by the following formula (1); [Chemical Formula 2] In formula (1), X ¹ represents -O-, -CR ^x1 R ^X2- , -S-, -NR ^x3 -or> C = NOR ^x4 , and R ^x1 to R ^x4 each independently represent a hydrogen atom or a substituent, R ^x1 and R ^x3 may be bonded to R ² , R ³ or a ring represented by B to form a ring. R ¹ to R ³ each independently represent a substituent, and L represents an alkylene group having 1 to 3 carbon atoms or -CR. ^L1 = CR ^L2- , R ^L1 and R ^L2 each independently represent a hydrogen atom or a substituent, B represents a ring containing at least one selected from an aromatic hydrocarbon ring and a heterocyclic ring, and Z ¹ represents a σ ^* constant value of Taft 3.5 or more electron attracting groups, n represents 0 or 1, m represents 0 or 1, q represents an integer of 1 or more, o and p each independently represent an integer of 0 or more, and when p is 2 or more, p R ² may be the same It may be different. Two R ² may be bonded to each other to form a ring. When o is 2 or more, o R ^3s may be the same or different. Two R ³ may be bonded to each other to form a ring. Q is 2 or more. In this case, q Z ¹ may be the same or different. The photosensitive composition according to any one of claims 1 to 3, wherein the cyclic oxime compound is a compound represented by the following formula (2); [Chemical Formula 3] In formula (2), X ¹ represents -O-, -CR ^x1 R ^X2- , -S-, -NR ^x3 -or> C = NOR ^x4 , and R ^x1 to R ^x4 each independently represent a hydrogen atom or a substituent, R ^x1 and R ^x3 may be bonded to R ² or R ^3a to form a ring, L represents an alkylene group having 1 to 3 carbon atoms or -CR ^L1 = CR ^L2- , and R ^L1 and R ^L2 each independently represent a hydrogen atom or Substituents, R ¹ , R ² , R ^3a and R ^3b each independently represent a substituent, Z ^1a and Z ^1b each independently represent an electron attracting group whose Taft σ ^* constant value is 3.5 or more, and Y ¹ represents -CR ^Y1 R ^Y2- , -NR ^Y3 -or -S-, R ^Y1 to R ^Y3 each independently represent a hydrogen atom or a substituent, n represents 0 or 1, m represents 0 or 1, o1, o2, p, q1 and q2 respectively Independently represents an integer of 0 or more, at least one of q1 and q2 represents an integer of 1 or more, and when p is 2 or more, p R ² may be the same or different, and two R ² may be bonded to each other to form a ring When o1 is 2 or more, o1 R ^3a may be the same or different. Two R ^3a may be bonded to each other to form a ring. When o2 is 2 or more, o2 R ^3b may be the same or different. 2 R ^3b can be bonded to each other to form a ring. When q1 is 2 or more, q1 Z ^1a may be the same or different. When q2 is 2 or more, q2 Z ^1b may be the same or different. The photosensitive composition according to any one of claims 1 to 3, wherein the cyclic oxime compound is a compound represented by the following formula (3a) or formula (3b); [Chemical Formula 4] In formula (3a), X ¹ represents -O-, -CR ^x1 R ^X2- , -S-, -NR ^x3 -or> C = NOR ^x4 , and R ^x1 to R ^x4 each independently represent a hydrogen atom or a substituent, R ^x1 and R ^x3 may be bonded to R ² or R ^3c to form a ring, Y ² represents -CR ^Y21 R ^Y22- , -NR ^Y23- , or -S-, and R ^Y21 to R ^Y23 each independently represent a hydrogen atom or a substitution In formula (3b), X ² represents> CR ^X10 -or> N-, R ^x10 represents a hydrogen atom or a substituent; in formula (3a) and formula (3b), R ¹ , R ² , R ^3c and R ^3d each independently represents a substituent, L represents an alkylene group having 1 to 3 carbon atoms or -CR ^L1 = CR ^L2- , R ^L1 and R ^L2 each independently represent a hydrogen atom or a substituent, and Z ^1c and Z ^1d are each independently Ground represents an electron attracting group with a σ ^* constant value of 3.5 or more, n represents 0 or 1, m represents 0 or 1, o3, o4, p, q3, and q4 each independently represent an integer of 0 or more, and q3 and q4 At least one of represents an integer of 1 or more. When p is 2 or more, p R ² may be the same or different. Two R ² may be bonded to each other to form a ring. When o 3 is 2 or more, o 3 R ^3c may be be the same or different and two R ^3c may be bonded to each other to form a ring o4 is 2 or more, a o4 R ^3d may be the same or different, two R ^3d may be bonded to each other to form a ring, q3 is 2 or more, q3 more Z ^1c may be the same or different, is 2 or more Q4 In this case, q4 Z ^1d may be the same or different. The photosensitive composition according to any one of claims 1 to 3, further comprising a resin. The photosensitive composition according to any one of claims 1 to 3, further comprising a color material. The photosensitive composition according to claim 11, wherein the color material contains a pigment. The photosensitive composition according to claim 11, wherein the color material contains at least one selected from a color colorant, a white colorant, a black colorant, and a near-infrared absorbing pigment. The photosensitive composition according to any one of claims 1 to 3, which is a composition for forming a pixel of a color filter. A cured film obtained by using the photosensitive composition according to any one of claims 1 to 14. A method for manufacturing a color filter includes: A process for forming a photosensitive composition layer by applying the photosensitive composition described in any one of claims 1 to 14 on a support; A process of exposing the photosensitive composition layer into a pattern; and A process of developing the photosensitive composition layer after exposure to form a pattern. A color filter having the cured film according to claim 15. A solid-state imaging device having the cured film according to claim 15. An image display device having the cured film according to claim 15.